U.S. patent application number 14/897909 was filed with the patent office on 2016-08-25 for thermal insulation.
The applicant listed for this patent is MATERIA, INC.. Invention is credited to Brian L. Conley, Christopher J. Cruce, Michael A. Giardello, Anthony R. Stephen.
Application Number | 20160244632 14/897909 |
Document ID | / |
Family ID | 52142632 |
Filed Date | 2016-08-25 |
United States Patent
Application |
20160244632 |
Kind Code |
A1 |
Cruce; Christopher J. ; et
al. |
August 25, 2016 |
THERMAL INSULATION
Abstract
The present invention is directed to addressing one or more of
the aforementioned concerns and relates to thermal insulation
materials and thermal insulation material compositions and methods
for thermally insulating pipelines and associated equipment,
structures, and objects used in offshore drilling. The present
invention is directed to articles of manufacture comprising the
thermal insulation materials and/or thermal insulation material
compositions of the invention. More particularly the present
invention relates to the use of ring opening metathesis
polymerization polymers (ROMP polymers) and/or ROMP polymer
composites for thermally insulating pipelines and associated
equipment, structures, and objects used in offshore oil
drilling.
Inventors: |
Cruce; Christopher J.;
(Poway, CA) ; Giardello; Michael A.; (Pasadena,
CA) ; Conley; Brian L.; (Santa Monica, CA) ;
Stephen; Anthony R.; (South Pasadena, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
MATERIA, INC. |
Pasadena |
CA |
US |
|
|
Family ID: |
52142632 |
Appl. No.: |
14/897909 |
Filed: |
June 24, 2014 |
PCT Filed: |
June 24, 2014 |
PCT NO: |
PCT/US14/43968 |
371 Date: |
December 11, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61838824 |
Jun 24, 2013 |
|
|
|
61948196 |
Mar 5, 2014 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
F16L 58/1054 20130101;
B05D 7/222 20130101; C08G 2261/3324 20130101; C08G 2261/3325
20130101; C08G 2261/90 20130101; C08G 61/02 20130101; C08G 2261/76
20130101; C08G 2261/58 20130101; C08G 2261/418 20130101; C08G 61/08
20130101; C08G 2261/596 20130101; F16L 59/20 20130101; F16L 59/143
20130101; C08L 65/00 20130101; C08G 2261/122 20130101; C08G
2261/592 20130101; F16L 59/028 20130101; C08G 2261/62 20130101;
C09D 165/00 20130101; C08G 2261/135 20130101; C08G 2261/1412
20130101; F16L 58/181 20130101; F16L 59/14 20130101 |
International
Class: |
C09D 165/00 20060101
C09D165/00; F16L 59/14 20060101 F16L059/14; B05D 7/22 20060101
B05D007/22 |
Claims
1. A thermal insulation material, comprising: a resin composition
comprising a cyclic olefin composition and a catalyst composition
comprising at least one metal carbene olefin metathesis catalyst,
wherein the cyclic olefin composition comprises 10.0 mol % to 80.0
mol % of at least one cyclic olefin containing multiunsaturation,
and up to 90.0 mol % of at least one cyclic olefin containing
monounsaturation, wherein the at least one cyclic olefin containing
multiunsaturation may be substituted or unsubstituted, and wherein
the at least one cyclic olefin containing monounsaturation may be
substituted or unsubstituted.
2. A method of coating at least a portion of at least one surface
of an object with a thermal insulation material, comprising:
combining a resin composition comprising a cyclic olefin
composition with a catalyst composition comprising at least one
metal carbene olefin metathesis catalyst, thereby forming a ROMP
composition, wherein the cyclic olefin composition comprises 10.0
mol % to 80.0 mol % of at least one cyclic olefin containing
multiunsaturation, and up to 90.0 mol % of at least one cyclic
olefin containing monounsaturation, wherein the at least one cyclic
olefin containing multiunsaturation may be substituted or
unsubstituted, and wherein the at least one cyclic olefin
containing monounsaturation may be substituted or unsubstituted;
contacting the ROMP composition with at least a portion of at least
one surface of the object; and subjecting the ROMP composition to
conditions effective to promote a ROMP reaction of the cyclic
olefin composition in the presence of the at least one metal
carbene olefin metathesis catalyst, wherein the thermal insulation
material is a ROMP polymer or a ROMP polymer composite.
3. The method of claim 2, wherein the object is object is a pipe,
pipeline, pipe fitting, hose, hose fitting, tank, container, drum,
manifold, riser, field joint, a subsea Christmas tree, jumper,
spool piece, pipeline end termination, pipeline end manifold,
robotic part, a robotic device, a robotic vehicle, wellhead
equipment, a subsea dog house, or combinations thereof.
4. An article of manufacture comprising an object, wherein at least
a portion of at least one surface of the object is coated with a
ROMP polymer, wherein the ROMP polymer is a reaction product of a
resin composition comprising a cyclic olefin composition and a
catalyst composition comprising at least one metal carbene olefin
metathesis catalyst, wherein the cyclic olefin composition
comprises 10.0 mol % to 80.0 mol % of at least one cyclic olefin
containing multiunsaturation, and up to 90.0 mol % of at least one
cyclic olefin containing monounsaturation, wherein the at least one
cyclic olefin containing multiunsaturation may be substituted or
unsubstituted, and wherein the at least one cyclic olefin
containing monounsaturation may be substituted or
unsubstituted.
5. The article of manufacture of claim 4, wherein the object is a
pipe, pipeline, pipe fitting, hose, hose fitting, tank, container,
drum, manifold, riser, field joint, a subsea Christmas tree,
jumper, spool piece, pipeline end termination, pipeline end
manifold, robotic part, a robotic device, a robotic vehicle,
wellhead equipment, a subsea dog house, or combinations
thereof.
6. An article of manufacture made by the method of claim 2.
7. (canceled)
Description
RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional
Patent Application No. 61/838,824, filed Jun. 24, 2013, and U.S.
Provisional Patent Application No. 61/948,196, filed Mar. 5, 2014,
the contents of each are incorporated herein by reference.
TECHNICAL FIELD
[0002] The present invention relates to the field of insulated
pipelines and structures, particularly to the field of subsea
pipelines and structures. More particularly, the present invention
relates to thermal insulation materials and compositions for
insulating offshore oil drilling equipment and structures,
particularly subsea pipelines and structures. The present invention
also relates to methods of using such thermal insulation materials
and compositions to insulate offshore oil drilling equipment and
structures, and articles of manufacture comprising such thermal
insulation materials and compositions.
BACKGROUND
[0003] Offshore oil drilling requires the transportation of
hydrocarbons from wellheads positioned underwater to shore or other
surface equipment for further distribution. As temperature
decreases the resistance to flow of liquids such as oil increases.
Pipelines used in the transportation of oil from the underwater
wellheads are generally insulated to avoid a substantial decrease
in the temperature of the oil. Moreover, the underwater environment
exposes pipelines and other oil drilling equipment to compressive
forces, salt water corrosion, near-freezing water temperatures,
possible water absorption, undersea currents, and marine life. Most
pipes and pipelines used in offshore oil drilling are constructed
of metal, typically some grade of steel.
[0004] Installation conditions for subterranean and subsea
pipelines and equipment tend to be demanding. As such, it is
possible that the material used to thermally insulate offshore
drilling equipment and pipelines, including but not limited to
subterranean pipelines and equipment as well as subsea pipelines
and equipment may become damaged during installation of the
pipeline. For example, during installation pipeline insulation
undergo bending (flexural stress) due to pipe sag and reeling,
particularly in what are commonly known as S-lay and J-lay
installation processes.
[0005] In recent years performance requirements for thermal
insulation materials have also become increasingly demanding.
Recent advances in drilling technology and depletion of readily
accessible sub-sea oil wells have resulted in the push toward deep
water drilling where oil temperatures are typically hotter. This
results in higher temperature pipelines and structures. Though
several materials (e.g., polymer materials and/or polymer composite
materials) with higher design temperatures have been developed, the
peak use temperature of these materials has plateaued near
150-160.degree. C. Thus, a need exists for easily applied thermal
insulation materials that pass the requisite qualification tests so
as to be suitable for use on subsea and subterranean pipelines with
maximum flowline operating temperatures (MFOTs) above
150-160.degree. C. These installation and performance demands, as
well as other needs, have led to the introduction of a number of
materials (e.g., polymer materials and/or polymer composite
materials) for the purpose of insulating offshore drilling
equipment and pipelines, including but not limited to subterranean
pipelines and equipment as well as subsea pipelines and
equipment.
[0006] Desirable characteristics and/or properties of thermal
insulation materials, in particular thermal insulation materials
for subsea applications include: thermal stability above
175.degree. C.; resistance to hydrolysis above 175.degree. C.;
flexibility greater than 5% elongation at break at 25.degree. C.;
compatibility with glass microspheres; fast cure times; low thermal
conductivity; high impact strength; castable (high throughput with
low capital expenditure cost); rigid for robust pipe handling
without external protection; can be processed in air; can be
applied in thick sections without multi-layering; can be applied to
complex geometries; rapid full cure under production conditions;
processable in the presence of trace moisture (water). Furthermore,
there has been a need in the industry for thermal insulation
materials, particularly thermal insulation materials for subsea
applications (e.g., thermal insulation for pipe and pipelines and
other subsea equipment and structures, such as coatings for field
joints, etc.) that possess all of these desirable characteristics
and/or properties. Thermal stability as used herein means that a
material maintains its structural integrity when subjected to
elevated temperatures.
[0007] Polyurethanes have been used for insulating subsea pipelines
and equipment due to somewhat general ease in processing and
generally good mechanical properties. However, polyurethane
insulation may suffer from hydrolytic degradation when exposed to
hot-wet environments. In offshore oil fields, particularly fields
where the oil temperature is high at the wellhead, there is a
possibility of hydrolytic degradation of the polyurethane polymer
network, particularly at elevated temperatures where water is able
to ingress the polymer network, which would negatively affect the
insulation capabilities of the polyurethane polymer.
[0008] Polypropylene is another polymer material that is used to
insulate subsea pipelines and equipment. However, unlike
polyurethanes, the application of polypropylene is a more difficult
process generally requiring extrusion of multiple layers. Moreover,
polypropylene does not possess attractive thermal and mechanical
properties.
[0009] Polystyrene is another polymer material that is used to
insulate subsea pipelines and equipment, however, polystyrene does
not possess attractive thermal and mechanical properties.
[0010] Another material used for insulating subsea pipelines and
equipment is rigid epoxy syntactic foam, where hollow glass or
ceramic spheres are combined with the epoxy resin. This material
possesses good thermal conductivity, but suffers from being very
brittle and rigid, making this material susceptible to damage when
exposed to high stress forces and/or sudden impacts. Moreover,
these materials are difficult to remove and replace as they are
attached to the surface mechanically or through the use of
adhesives. Epoxy resin in general, in the absence of glass or
ceramic microspheres, have poor thermal conductivity, generally
require long cure cycles and also suffer from being very brittle
and rigid, and well as having other limitations.
[0011] Silicones and syntactic silicones where hollow glass or
ceramic spheres are combined with the silicones are another polymer
material that is used to insulate subsea pipelines and equipment,
however, silicones and syntactic silicones may suffer from
hydrolytic degradation when exposed to hot wet environments.
Moreover, silicones generally require long cure cycles.
[0012] Phenolics are another polymer material that is used to
insulate subsea pipelines and equipment; however, phenolics are
generally difficult to apply to such objects. These materials also
suffer from being very brittle and rigid, making this material
susceptible to damage when exposed to high stress forces and/or
sudden impacts.
[0013] Another material for insulating subsea pipelines and
equipment is elastomeric amine cured epoxy resins. While
elastomeric amine cured epoxy resins may offer some advantages over
polyurethanes, these materials possess several limitations,
particularly in that at least two steps and specialized equipment
are required to prepare such elastomeric amine cured epoxy resins.
Moreover, these materials are viscous liquids (e.g., 90,000 cP at
25.degree. C.), making the filling of complex molds difficult.
[0014] Rubber materials, including silicone rubber, are examples of
other materials used to insulate subsea pipelines and equipment.
These materials do not possess attractive thermal and mechanical
properties, and generally require long cure cycles, as well as
having other limitations.
[0015] Dicyclopentadiene polymer (pDCPD) prepared from Telene.RTM.
1650 DCPD resin is another example of a material that has been
reported for use as a field joint coating material, however, this
material (including similar materials such as Metton.RTM. DCPD
resin and Pentam.RTM. DCPD resin) possess several limitations,
which are well known in the art. Telene.RTM. 1650 DCPD resin
(BFGoodrich/Telene SAS) and Metton.RTM. DCPD resin (Metton
America/Hercules) are both based on a two component system
comprising molybdenum (Telene SAS/BFGoodrich) or tungsten (Metton
America/Hercules) pre-catalyst dissolved in DCPD monomer
(B-component) and an aluminum alkyl or aluminum alkyl halide
co-catalyst dissolved in DCPD monomer (A-component). These
molybendum and tungsten catalyzed DCPD resins are extremely
sensitive to chemical functional groups and to air (oxygen) and
moisture (water), even at trace levels. As a result of this
sensitivity, such molybendum and tungsten catalyzed DCPD resin are
typically limited to being processed using Reaction Injection
Molding (RIM) techniques, which require specialized and expensive
processing and handling conditions and equipment, including
specialized and expensive molds, injection equipment, and storage
tanks. Moreover, as a further result of this sensitivity,
particularly their sensitivity to chemical functional groups, such
molybdenum and tungsten catalyzed DCPD resins are generally not
suitable for use to prepare DCPD polymer composites.
[0016] Therefore, despite the advances achieved in the art, there
continues to be need for improvements in the materials,
particularly polymer materials and/or polymer composite materials,
used for thermally insulating pipelines and associated equipment
and structures used in offshore oil drilling.
SUMMARY
[0017] The present invention is directed to addressing one or more
of the aforementioned concerns and relates to thermal insulation
materials and thermal insulation material compositions and methods
for thermally insulating pipelines and associated equipment,
structures, and objects used in offshore drilling. The present
invention is also relates to articles of manufacture comprising the
thermal insulation materials and/or thermal insulation material
compositions of the invention.
[0018] More particularly the present invention relates to the use
of ring opening metathesis polymerization polymers (ROMP polymers)
and/or ROMP polymer composites for thermally insulating pipelines
and associated equipment, structures, and objects used in offshore
oil drilling. ROMP polymers and/or ROMP polymer composites of the
invention offer several advantages over prior art materials used
for thermally insulating pipelines and associated equipment,
structures, and objects used in offshore oil drilling.
[0019] In one embodiment the invention provides a cyclic olefin
composition comprising 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation.
[0020] In another embodiment the invention provides a cyclic olefin
composition comprising 10.0 mol % to 70.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation.
[0021] In another embodiment the invention provides a cyclic olefin
composition comprising 10.0 mol % to 60.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation.
[0022] In another embodiment the invention provides a cyclic olefin
composition comprising 10.0 mol % to 50.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation.
[0023] In another embodiment the invention provides a cyclic olefin
composition comprising 10.0 mol % to 40.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation.
[0024] In one embodiment the invention provides a cyclic olefin
composition comprising 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation, wherein the
at least one cyclic olefin containing multiunsaturation may be
substituted or unsubstituted, and wherein the at least one cyclic
olefin containing monounsaturation may be substituted or
unsubstituted, and wherein the substituents are independently
selected from hydrogen, hydrocarbyl, substituted hydrocarbyl,
heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, --(Z*).sub.n-Fn where n is zero
or 1, Z* and Fn, and functional groups (Fn).
[0025] In one embodiment the invention provides a cyclic olefin
composition comprising 10.0 mol % to 70.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation, wherein the
at least one cyclic olefin containing multiunsaturation may be
substituted or unsubstituted, and wherein the at least one cyclic
olefin containing monounsaturation may be substituted or
unsubstituted, and wherein the substituents are independently
selected from hydrogen, hydrocarbyl, substituted hydrocarbyl,
heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, --(Z*).sub.n-Fn where n is zero
or 1, Z* and Fn, and functional groups (Fn).
[0026] In one embodiment the invention provides a cyclic olefin
composition comprising 10.0 mol % to 60.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation, wherein the
at least one cyclic olefin containing multiunsaturation may be
substituted or unsubstituted, and wherein the at least one cyclic
olefin containing monounsaturation may be substituted or
unsubstituted, and wherein the substituents are independently
selected from hydrogen, hydrocarbyl, substituted hydrocarbyl,
heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, --(Z*).sub.n-Fn where n is zero
or 1, Z* and Fn, and functional groups (Fn).
[0027] In one embodiment the invention provides a cyclic olefin
composition comprising 10.0 mol % to 50.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation, wherein the
at least one cyclic olefin containing multiunsaturation may be
substituted or unsubstituted, and wherein the at least one cyclic
olefin containing monounsaturation may be substituted or
unsubstituted, and wherein the substituents are independently
selected from hydrogen, hydrocarbyl, substituted hydrocarbyl,
heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, --(Z*).sub.n-Fn where n is zero
or 1, Z* and Fn, and functional groups (Fn).
[0028] In one embodiment the invention provides a cyclic olefin
composition comprising 10.0 mol % to 40.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation, wherein the
at least one cyclic olefin containing multiunsaturation may be
substituted or unsubstituted, and wherein the at least one cyclic
olefin containing monounsaturation may be substituted or
unsubstituted, and wherein the substituents are independently
selected from hydrogen, hydrocarbyl, substituted hydrocarbyl,
heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, --(Z*).sub.n-Fn where n is zero
or 1, Z* and Fn, and functional groups (Fn).
[0029] In another embodiment the invention provides a resin
composition comprising a cyclic olefin composition, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation.
[0030] In another embodiment the invention provides a resin
composition comprising a cyclic olefin composition, wherein the
cyclic olefin composition comprises 10.0 mol % to 70.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation.
[0031] In another embodiment the invention provides a resin
composition comprising a cyclic olefin composition, wherein the
cyclic olefin composition comprises 10.0 mol % to 60.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation.
[0032] In another embodiment the invention provides a resin
composition comprising a cyclic olefin composition, wherein the
cyclic olefin composition comprises 10.0 mol % to 50.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation.
[0033] In another embodiment the invention provides a resin
composition comprising a cyclic olefin composition, wherein the
cyclic olefin composition comprises 10.0 mol % to 40.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation.
[0034] In another embodiment the invention provides a resin
composition comprising a cyclic olefin composition, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation, wherein the at least one cyclic olefin containing
multiunsaturation may be substituted or unsubstituted, and wherein
the at least one cyclic olefin containing monounsaturation may be
substituted or unsubstituted, and wherein the substituents are
independently selected from hydrogen, hydrocarbyl, substituted
hydrocarbyl, heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, --(Z*).sub.n-Fn where n is zero
or 1, Z* and Fn, and functional groups (Fn).
[0035] In another embodiment the invention provides a resin
composition comprising a cyclic olefin composition, wherein the
cyclic olefin composition comprises 10.0 mol % to 70.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation, wherein the at least one cyclic olefin containing
multiunsaturation may be substituted or unsubstituted, and wherein
the at least one cyclic olefin containing monounsaturation may be
substituted or unsubstituted, and wherein the substituents are
independently selected from hydrogen, hydrocarbyl, substituted
hydrocarbyl, heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, --(Z*).sub.n-Fn where n is zero
or 1, Z* and Fn, and functional groups (Fn).
[0036] In another embodiment the invention provides a resin
composition comprising a cyclic olefin composition, wherein the
cyclic olefin composition comprises 10.0 mol % to 60.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation, wherein the at least one cyclic olefin containing
multiunsaturation may be substituted or unsubstituted, and wherein
the at least one cyclic olefin containing monounsaturation may be
substituted or unsubstituted, and wherein the substituents are
independently selected from hydrogen, hydrocarbyl, substituted
hydrocarbyl, heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, --(Z*).sub.n-Fn where n is zero
or 1, Z* and Fn, and functional groups (Fn).
[0037] In another embodiment the invention provides a resin
composition comprising a cyclic olefin composition, wherein the
cyclic olefin composition comprises 10.0 mol % to 50.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation, wherein the at least one cyclic olefin containing
multiunsaturation may be substituted or unsubstituted, and wherein
the at least one cyclic olefin containing monounsaturation may be
substituted or unsubstituted, and wherein the substituents are
independently selected from hydrogen, hydrocarbyl, substituted
hydrocarbyl, heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, --(Z*).sub.n-Fn where n is zero
or 1, Z* and Fn, and functional groups (Fn).
[0038] In another embodiment the invention provides a resin
composition comprising a cyclic olefin composition, wherein the
cyclic olefin composition comprises 10.0 mol % to 40.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation, wherein the at least one cyclic olefin containing
multiunsaturation may be substituted or unsubstituted, and wherein
the at least one cyclic olefin containing monounsaturation may be
substituted or unsubstituted, and wherein the substituents are
independently selected from hydrogen, hydrocarbyl, substituted
hydrocarbyl, heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, --(Z*).sub.n-Fn where n is zero
or 1, Z* and Fn, and functional groups (Fn).
[0039] In one embodiment the invention provides a method of
thermally insulating an object from a surrounding fluid, the method
comprising interposing a thermal insulation material between the
object and the fluid wherein the thermal insulation material
comprises the reaction product of a resin composition comprising at
least one cyclic olefin and a catalyst composition comprising at
least one metal carbene olefin metathesis catalyst
[0040] In one embodiment the invention provides a method of
thermally insulating an object from a surrounding fluid, the method
comprising interposing a thermal insulation material between the
object and the fluid wherein the thermal insulation material
comprises the reaction product of a resin composition comprising a
cyclic olefin composition and a catalyst composition comprising at
least one metal carbene olefin metathesis catalyst, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation.
[0041] In another embodiment the invention provides a method of
thermally insulating an object from a surrounding fluid, the method
comprising interposing a thermal insulation material between the
object and the fluid wherein the thermal insulation material
comprises a ROMP polymer.
[0042] In another embodiment the invention provides a method of
thermally insulating an object from a surrounding fluid, the method
comprising interposing a thermal insulation material between the
object and the fluid wherein the thermal insulation material
comprises a ROMP polymer, wherein the ROMP polymer is a reaction
product of a resin composition comprising a cyclic olefin
composition and a catalyst composition comprising at least one
metal carbene olefin metathesis catalyst, wherein the cyclic olefin
composition comprises 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation.
[0043] In another embodiment the invention provides a method of
thermally insulating an object from a surrounding fluid, the method
comprising interposing a thermal insulation material between the
object and the fluid wherein the thermal insulation material
comprises a ROMP polymer composite.
[0044] In another embodiment the invention provides a method of
thermally insulating an object from a surrounding fluid, the method
comprising interposing a thermal insulation material between the
object and the fluid wherein the thermal insulation material
comprises a ROMP polymer composite, wherein the ROMP polymer
composite is a reaction product of a resin composition comprising a
cyclic olefin composition and a catalyst composition comprising at
least one metal carbene olefin metathesis catalyst, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation.
[0045] In another embodiment a reaction product of a resin
composition comprising at least one cyclic olefin and a catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst is used to thermally insulate any object from a
surrounding environment.
[0046] In another embodiment a reaction product of a resin
composition comprising a cyclic olefin composition and a catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst is used to thermally insulate any object from a
surrounding environment, wherein the cyclic olefin composition
comprises 10.0 mol % to 80.0 mol % of at least one cyclic olefin
containing multiunsaturation, and up to 90.0 mol % of at least one
cyclic olefin containing monounsaturation.
[0047] In another embodiment a ROMP polymer is used to thermally
insulate any object from a surrounding environment.
[0048] In another embodiment a ROMP polymer is used to thermally
insulate any object from a surrounding environment, wherein the
ROMP polymer is a reaction product of a resin composition
comprising a cyclic olefin composition and a catalyst composition
comprising at least one metal carbene olefin metathesis catalyst,
wherein the cyclic olefin composition comprises 10.0 mol % to 80.0
mol % of at least one cyclic olefin containing multiunsaturation,
and up to 90.0 mol % of at least one cyclic olefin containing
monounsaturation.
[0049] In another embodiment a ROMP polymer composite is used to
thermally insulate any object from a surrounding environment.
[0050] In another embodiment a ROMP polymer composite is used to
thermally insulate any object from a surrounding environment,
wherein the ROMP polymer composite is a reaction product of a resin
composition comprising a cyclic olefin composition and a catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst, wherein the cyclic olefin composition comprises 10.0 mol
% to 80.0 mol % of at least one cyclic olefin containing
multiunsaturation, and up to 90.0 mol % of at least one cyclic
olefin containing monounsaturation.
[0051] In another embodiment a reaction product of a resin
composition comprising at least one cyclic olefin and a catalyst
composition comprising at least one olefin metathesis catalyst is
used to thermally insulate objects, equipment, structures, systems
used in offshore oil drilling.
[0052] In another embodiment a reaction product of a resin
composition comprising at a cyclic olefin composition and a
catalyst composition comprising at least one olefin metathesis
catalyst is used to thermally insulate objects, equipment,
structures, systems used in offshore oil drilling, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation.
[0053] In another embodiment a reaction product of a resin
composition comprising at least one cyclic olefin and a catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst is used to thermally insulate undersea pipes and well head
equipment from sea water.
[0054] In another embodiment a reaction product of a resin
composition comprising a cyclic olefin composition and a catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst is used to thermally insulate undersea pipes and well head
equipment from sea water, wherein the cyclic olefin composition
comprises 10.0 mol % to 80.0 mol % of at least one cyclic olefin
containing multiunsaturation, and up to 90.0 mol % of at least one
cyclic olefin containing monounsaturation.
[0055] In another embodiment thermal insulation materials of the
invention are prepared by combining a resin composition comprising
at least one cyclic olefin with a catalyst composition comprising
at least one metal carbene olefin metathesis catalyst to form a
ROMP composition, and subjecting the ROMP composition to conditions
effective to polymerize the ROMP composition, thereby forming a
ROMP polymer for use as a thermal insulation material.
[0056] In another embodiment thermal insulation materials of the
invention are prepared by combining a resin composition comprising
a cyclic olefin composition with a catalyst composition comprising
at least one metal carbene olefin metathesis catalyst to form a
ROMP composition, wherein the cyclic olefin composition comprises
10.0 mol % to 80.0 mol % of at least one cyclic olefin containing
multiunsaturation, and up to 90.0 mol % of at least one cyclic
olefin containing monounsaturation, and subjecting the ROMP
composition to conditions effective to polymerize the ROMP
composition, thereby forming a ROMP polymer for use as a thermal
insulation material.
[0057] In another embodiment thermal insulation materials of the
invention are prepared by combining a resin composition comprising
at least one cyclic olefin with a catalyst composition comprising
at least one metal carbene olefin metathesis catalyst to form a
ROMP composition, contacting the ROMP composition with a substrate
material, subjecting the ROMP composition to conditions effective
to polymerize the ROMP composition, thereby forming a ROMP polymer
composite for use as a thermal insulation material.
[0058] In another embodiment thermal insulation materials of the
invention are prepared by combining a resin composition comprising
a cyclic olefin composition with a catalyst composition comprising
at least one metal carbene olefin metathesis catalyst to form a
ROMP composition, wherein the cyclic olefin composition comprises
10.0 mol % to 80.0 mol % of at least one cyclic olefin containing
multiunsaturation, and up to 90.0 mol % of at least one cyclic
olefin containing monounsaturation, contacting the ROMP composition
with a substrate material, subjecting the ROMP composition to
conditions effective to polymerize the ROMP composition, thereby
forming a ROMP polymer composite for use as a thermal insulation
material.
[0059] In another embodiment thermal insulation materials of the
invention are prepared by combining a resin composition comprising
at least one cyclic olefin and at least one substrate material with
a catalyst composition comprising at least one metal carbene olefin
metathesis catalyst to form a ROMP composition, subjecting the ROMP
composition to conditions effective to polymerize the ROMP
composition, thereby forming a ROMP polymer composite for use as a
thermal insulation material.
[0060] In another embodiment thermal insulation materials of the
invention are prepared by combining a resin composition comprising
a cyclic olefin composition and at least one substrate material
with a catalyst composition comprising at least one metal carbene
olefin metathesis catalyst to form a ROMP composition, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation, subjecting the ROMP composition to conditions
effective to polymerize the ROMP composition, thereby forming a
ROMP polymer composite for use as a thermal insulation
material.
[0061] In another embodiment a process for providing a ROMP polymer
coating for offshore applications is provided, the process
comprising, providing an object surface to be coated, providing a
resin composition comprising at least one cyclic olefin, providing
a catalyst composition comprising at least one metal carbene olefin
metathesis catalyst, combining the resin composition comprising at
least one cyclic olefin and the catalyst composition comprising at
least one metal carbene olefin metathesis catalyst to form a ROMP
composition, contacting the object surface with the ROMP
composition, and subjecting the ROMP composition to conditions
effective to polymerize the ROMP composition.
[0062] In another embodiment a process for providing a ROMP polymer
coating for offshore applications is provided, the process
comprising, providing an object surface to be coated, providing a
resin composition comprising a one cyclic olefin composition,
providing a catalyst composition comprising at least one metal
carbene olefin metathesis catalyst, combining the resin composition
comprising at least one cyclic olefin composition and the catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst to form a ROMP composition, wherein the cyclic olefin
composition comprises 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation, contacting
the object surface with the ROMP composition, and subjecting the
ROMP composition to conditions effective to polymerize the ROMP
composition.
[0063] In another embodiment a process for providing a ROMP polymer
coating for offshore applications is provided, the process
comprising, providing an object surface to be coated, providing a
resin composition comprising at least one cyclic olefin, providing
a catalyst composition comprising at least one metal carbene olefin
metathesis catalyst, combining the resin composition comprising at
least one cyclic olefin and the catalyst composition comprising at
least one metal carbene olefin metathesis catalyst to form a ROMP
composition, applying the ROMP composition to the object surface,
and subjecting the ROMP composition to conditions effective to
polymerize the ROMP composition.
[0064] In another embodiment a process for providing a ROMP polymer
coating for offshore applications is provided, the process
comprising, providing an object surface to be coated, providing a
resin composition comprising a one cyclic olefin composition,
providing a catalyst composition comprising at least one metal
carbene olefin metathesis catalyst, combining the resin composition
comprising at least one cyclic olefin composition and the catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst to form a ROMP composition, wherein the cyclic olefin
composition comprises 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation, applying
the ROMP composition to the object surface, and subjecting the ROMP
composition to conditions effective to polymerize the ROMP
composition.
[0065] In another embodiment, the invention provides a thermal
insulation material comprising a resin composition comprising at
least one cyclic olefin and a catalyst composition comprising at
least one metal carbene olefin metathesis catalyst.
[0066] In another embodiment, the invention provides a thermal
insulation material comprising a resin composition comprising a one
cyclic olefin composition and a catalyst composition comprising at
least one metal carbene olefin metathesis catalyst, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation.
[0067] In another embodiment the invention provides a thermal
insulation material, comprising: a resin composition comprising at
least one cyclic olefin; and a catalyst composition comprising at
least one metal carbene olefin metathesis catalyst.
[0068] In another embodiment the invention provides a thermal
insulation material, comprising: a resin composition comprising a
one cyclic olefin composition, wherein the cyclic olefin
composition comprises 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation; and a
catalyst composition comprising at least one metal carbene olefin
metathesis catalyst.
[0069] In another embodiment, the invention provides a thermal
insulation material, wherein the thermal insulation material
comprises the reaction product of a resin composition comprising at
least one cyclic olefin and a catalyst composition comprising at
least one metal carbene olefin metathesis catalyst.
[0070] In another embodiment, the invention provides a thermal
insulation material, wherein the thermal insulation material
comprises the reaction product of a resin composition comprising at
least one cyclic olefin composition and a catalyst composition
comprising at least one metal carbene olefin metathesis catalyst,
wherein the cyclic olefin composition comprises 10.0 mol % to 80.0
mol % of at least one cyclic olefin containing multiunsaturation,
and up to 90.0 mol % of at least one cyclic olefin containing
monounsaturation; and a catalyst composition comprising at least
one metal carbene olefin metathesis catalyst.
[0071] In another embodiment, the invention provides a thermal
insulation material for subsea applications comprising a resin
composition comprising at least one cyclic olefin and a catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst.
[0072] In another embodiment, the invention provides a thermal
insulation material for subsea applications comprising a resin
composition comprising a cyclic olefin composition and a catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst, wherein the cyclic olefin composition comprises 10.0 mol
% to 80.0 mol % of at least one cyclic olefin containing
multiunsaturation, and up to 90.0 mol % of at least one cyclic
olefin containing monounsaturation.
[0073] In another embodiment, the invention provides a thermal
insulation material for subsea applications, wherein the thermal
insulation material comprises the reaction product of a resin
composition comprising at least one cyclic olefin and a catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst.
[0074] In another embodiment, the invention provides a thermal
insulation material for subsea applications, wherein the thermal
insulation material comprises the reaction product of a resin
composition comprising a cyclic olefin composition and a catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst, wherein the cyclic olefin composition comprises 10.0 mol
% to 80.0 mol % of at least one cyclic olefin containing
multiunsaturation, and up to 90.0 mol % of at least one cyclic
olefin containing monounsaturation.
[0075] In another embodiment, the invention provides a subsea
thermal insulation material comprising a resin composition
comprising at least one cyclic olefin and a catalyst composition
comprising at least one metal carbene olefin metathesis
catalyst.
[0076] In another embodiment, the invention provides a subsea
thermal insulation material comprising a resin composition
comprising a cyclic olefin composition and a catalyst composition
comprising at least one metal carbene olefin metathesis catalyst,
wherein the cyclic olefin composition comprises 10.0 mol % to 80.0
mol % of at least one cyclic olefin containing multiunsaturation,
and up to 90.0 mol % of at least one cyclic olefin containing
monounsaturation.
[0077] In another embodiment, the invention provides a subsea
thermal insulation material, wherein the subsea thermal insulation
material comprises the reaction product of a resin composition
comprising at least one cyclic olefin and a catalyst composition
comprising at least one metal carbene olefin metathesis
catalyst.
[0078] In another embodiment, the invention provides a subsea
thermal insulation material, wherein the subsea thermal insulation
material comprises the reaction product of a resin composition
comprising a cyclic olefin and a catalyst composition comprising at
least one metal carbene olefin metathesis catalyst, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation.
[0079] In another embodiment the invention provides a thermal
insulation material, comprising a ROMP polymer or a ROMP polymer
composite.
[0080] In another embodiment the invention provides a thermal
insulation material, comprising a ROMP polymer or a ROMP polymer
composite, wherein the ROMP polymer or ROMP polymer composite is a
reaction product of a resin composition comprising a cyclic olefin
composition and a catalyst composition comprising at least one
metal carbene olefin metathesis catalyst, wherein the cyclic olefin
composition comprises 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation.
[0081] In another embodiment the invention provides a thermal
insulation material for subsea applications, wherein the thermal
insulation material comprises a ROMP polymer or a ROMP polymer
composite.
[0082] In another embodiment the invention provides a thermal
insulation material for subsea applications, wherein the thermal
insulation material comprises a ROMP polymer or a ROMP polymer
composite, wherein the ROMP polymer or ROMP polymer composite is a
reaction product of a resin composition comprising a cyclic olefin
composition and a catalyst composition comprising at least one
metal carbene olefin metathesis catalyst, wherein the cyclic olefin
composition comprises 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation.
[0083] In another embodiment the invention provides a thermal
insulation material composition comprising a resin composition
comprising at least one cyclic olefin; and a catalyst composition
comprising at least one metal carbene olefin metathesis
catalyst.
[0084] In another embodiment the invention provides a thermal
insulation material composition comprising a resin composition
comprising a cyclic olefin composition, wherein the cyclic olefin
composition comprises 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation; and a
catalyst composition comprising at least one metal carbene olefin
metathesis catalyst.
[0085] In another embodiment the present invention provides ROMP
polymer materials for use as thermal insulation materials, where
the ROMP polymer materials have good low temperature
flexibility.
[0086] In another embodiment the present invention provides ROMP
polymer materials for use as thermal insulation materials, where
the ROMP polymer materials have good low temperature flexibility,
wherein the ROMP polymer materials are a reaction product of a
resin composition comprising a cyclic olefin composition and a
catalyst composition comprising at least one metal carbene olefin
metathesis catalyst, wherein the cyclic olefin composition
comprises 10.0 mol % to 80.0 mol % of at least one cyclic olefin
containing multiunsaturation, and up to 90.0 mol % of at least one
cyclic olefin containing monounsaturation.
[0087] In another embodiment the present invention provides ROMP
polymer composite materials for use as thermal insulation
materials, where the ROMP polymer composites have good low
temperature flexibility.
[0088] In another embodiment the present invention provides ROMP
polymer composite materials for use as thermal insulation
materials, where the ROMP polymer composites have good low
temperature flexibility, wherein the ROMP polymer composites are a
reaction product of a resin composition comprising a cyclic olefin
composition and a catalyst composition comprising at least one
metal carbene olefin metathesis catalyst, wherein the cyclic olefin
composition comprises 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation.
[0089] In another embodiment the present invention provides ROMP
polymer materials for use as thermal insulation materials, where
the ROMP polymer materials have good low temperature impact
properties.
[0090] In another embodiment the present invention provides ROMP
polymer materials for use as thermal insulation materials, where
the ROMP polymer materials have good low temperature impact
properties, wherein the ROMP polymer materials are a reaction
product of a resin composition comprising a cyclic olefin
composition and a catalyst composition comprising at least one
metal carbene olefin metathesis catalyst, wherein the cyclic olefin
composition comprises 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation.
[0091] In another embodiment the present invention provides ROMP
polymer composite materials for use as thermal insulation
materials, where the ROMP polymer composites have good low
temperature impact properties.
[0092] In another embodiment the present invention provides ROMP
polymer composite materials for use as thermal insulation
materials, where the ROMP polymer composites have good low
temperature impact properties, wherein the ROMP polymer composites
are a reaction product of a resin composition comprising a cyclic
olefin composition and a catalyst composition comprising at least
one metal carbene olefin metathesis catalyst, wherein the cyclic
olefin composition comprises 10.0 mol % to 80.0 mol % of at least
one cyclic olefin containing multiunsaturation, and up to 90.0 mol
% of at least one cyclic olefin containing monounsaturation.
[0093] In another embodiment the present invention provides ROMP
polymer materials for use as thermal insulation materials, where
the ROMP polymer materials have good corrosion resistance to sea
water (salt water).
[0094] In another embodiment the present invention provides ROMP
polymer materials for use as thermal insulation materials, where
the ROMP polymer materials have good corrosion resistance to sea
water (salt water), wherein the ROMP polymer materials are a
reaction product of a resin composition comprising a cyclic olefin
composition and a catalyst composition comprising at least one
metal carbene olefin metathesis catalyst, wherein the cyclic olefin
composition comprises 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation.
[0095] In another embodiment the present invention provides ROMP
polymer composite materials for use as thermal insulation
materials, where the ROMP polymer composites have good corrosion
resistance to sea water (salt water).
[0096] In another embodiment the present invention provides ROMP
polymer composite materials for use as thermal insulation
materials, where the ROMP polymer composites have good corrosion
resistance to sea water (salt water), wherein the ROMP polymer
composites are a reaction product of a resin composition comprising
a cyclic olefin composition and a catalyst composition comprising
at least one metal carbene olefin metathesis catalyst, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation.
[0097] In another embodiment the present invention provides ROMP
polymer materials for use as thermal insulation materials, where
the ROMP polymer materials have good thermal conductivity (e.g.,
low k value).
[0098] In another embodiment the present invention provides ROMP
polymer materials for use as thermal insulation materials, where
the ROMP polymer materials have good thermal conductivity (e.g.,
low k value), wherein the ROMP polymer materials are a reaction
product of a resin composition comprising a cyclic olefin
composition and a catalyst composition comprising at least one
metal carbene olefin metathesis catalyst, wherein the cyclic olefin
composition comprises 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation.
[0099] In another embodiment the present invention provides ROMP
polymer composite materials for use as thermal insulation
materials, where the ROMP polymer composites have good thermal
conductivity (e.g., low k value).
[0100] In another embodiment the present invention provides ROMP
polymer composite materials for use as thermal insulation
materials, where the ROMP polymer composites have good thermal
conductivity (e.g., low k value), wherein the ROMP polymer
composites are a reaction product of a resin composition comprising
a cyclic olefin composition and a catalyst composition comprising
at least one metal carbene olefin metathesis catalyst, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation.
[0101] The ROMP polymers and/or ROMP polymer composites of the
invention may be applied to an object using a variety of methods
known in the art. In one method, a form or mold is placed or
constructed around the object to be insulated. The resin
composition comprising at least one cyclic olefin and the catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst are combined to form a ROMP composition and the ROMP
composition is the applied between the object and the mold and the
ROMP composition is then subjected to conditions effective to cure
the ROMP composition. Once the ROMP composition has cured, the mold
is removed.
[0102] The ROMP polymers and/or ROMP polymer composites of the
invention may be applied to an object using a variety of methods
known in the art. In one method, a form or mold is placed or
constructed around the object to be insulated. The resin
composition comprising a cyclic olefin composition and the catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst are combined to form a ROMP composition, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation, and the ROMP composition is the applied between
the object and the mold and the ROMP composition is then subjected
to conditions effective to cure the ROMP composition. Once the ROMP
composition has cured, the mold is removed.
[0103] The ROMP polymer and/or ROMP polymer composite thermal
insulation materials of the invention need not necessarily be
molded around an object to be insulated. In the alternative, a ROMP
polymer article and/or ROMP polymer composite article may be
independently prepared and then subsequently affixed to or placed
around an object to thermally insulate the object from the
surrounding environment. Moreover, the means for affixing a ROMP
polymer article and/or ROMP polymer composite article to an object
may be by any known means including an adhesive means and/or
mechanical means such as fasteners, bolts, screws, etc. For
example, a ROMP polymer thermal insulation material and/or a ROMP
polymer composite thermal insulation material can be pre-made into
sections which are shaped to complement the object to be insulated.
The pre-made sections may then be secured or affixed to the object
using any known means. wherein the ROMP polymer and/or ROMP polymer
composites are a reaction product of a resin composition comprising
a cyclic olefin composition and a catalyst composition comprising
at least one metal carbene olefin metathesis catalyst, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation
[0104] The ROMP polymer and/or ROMP polymer composite thermal
insulation materials of the invention, wherein the ROMP polymer
and/or ROMP polymer composite thermal insulation materials are a
reaction product of a resin composition comprising a cyclic olefin
composition and a catalyst composition comprising at least one
metal carbene olefin metathesis catalyst, wherein the cyclic olefin
composition comprises 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation, need not
necessarily be molded around an object to be insulated. In the
alternative, a ROMP polymer article and/or ROMP polymer composite
article may be independently prepared and then subsequently affixed
to or placed around an object to thermally insulate the object from
the surrounding environment. Moreover, the means for affixing a
ROMP polymer article and/or ROMP polymer composite article to an
object may be by any known means including an adhesive means and/or
mechanical means such as fasteners, bolts, screws, etc. For
example, a ROMP polymer thermal insulation material and/or a ROMP
polymer composite thermal insulation material can be pre-made into
sections which are shaped to complement the object to be insulated.
The pre-made sections may then be secured or affixed to the object
using any known means.
[0105] The thermal insulation material compositions and/or ROMP
polymer compositions and/or ROMP polymer composite compositions of
the invention can be formulated so as to have a wide range of
tunable cure times.
[0106] The thermal insulation material compositions and/or ROMP
polymer compositions and/or ROMP polymer composite compositions of
the invention can be formulated so as to have a wide range of
tunable cure times, wherein the ROMP polymer compositions and/or
ROMP polymer composite compositions comprise a resin composition
comprising a cyclic olefin composition contacted with a catalyst
composition comprising at least one metal carbene olefin metathesis
catalysts, wherein the cyclic olefin composition comprises 10.0 mol
% to 80.0 mol % of at least one cyclic olefin containing
multiunsaturation, and up to 90.0 mol % of at least one cyclic
olefin containing monounsaturation.
[0107] In another embodiment the invention provides a method of
thermally insulating an object from a surrounding fluid, the method
comprising interposing a thermal insulation material between the
object and the fluid wherein the thermal insulation material
comprises the reaction product of at least one cyclic olefin and at
least one metal carbene olefin metathesis catalyst.
[0108] In another embodiment the invention provides a method of
thermally insulating an object from a surrounding fluid, the method
comprising interposing a thermal insulation material between the
object and the fluid wherein the thermal insulation material
comprises the reaction product of a resin composition comprising a
cyclic olefin composition and at least one metal carbene olefin
metathesis catalyst, wherein the cyclic olefin composition
comprises 10.0 mol % to 80.0 mol % of at least one cyclic olefin
containing multiunsaturation, and up to 90.0 mol % of at least one
cyclic olefin containing monounsaturation.
[0109] In another embodiment the invention provides a method of
thermally insulating an object from a surrounding fluid, the method
comprising interposing a thermal insulation material between the
object and the fluid wherein the thermal insulation material
comprises the reaction product of at least one cyclic olefin and at
least one metal carbene olefin metathesis catalyst, wherein the
interposition of the thermal insulation material is achieved by
positioning a mold a predetermined distance from the object and
applying the thermal insulation material between the object and the
mold, wherein the object is a pipe, pipeline, pipe fitting, hose,
hose fitting, tank, container, drum, manifold, riser, field joint,
a subsea Christmas tree, jumper, spool piece, pipeline end
termination, pipeline end manifold, robotic part, a robotic device,
a robotic vehicle, wellhead equipment, a subsea dog house, or
combinations thereof.
[0110] In another embodiment the invention provides a method of
thermally insulating an object from a surrounding fluid, the method
comprising interposing a thermal insulation material between the
object and the fluid wherein the thermal insulation material
comprises the reaction product of a resin composition comprising a
cyclic olefin composition and at least one metal carbene olefin
metathesis catalyst, wherein the cyclic olefin composition
comprises 10.0 mol % to 80.0 mol % of at least one cyclic olefin
containing multiunsaturation, and up to 90.0 mol % of at least one
cyclic olefin containing monounsaturation, wherein the
interposition of the thermal insulation material is achieved by
positioning a mold a predetermined distance from the object and
applying the thermal insulation material between the object and the
mold, wherein the object is a pipe, pipeline, pipe fitting, hose,
hose fitting, tank, container, drum, manifold, riser, field joint,
a subsea Christmas tree, jumper, spool piece, pipeline end
termination, pipeline end manifold, robotic part, a robotic device,
a robotic vehicle, wellhead equipment, a subsea dog house, or
combinations thereof.
[0111] In another embodiment the invention provides a method of
thermally insulating an object from a surrounding fluid, the method
comprising interposing a thermal insulation material between the
object and the fluid where the thermal insulation material
comprises a ROMP composition.
[0112] In another embodiment the invention provides a method of
thermally insulating an object from a surrounding fluid, the method
comprising interposing a thermal insulation material between the
object and the fluid where the thermal insulation material
comprises a ROMP composition, wherein the ROMP composition
comprises a resin composition comprising a cyclic olefin
composition contacted with a catalyst composition comprising at
least one metal carbene olefin metathesis catalysts, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation.
[0113] In another embodiment the invention provides a method of
thermally insulating an object from a surrounding fluid, the method
comprising interposing a thermal insulation material between the
object and the fluid where the thermal insulation material
comprises a ROMP composition, wherein the interposition of the
thermal insulation material is achieved by positioning a mold a
predetermined distance from the object and applying the thermal
insulation material between the object and the mold, wherein the
object is a pipe, pipeline, pipe fitting, hose, hose fitting, tank,
container, drum, manifold, riser, field joint, a subsea Christmas
tree, jumper, spool piece, pipeline end termination, pipeline end
manifold, robotic part, a robotic device, a robotic vehicle,
wellhead equipment, a subsea dog house, or combinations
thereof.
[0114] In another embodiment the invention provides a method of
thermally insulating an object from a surrounding fluid, the method
comprising interposing a thermal insulation material between the
object and the fluid where the thermal insulation material
comprises a ROMP composition, wherein the ROMP composition
comprises a resin composition comprising a cyclic olefin
composition contacted with a catalyst composition comprising at
least one metal carbene olefin metathesis catalysts, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation, wherein the interposition of the thermal
insulation material is achieved by positioning a mold a
predetermined distance from the object and applying the thermal
insulation material between the object and the mold, wherein the
object is a pipe, pipeline, pipe fitting, hose, hose fitting, tank,
container, drum, manifold, riser, field joint, a subsea Christmas
tree, jumper, spool piece, pipeline end termination, pipeline end
manifold, robotic part, a robotic device, a robotic vehicle,
wellhead equipment, a subsea dog house, or combinations
thereof.
[0115] In another embodiment the invention provides a method of
thermally insulating an object from a surrounding fluid, the method
comprising interposing a thermal insulation material between the
object and the fluid, where the thermal insulation material
comprises a ROMP polymer.
[0116] In another embodiment the invention provides a method of
thermally insulating an object from a surrounding fluid, the method
comprising interposing a thermal insulation material between the
object and the fluid, where the thermal insulation material
comprises a ROMP polymer, wherein the ROMP polymer is a reaction
product of a resin composition comprising a cyclic olefin
composition and a catalyst composition comprising at least one
metal carbene olefin metathesis catalyst, wherein the cyclic olefin
composition comprises 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation.
[0117] In another embodiment the invention provides a method of
thermally insulating an object from a surrounding fluid, the method
comprising interposing a thermal insulation material between the
object and the fluid, where the thermal insulation material
comprises a ROMP polymer, wherein the interposition of the thermal
insulation material is achieved by positioning a mold a
predetermined distance from the object and applying the thermal
insulation material between the object and the mold, wherein the
object is a pipe, pipeline, pipe fitting, hose, hose fitting, tank,
container, drum, manifold, riser, field joint, a subsea Christmas
tree, jumper, spool piece, pipeline end termination, pipeline end
manifold, robotic part, a robotic device, a robotic vehicle,
wellhead equipment, a subsea dog house, or combinations
thereof.
[0118] In another embodiment the invention provides a method of
thermally insulating an object from a surrounding fluid, the method
comprising interposing a thermal insulation material between the
object and the fluid, where the thermal insulation material
comprises a ROMP polymer, wherein the ROMP polymer is a reaction
product of a resin composition comprising a cyclic olefin
composition and a catalyst composition comprising at least one
metal carbene olefin metathesis catalyst, wherein the cyclic olefin
composition comprises 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation, wherein the
interposition of the thermal insulation material is achieved by
positioning a mold a predetermined distance from the object and
applying the thermal insulation material between the object and the
mold, wherein the object is a pipe, pipeline, pipe fitting, hose,
hose fitting, tank, container, drum, manifold, riser, field joint,
a subsea Christmas tree, jumper, spool piece, pipeline end
termination, pipeline end manifold, robotic part, a robotic device,
a robotic vehicle, wellhead equipment, a subsea dog house, or
combinations thereof.
[0119] In another embodiment the invention provides a method for
coating at least a portion of at least one surface of an object
with a thermal insulation material, comprising: combining a resin
composition comprising at least one cyclic olefin with a catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst, thereby forming a thermal insulation material
composition; applying the thermal insulation material composition
to the at least a portion of at least one surface of the object;
and subjecting the thermal insulation material composition to
conditions effective to promote ROMP reaction of the at least one
cyclic olefin in the presence of the at least one metal carbene
olefin metathesis catalyst, wherein the thermal insulation material
is a ROMP polymer or a ROMP polymer composite.
[0120] In another embodiment the invention provides a method for
coating at least a portion of at least one surface of an object
with a thermal insulation material, comprising: combining a resin
composition comprising a cyclic olefin composition with a catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst, thereby forming a thermal insulation material
composition, wherein the cyclic olefin composition comprises 10.0
mol % to 80.0 mol % of at least one cyclic olefin containing
multiunsaturation, and up to 90.0 mol % of at least one cyclic
olefin containing monounsaturation; applying the thermal insulation
material composition to the at least a portion of at least one
surface of the object; and subjecting the thermal insulation
material composition to conditions effective to promote ROMP
reaction of the cyclic olefin composition in the presence of the at
least one metal carbene olefin metathesis catalyst, wherein the
thermal insulation material is a ROMP polymer or a ROMP polymer
composite.
[0121] In another embodiment the invention provides a method for
coating at least a portion of an object with a thermal insulation
material, comprising: combining a resin composition comprising at
least one cyclic olefin with a catalyst composition comprising at
least one metal carbene olefin metathesis catalyst, thereby forming
a thermal insulation material composition; applying the thermal
insulation material composition to the at least a portion of at
least one surface of the object; and subjecting the thermal
insulation material composition to conditions effective to promote
a ROMP reaction of the at least one cyclic olefin in the presence
of the at least one metal carbene olefin metathesis catalyst,
wherein the thermal insulation material is a ROMP polymer or a ROMP
polymer composite.
[0122] In another embodiment the invention provides a method for
coating at least a portion of an object with a thermal insulation
material, comprising: combining a resin composition comprising a
cyclic olefin composition with a catalyst composition comprising at
least one metal carbene olefin metathesis catalyst, thereby forming
a thermal insulation material composition, wherein the cyclic
olefin composition comprises 10.0 mol % to 80.0 mol % of at least
one cyclic olefin containing multiunsaturation, and up to 90.0 mol
% of at least one cyclic olefin containing monounsaturation;
applying the thermal insulation material composition to the at
least a portion of at least one surface of the object; and
subjecting the thermal insulation material composition to
conditions effective to promote a ROMP reaction of the cyclic
olefin composition in the presence of the at least one metal
carbene olefin metathesis catalyst, wherein the thermal insulation
material is a ROMP polymer or a ROMP polymer composite.
[0123] In another embodiment the invention provides a method for
encasing at least a portion of an object with a thermal insulation
material, comprising: combining a resin composition comprising at
least one cyclic olefin with a catalyst composition comprising at
least one metal carbene olefin metathesis catalyst, thereby forming
a thermal insulation material composition; applying the thermal
insulation material composition to the at least a portion of at
least one surface of the object; and subjecting the thermal
insulation material composition to conditions effective to promote
a ROMP reaction of the at least one cyclic olefin in the presence
of the at least one metal carbene olefin metathesis catalyst,
wherein the thermal insulation material is a ROMP polymer or a ROMP
polymer composite.
[0124] In another embodiment the invention provides a method for
encasing at least a portion of an object with a thermal insulation
material, comprising: combining a resin composition comprising a
cyclic olefin composition with a catalyst composition comprising at
least one metal carbene olefin metathesis catalyst, thereby forming
a thermal insulation material composition, wherein the cyclic
olefin composition comprises 10.0 mol % to 80.0 mol % of at least
one cyclic olefin containing multiunsaturation, and up to 90.0 mol
% of at least one cyclic olefin containing monounsaturation;
applying the thermal insulation material composition to the at
least a portion of at least one surface of the object; and
subjecting the thermal insulation material composition to
conditions effective to promote a ROMP reaction of the cyclic
olefin composition in the presence of the at least one metal
carbene olefin metathesis catalyst, wherein the thermal insulation
material is a ROMP polymer or a ROMP polymer composite.
[0125] In another embodiment the invention provides a method for
coating at least a portion of at least one surface of an object
with a thermal insulation material, comprising: combining a resin
composition comprising at least one cyclic olefin with a catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst, thereby forming a ROMP composition; contacting the ROMP
composition with at least a portion of at least one surface of the
object; and subjecting the ROMP composition to conditions effective
to promote a ROMP reaction of the at least one cyclic olefin in the
presence of the at least one metal carbene olefin metathesis
catalyst, wherein the thermal insulation material is a ROMP polymer
or a ROMP polymer composite.
[0126] In another embodiment the invention provides a method for
coating at least a portion of at least one surface of an object
with a thermal insulation material, comprising: combining a resin
composition comprising a cyclic olefin composition with a catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst, thereby forming a ROMP composition, wherein the cyclic
olefin composition comprises 10.0 mol % to 80.0 mol % of at least
one cyclic olefin containing multiunsaturation, and up to 90.0 mol
% of at least one cyclic olefin containing monounsaturation;
contacting the ROMP composition with at least a portion of at least
one surface of the object; and subjecting the ROMP composition to
conditions effective to promote a ROMP reaction of the cyclic
olefin composition in the presence of the at least one metal
carbene olefin metathesis catalyst, wherein the thermal insulation
material is a ROMP polymer or a ROMP polymer composite.
[0127] In another embodiment the invention provides a method for
coating an object with a thermal insulation material, comprising:
combining a resin composition comprising at least one cyclic olefin
with a catalyst composition comprising at least one metal carbene
olefin metathesis catalyst, thereby forming a ROMP composition;
contacting the ROMP composition with at least a portion of at least
one surface of the object; and subjecting the ROMP composition to
conditions effective to promote a ROMP reaction of the at least one
cyclic olefin in the presence of the at least one metal carbene
olefin metathesis catalyst, wherein the thermal insulation material
is a ROMP polymer or a ROMP polymer composite.
[0128] In another embodiment the invention provides a method for
coating an object with a thermal insulation material, comprising:
combining a resin composition comprising a cyclic olefin
composition with a catalyst composition comprising at least one
metal carbene olefin metathesis catalyst, thereby forming a ROMP
composition, wherein the cyclic olefin composition comprises 10.0
mol % to 80.0 mol % of at least one cyclic olefin containing
multiunsaturation, and up to 90.0 mol % of at least one cyclic
olefin containing monounsaturation; contacting the ROMP composition
with at least a portion of at least one surface of the object; and
subjecting the ROMP composition to conditions effective to promote
a ROMP reaction of the cyclic olefin composition in the presence of
the at least one metal carbene olefin metathesis catalyst, wherein
the thermal insulation material is a ROMP polymer or a ROMP polymer
composite.
[0129] In another embodiment the invention provides a method for
coating at least a portion of at least one surface of an object
with a thermal insulation material, comprising: combining a resin
composition comprising at least one cyclic olefin with a catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst, thereby forming a ROMP composition; contacting the ROMP
composition with at least a portion of at least one surface of the
object; and subjecting the ROMP composition to conditions effective
to promote a ROMP reaction of the at least one cyclic olefin in the
presence of the at least one metal carbene olefin metathesis
catalyst, wherein the thermal insulation material is a ROMP polymer
or a ROMP polymer composite.
[0130] In another embodiment the invention provides a method for
coating at least a portion of at least one surface of an object
with a thermal insulation material, comprising: combining a resin
composition comprising a cyclic olefin with a catalyst composition
comprising at least one metal carbene olefin metathesis catalyst,
thereby forming a ROMP composition, wherein the cyclic olefin
composition comprises 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation; contacting
the ROMP composition with at least a portion of at least one
surface of the object; and subjecting the ROMP composition to
conditions effective to promote a ROMP reaction of the at least one
cyclic olefin in the presence of the at least one metal carbene
olefin metathesis catalyst, wherein the thermal insulation material
is a ROMP polymer or a ROMP polymer composite.
[0131] In another embodiment the invention provides a method for
encasing an object with a thermal insulation material, comprising:
combining a resin composition comprising at least one cyclic olefin
with a catalyst composition comprising at least one metal carbene
olefin metathesis catalyst, thereby forming a ROMP composition;
contacting the ROMP composition with the object; and subjecting the
ROMP composition to conditions effective to promote a ROMP reaction
of the at least one cyclic olefin in the presence of the at least
one metal carbene olefin metathesis catalyst, wherein the thermal
insulation material is a ROMP polymer or a ROMP polymer
composite.
[0132] In another embodiment the invention provides a method for
encasing an object with a thermal insulation material, comprising:
combining a resin composition comprising a cyclic olefin
composition with a catalyst composition comprising at least one
metal carbene olefin metathesis catalyst, thereby forming a ROMP
composition, wherein the cyclic olefin composition comprises 10.0
mol % to 80.0 mol % of at least one cyclic olefin containing
multiunsaturation, and up to 90.0 mol % of at least one cyclic
olefin containing monounsaturation; contacting the ROMP composition
with the object; and subjecting the ROMP composition to conditions
effective to promote a ROMP reaction of the cyclic olefin
composition in the presence of the at least one metal carbene
olefin metathesis catalyst, wherein the thermal insulation material
is a ROMP polymer or a ROMP polymer composite.
[0133] In another embodiment the invention provides a method for
encasing at least a portion of an object with a thermal insulation
material, comprising: combining a resin composition comprising at
least one cyclic olefin with a catalyst composition comprising at
least one metal carbene olefin metathesis catalyst, thereby forming
a ROMP composition; applying the ROMP composition to the at least a
portion of the object; and subjecting the ROMP composition to
conditions effective to promote a ROMP reaction of the at least one
cyclic olefin in the presence of the at least one metal carbene
olefin metathesis catalyst, wherein the thermal insulation material
is a ROMP polymer or a ROMP polymer composite.
[0134] In another embodiment the invention provides a method for
encasing at least a portion of an object with a thermal insulation
material, comprising: combining a resin composition comprising a
cyclic olefin composition with a catalyst composition comprising at
least one metal carbene olefin metathesis catalyst, thereby forming
a ROMP composition, wherein the cyclic olefin composition comprises
10.0 mol % to 80.0 mol % of at least one cyclic olefin containing
multiunsaturation, and up to 90.0 mol % of at least one cyclic
olefin containing monounsaturation; applying the ROMP composition
to the at least a portion of the object; and subjecting the ROMP
composition to conditions effective to promote a ROMP reaction of
the cyclic olefin composition in the presence of the at least one
metal carbene olefin metathesis catalyst, wherein the thermal
insulation material is a ROMP polymer or a ROMP polymer
composite.
[0135] In another embodiment the invention provides a method for
coating at least a portion of at least one surface of an object
with a thermal insulation material, wherein the thermal insulation
material is a reaction product of a resin composition comprising a
cyclic olefin composition and a catalyst composition comprising at
least one metal carbene olefin metathesis catalyst, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation.
[0136] A process for applying a thermal insulation material
composition to a pipe, comprising: placing a mold around a pipe to
define a cavity between an internal surface of the mold and the
pipe; injecting a thermal insulation material composition in the
cavity, wherein the thermal insulation material composition
comprises a resin composition comprising at least one cyclic olefin
and a catalyst composition comprising at least one metal carbene
olefin metathesis catalyst; and subjecting the thermal insulation
material composition to conditions effective to promote a ROMP
reaction between the at least one cyclic olefin and the at least
one metal carbene olefin metathesis catalyst.
[0137] A process for applying a thermal insulation material
composition to a pipe, comprising: placing a mold around a pipe to
define a cavity between an internal surface of the mold and the
pipe; injecting a thermal insulation material composition in the
cavity, wherein the thermal insulation material composition
comprises a resin composition comprising a cyclic olefin
composition and a catalyst composition comprising at least one
metal carbene olefin metathesis catalyst, wherein the cyclic olefin
composition comprises 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation; and
subjecting the thermal insulation material composition to
conditions effective to promote a ROMP reaction between the at
least one cyclic olefin and the at least one metal carbene olefin
metathesis catalyst.
[0138] A process for applying a thermal insulation material
composition to an object, comprising: placing a mold around an
object to define a cavity between an internal surface of the mold
and the object; injecting a thermal insulation material composition
in the cavity, wherein the thermal insulation material composition
comprises a resin composition comprising at least one cyclic olefin
and a catalyst composition comprising at least one metal carbene
olefin metathesis catalyst; and subjecting the thermal insulation
material composition to conditions effective to promote a ROMP
reaction between the at least one cyclic olefin and the at least
one metal carbene olefin metathesis catalyst.
[0139] A process for applying a thermal insulation material
composition to an object, comprising: placing a mold around an
object to define a cavity between an internal surface of the mold
and the object; injecting a thermal insulation material composition
in the cavity, wherein the thermal insulation material composition
comprises a resin composition comprising a cyclic olefin
composition and a catalyst composition comprising at least one
metal carbene olefin metathesis catalyst, wherein the thermal
insulation material composition comprises a resin composition
comprising at least one cyclic olefin composition and a catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst, wherein the cyclic olefin composition comprises 10.0 mol
% to 80.0 mol % of at least one cyclic olefin containing
multiunsaturation, and up to 90.0 mol % of at least one cyclic
olefin containing monounsaturation; and subjecting the thermal
insulation material composition to conditions effective to promote
a ROMP reaction between the at least one cyclic olefin and the at
least one metal carbene olefin metathesis catalyst.
[0140] A process for applying a thermal insulation material
composition to a field joint, comprising: placing a mold around a
field joint to define a cavity between an internal surface of the
mold and the field joint; injecting a thermal insulation material
composition in the cavity, wherein the thermal insulation material
composition comprises a resin composition comprising at least one
cyclic olefin and a catalyst composition comprising at least one
metal carbene olefin metathesis catalyst; and subjecting the
thermal insulation material composition to conditions effective to
promote a ROMP reaction between the at least one cyclic olefin and
the at least one metal carbene olefin metathesis catalyst.
[0141] A process for applying a thermal insulation material
composition to a field joint, comprising: placing a mold around a
field joint to define a cavity between an internal surface of the
mold and the field joint; injecting a thermal insulation material
composition in the cavity, wherein the thermal insulation material
composition comprises a resin composition comprising a cyclic
olefin composition and a catalyst composition comprising at least
one metal carbene olefin metathesis catalyst, wherein the cyclic
olefin composition comprises 10.0 mol % to 80.0 mol % of at least
one cyclic olefin containing multiunsaturation, and up to 90.0 mol
% of at least one cyclic olefin containing monounsaturation; and
subjecting the thermal insulation material composition to
conditions effective to promote a ROMP reaction between the at
least one cyclic olefin and the at least one metal carbene olefin
metathesis catalyst.
[0142] In another embodiment the invention provides an object at
least partially encased by a thermal insulation material, wherein
the thermal insulation material comprises the reaction product of
at least one cyclic olefin and at least one metal carbene olefin
metathesis catalyst.
[0143] In another embodiment the invention provides an object at
least partially encased by a thermal insulation material, wherein
the thermal insulation material comprises the reaction product of a
resin composition comprising a cyclic olefin composition and a
catalyst composition comprising at least one metal carbene olefin
metathesis catalyst, wherein the cyclic olefin composition
comprises 10.0 mol % to 80.0 mol % of at least one cyclic olefin
containing multiunsaturation, and up to 90.0 mol % of at least one
cyclic olefin containing monounsaturation.
[0144] In another embodiment the invention provides an object at
least partially encased by a thermal insulation material, where the
thermal insulation material comprises a ROMP composition.
[0145] In another embodiment the invention provides an object at
least partially encased by a thermal insulation material, where the
thermal insulation material comprises a ROMP composition, wherein
the ROMP composition comprises a resin composition comprising a
cyclic olefin composition and a catalyst composition comprising at
least one metal carbene olefin metathesis catalyst, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation.
[0146] In another embodiment the invention provides an object at
least partially encased by a thermal insulation material, where the
thermal insulation material comprises a ROMP polymer or ROMP
polymer composite.
[0147] In another embodiment the invention provides an object at
least partially encased by a thermal insulation material, where the
thermal insulation material comprises a ROMP polymer or ROMP
polymer composite, where the ROMP polymer or ROMP polymer composite
are a reaction product of a resin composition comprising a cyclic
olefin composition and a catalyst composition comprising at least
one metal carbene olefin metathesis catalyst, wherein the cyclic
olefin composition comprises 10.0 mol % to 80.0 mol % of at least
one cyclic olefin containing multiunsaturation, and up to 90.0 mol
% of at least one cyclic olefin containing monounsaturation.
[0148] In another embodiment the invention provides a pipe at least
partially encased by a thermal insulation material, where the
thermal insulation material comprises the reaction product of at
least one cyclic olefin and at least one metal carbene olefin
metathesis catalyst.
[0149] In another embodiment the invention provides a pipe at least
partially encased by a thermal insulation material, where the
thermal insulation material comprises the reaction product of a
resin composition comprising a cyclic olefin composition and a
catalyst composition comprising at least one metal carbene olefin
metathesis catalyst, wherein the cyclic olefin composition
comprises 10.0 mol % to 80.0 mol % of at least one cyclic olefin
containing multiunsaturation, and up to 90.0 mol % of at least one
cyclic olefin containing monounsaturation.
[0150] In another embodiment the invention provides a pipe at least
partially encased by a thermal insulation material, where the
thermal insulation material comprises a ROMP polymer or ROMP
polymer composite.
[0151] In another embodiment the invention provides a pipe at least
partially encased by a thermal insulation material, where the
thermal insulation material comprises a ROMP polymer or ROMP
polymer composite, where the ROMP polymer or ROMP polymer composite
are a reaction product of a resin composition comprising a cyclic
olefin composition and a catalyst composition comprising at least
one metal carbene olefin metathesis catalyst, wherein the cyclic
olefin composition comprises 10.0 mol % to 80.0 mol % of at least
one cyclic olefin containing multiunsaturation, and up to 90.0 mol
% of at least one cyclic olefin containing monounsaturation.
[0152] In another embodiment the invention provides a field joint
at least partially coated with a thermal insulation material, where
the thermal insulation material comprises the reaction product of
at least one cyclic olefin and at least one metal carbene olefin
metathesis catalyst.
[0153] In another embodiment the invention provides a field joint
at least partially coated with a thermal insulation material, where
the thermal insulation material comprises the reaction product of a
resin composition comprising a cyclic olefin composition and a
catalyst composition comprising at least one metal carbene olefin
metathesis catalyst, wherein the cyclic olefin composition
comprises 10.0 mol % to 80.0 mol % of at least one cyclic olefin
containing multiunsaturation, and up to 90.0 mol % of at least one
cyclic olefin containing monounsaturation.
[0154] In another embodiment the invention provides a field joint
at least partially coated with a thermal insulation material, where
the thermal insulation material comprises a ROMP polymer or ROMP
polymer composite.
[0155] In another embodiment the invention provides a field joint
at least partially coated with a thermal insulation material, where
the thermal insulation material comprises a ROMP polymer or ROMP
polymer composite, where the ROMP polymer or ROMP polymer composite
are a reaction product of a resin composition comprising a cyclic
olefin composition and a catalyst composition comprising at least
one metal carbene olefin metathesis catalyst, wherein the cyclic
olefin composition comprises 10.0 mol % to 80.0 mol % of at least
one cyclic olefin containing multiunsaturation, and up to 90.0 mol
% of at least one cyclic olefin containing monounsaturation.
[0156] In another embodiment the invention provides a field joint
at least partially coated with a thermal insulation material, where
the thermal insulation material comprises the reaction product of a
resin composition comprising at least one cyclic olefin and a
catalyst composition comprising at least one metal carbene olefin
metathesis catalyst.
[0157] In another embodiment the invention provides a field joint
at least partially coated with a thermal insulation material, where
the thermal insulation material comprises the reaction product of a
resin composition comprising a cyclic olefin composition and a
catalyst composition comprising at least one metal carbene olefin
metathesis catalyst, wherein the cyclic olefin composition
comprises 10.0 mol % to 80.0 mol % of at least one cyclic olefin
containing multiunsaturation, and up to 90.0 mol % of at least one
cyclic olefin containing monounsaturation.
[0158] In another embodiment the invention provides a field joint
at least partially encased with a thermal insulation material,
where the thermal insulation material comprises the reaction
product of at least one cyclic olefin and at least one metal
carbene olefin metathesis catalyst.
[0159] In another embodiment the invention provides a field joint
at least partially encased with a thermal insulation material,
where the thermal insulation material comprises the reaction
product of a resin composition comprising a cyclic olefin
composition and a catalyst composition comprising at least one
metal carbene olefin metathesis catalyst, wherein the cyclic olefin
composition comprises 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation.
[0160] In another embodiment the invention provides a field joint
at least partially encased with a thermal insulation material,
where the thermal insulation material comprises a ROMP polymer or
ROMP polymer composite.
[0161] In another embodiment the invention provides a field joint
at least partially encased with a thermal insulation material,
where the thermal insulation material comprises a ROMP polymer or
ROMP polymer composite, where the ROMP polymer or ROMP polymer
composite are a reaction product of a resin composition comprising
a cyclic olefin composition and a catalyst composition comprising
at least one metal carbene olefin metathesis catalyst, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation.
[0162] In another embodiment the invention provides a thermal
insulation material for use in coating a field joint, the thermal
insulation material comprising a resin composition comprising at
least one cyclic olefin and at least one metal carbene olefin
metathesis catalyst.
[0163] In another embodiment the invention provides a thermal
insulation material for use in coating a field joint, the thermal
insulation material comprising a resin composition comprising a
cyclic olefin composition and a catalyst composition comprising at
least one metal carbene olefin metathesis catalyst, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation.
[0164] In another embodiment the invention provides a thermal
insulation material for use in coating an object, the thermal
insulation material comprising a resin composition comprising at
least one cyclic olefin and at least one metal carbene olefin
metathesis catalyst.
[0165] In another embodiment the invention provides a thermal
insulation material for use in coating an object, the thermal
insulation material comprising a resin composition comprising
cyclic olefin composition and a catalyst composition comprising at
least one metal carbene olefin metathesis catalyst, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation.
[0166] In another embodiment the invention provides for use of at
least one thermal insulation material composition for coating at
least a portion of at least one surface of an object, wherein the
at least one thermal insulation material composition comprises a
resin composition comprising at least one cyclic olefin and a
catalyst composition comprising at least one metal carbene olefin
metathesis catalyst.
[0167] In another embodiment the invention provides for use of at
least one thermal insulation material composition for coating at
least a portion of at least one surface of an object, wherein the
at least one thermal insulation material composition comprises a
resin composition comprising a cyclic olefin composition and a
catalyst composition comprising at least one metal carbene olefin
metathesis catalyst, wherein the cyclic olefin composition
comprises 10.0 mol % to 80.0 mol % of at least one cyclic olefin
containing multiunsaturation, and up to 90.0 mol % of at least one
cyclic olefin containing monounsaturation.
[0168] In another embodiment the invention provides for use of at
least one thermal insulation material for coating at least a
portion of at least one surface of an object, wherein the at least
one thermal insulation material comprises a ROMP polymer or a ROMP
polymer composite.
[0169] In another embodiment the invention provides for use of at
least one thermal insulation material for coating at least a
portion of at least one surface of an object, wherein the at least
one thermal insulation material comprises a ROMP polymer or a ROMP
polymer composite, where the ROMP polymer or ROMP polymer composite
are a reaction product of a resin composition comprising a cyclic
olefin composition and a catalyst composition comprising at least
one metal carbene olefin metathesis catalyst, wherein the cyclic
olefin composition comprises 10.0 mol % to 80.0 mol % of at least
one cyclic olefin containing multiunsaturation, and up to 90.0 mol
% of at least one cyclic olefin containing monounsaturation.
[0170] Embodiments herein are not meant to be construed in a
limiting sense. Various modifications in form and detail of the
embodiments of the invention, as well as other aspects and
variations of the invention, will be apparent to the skilled
artisan in light of the following detailed description and
examples.
BRIEF DESCRIPTION OF THE DRAWINGS
[0171] Various other objects, features and attendant advantages of
the present invention will be more fully appreciated as the same
becomes better understood when considered in conjunction with the
accompanying drawings/figures, in which like reference characters
designate the same or similar parts throughout the several views,
and wherein:
[0172] FIG. 1 is a photograph showing a pipe coated with a thermal
insulation material comprising a ROMP polymer of Example 2, where
an exposed section of the pipe is simulating a field joint.
[0173] FIG. 2 is a photograph showing a pipe coated with a thermal
insulation material comprising a ROMP polymer of Example 2, where
the previously exposed section of the pipe simulating a field joint
(FIG. 1) is now coated with (encased by) a thermal insulation
material comprising a ROMP polymer of Example 2.
[0174] FIG. 3 is a graph of the cure profile of the ROMP
composition (thermal insulation composition) applied to Pipe Sample
(B). The peak temperatures at the three thermocouple positions:
thermocouple (1)--positioned in the middle of the ROMP composition
(1'' from the mold and the pipe), thermocouple (2)--positioned at
the ROMP composition/mold interface, and thermocouple
(3)--positioned at the ROMP composition/pipe interface, were
183.degree. C., 182.degree. C., and 158.degree. C.,
respectively.
DETAILED DESCRIPTION
Terminology and Definitions
[0175] Unless otherwise indicated, the invention is not limited to
specific reactants, substituents, catalysts, catalyst compositions,
resin compositions, cyclic olefins, reaction conditions, or the
like, as such may vary. It is also to be understood that the
terminology used herein is for the purpose of describing particular
embodiments only and is not to be interpreted as being
limiting.
[0176] As used in the specification and the appended claims, the
singular forms "a," "an," and "the" include plural referents unless
the context clearly dictates otherwise. Thus, for example,
reference to "an oi-olefin" includes a single oi-olefin as well as
a combination or mixture of two or more a-olefins, reference to "a
substituent" encompasses a single substituent as well as two or
more substituents, and the like.
[0177] As used in the specification and the appended claims, the
terms "for example," "for instance," "such as," or "including" are
meant to introduce examples that further clarify more general
subject matter. Unless otherwise specified, these examples are
provided only as an aid for understanding the invention, and are
not meant to be limiting in any fashion.
[0178] In this specification and in the claims that follow,
reference will be made to a number of terms, which shall be defined
to have the following meanings:
[0179] The term "alkyl" as used herein refers to a linear,
branched, or cyclic saturated hydrocarbon group typically although
not necessarily containing 1 to about 24 carbon atoms, preferably 1
to about 12 carbon atoms, such as methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, and the like,
as well as cycloalkyl groups such as cyclopentyl, cyclohexyl, and
the like. Generally, although again not necessarily, alkyl groups
herein contain 1 to about 12 carbon atoms. The term "lower alkyl"
refers to an alkyl group of 1 to 6 carbon atoms, and the specific
term "cycloalkyl" refers to a cyclic alkyl group, typically having
4 to 8, preferably 5 to 7, carbon atoms. The term "substituted
alkyl" refers to alkyl substituted with one or more substituent
groups, and the terms "heteroatom-containing alkyl" and
"heteroalkyl" refer to alkyl in which at least one carbon atom is
replaced with a heteroatom. If not otherwise indicated, the terms
"alkyl" and "lower alkyl" include linear, branched, cyclic,
unsubstituted, substituted, and/or heteroatom-containing alkyl and
lower alkyl, respectively.
[0180] The term "alkylene" as used herein refers to a difunctional
linear, branched, or cyclic alkyl group, where "alkyl" is as
defined above.
[0181] The term "alkenyl" as used herein refers to a linear,
branched, or cyclic hydrocarbon group of 2 to about 24 carbon atoms
containing at least one double bond, such as ethenyl, n-propenyl,
isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, tetradecenyl,
hexadecenyl, eicosenyl, tetracosenyl, and the like. Preferred
alkenyl groups herein contain 2 to about 12 carbon atoms. The term
"lower alkenyl" refers to an alkenyl group of 2 to 6 carbon atoms,
and the specific term "cycloalkenyl" refers to a cyclic alkenyl
group, preferably having 5 to 8 carbon atoms. The term "substituted
alkenyl" refers to alkenyl substituted with one or more substituent
groups, and the terms "heteroatom-containing alkenyl" and
"heteroalkenyl" refer to alkenyl in which at least one carbon atom
is replaced with a heteroatom. If not otherwise indicated, the
terms "alkenyl" and "lower alkenyl" include linear, branched,
cyclic, unsubstituted, substituted, and/or heteroatom-containing
alkenyl and lower alkenyl, respectively.
[0182] The term "alkenylene" as used herein refers to a
difunctional linear, branched, or cyclic alkenyl group, where
"alkenyl" is as defined above.
[0183] The term "alkynyl" as used herein refers to a linear or
branched hydrocarbon group of 2 to about 24 carbon atoms containing
at least one triple bond, such as ethynyl, n-propynyl, and the
like. Preferred alkynyl groups herein contain 2 to about 12 carbon
atoms. The term "lower alkynyl" refers to an alkynyl group of 2 to
6 carbon atoms. The term "substituted alkynyl" refers to alkynyl
substituted with one or more substituent groups, and the terms
"heteroatom-containing alkynyl" and "heteroalkynyl" refer to
alkynyl in which at least one carbon atom is replaced with a
heteroatom. If not otherwise indicated, the terms "alkynyl" and
"lower alkynyl" include linear, branched, unsubstituted,
substituted, and/or heteroatom-containing alkynyl and lower
alkynyl, respectively.
[0184] The term "alkoxy" as used herein refers to an alkyl group
bound through a single, terminal ether linkage; that is, an
"alkoxy" group may be represented as --O-alkyl where alkyl is as
defined above. A "lower alkoxy" group refers to an alkoxy group
containing 1 to 6 carbon atoms. Analogously, "alkenyloxy" and
"lower alkenyloxy" respectively refer to an alkenyl and lower
alkenyl group bound through a single, terminal ether linkage, and
"alkynyloxy" and "lower alkynyloxy" respectively refer to an
alkynyl and lower alkynyl group bound through a single, terminal
ether linkage.
[0185] The term "aryl" as used herein, and unless otherwise
specified, refers to an aromatic substituent containing a single
aromatic ring or multiple aromatic rings that are fused together,
directly linked, or indirectly linked (such that the different
aromatic rings are bound to a common group such as a methylene or
ethylene moiety). Preferred aryl groups contain 5 to 24 carbon
atoms, and particularly preferred aryl groups contain 5 to 14
carbon atoms. Exemplary aryl groups contain one aromatic ring or
two fused or linked aromatic rings, e.g., phenyl, naphthyl,
biphenyl, diphenylether, diphenylamine, benzophenone, and the like.
"Substituted aryl" refers to an aryl moiety substituted with one or
more substituent groups, and the terms "heteroatom-containing aryl"
and "heteroaryl" refer to aryl substituents in which at least one
carbon atom is replaced with a heteroatom, as will be described in
further detail infra.
[0186] The term "aryloxy" as used herein refers to an aryl group
bound through a single, terminal ether linkage, wherein "aryl" is
as defined above. An "aryloxy" group may be represented as --O-aryl
where aryl is as defined above. Preferred aryloxy groups contain 5
to 24 carbon atoms, and particularly preferred aryloxy groups
contain 5 to 14 carbon atoms. Examples of aryloxy groups include,
without limitation, phenoxy, o-halo-phenoxy, m-halo-phenoxy,
p-halo-phenoxy, o-methoxy-phenoxy, m-methoxy-phenoxy,
p-methoxy-phenoxy, 2,4-dimethoxy-phenoxy, 3,4,5-trimethoxy-phenoxy,
and the like.
[0187] The term "alkaryl" refers to an aryl group with an alkyl
substituent, and the term "aralkyl" refers to an alkyl group with
an aryl substituent, wherein "aryl" and "alkyl" are as defined
above. Preferred alkaryl and aralkyl groups contain 6 to 24 carbon
atoms, and particularly preferred alkaryl and aralkyl groups
contain 6 to 16 carbon atoms. Alkaryl groups include, without
limitation, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl,
2,7-dimethylnaphthyl, 7-cyclooctylnaphthyl,
3-ethyl-cyclopenta-1,4-diene, and the like. Examples of aralkyl
groups include, without limitation, benzyl, 2-phenyl-ethyl,
3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl,
4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl,
4-benzylcyclohexylmethyl, and the like. The terms "alkaryloxy" and
"aralkyloxy" refer to substituents of the formula --OR wherein R is
alkaryl or aralkyl, respectively, as just defined.
[0188] The term "acyl" refers to substituents having the formula
--(CO)-alkyl, --(CO)-aryl, --(CO)-aralkyl, --(CO)-alkaryl,
--(CO)-alkenyl, or --(CO)-alkynyl, and the term "acyloxy" refers to
substituents having the formula --O(CO)-alkyl, --O(CO)-aryl,
--O(CO)-aralkyl, --O(CO)-alkaryl, --O(CO)-alkenyl, --O(CO)-alkynyl
wherein "alkyl," "aryl," "aralkyl", alkaryl, alkenyl, and alkynyl
are as defined above.
[0189] The terms "cyclic" and "ring" refer to alicyclic or aromatic
groups that may or may not be substituted and/or heteroatom
containing, and that may be monocyclic, bicyclic, or polycyclic.
The term "alicyclic" is used in the conventional sense to refer to
an aliphatic cyclic moiety, as opposed to an aromatic cyclic
moiety, and may be monocyclic, bicyclic, or polycyclic.
[0190] The terms "halo" and "halogen" are used in the conventional
sense to refer to a chloro, bromo, fluoro, or iodo substituent.
[0191] "Hydrocarbyl" refers to univalent hydrocarbyl radicals
containing 1 to about 30 carbon atoms, preferably 1 to about 24
carbon atoms, most preferably 1 to about 12 carbon atoms, including
linear, branched, cyclic, saturated, and unsaturated species, such
as alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and
the like. The term "lower hydrocarbyl" intends a hydrocarbyl group
of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and the
term "hydrocarbylene" refers to a divalent hydrocarbyl moiety
containing 1 to about 30 carbon atoms, preferably 1 to about 24
carbon atoms, most preferably 1 to about 12 carbon atoms, including
linear, branched, cyclic, saturated, and unsaturated species. The
term "lower hydrocarbylene" refers to a hydrocarbylene group of 1
to 6 carbon atoms. "Substituted hydrocarbyl" refers to hydrocarbyl
substituted with one or more substituent groups, and the terms
"heteroatom-containing hydrocarbyl" and "heterohydrocarbyl" refer
to hydrocarbyl in which at least one carbon atom is replaced with a
heteroatom. Similarly, "substituted hydrocarbylene" refers to
hydrocarbylene substituted with one or more substituent groups, and
the terms "heteroatom-containing hydrocarbylene" and
"heterohydrocarbylene" refer to hydrocarbylene in which at least
one carbon atom is replaced with a heteroatom. Unless otherwise
indicated, the term "hydrocarbyl" and "hydrocarbylene" are to be
interpreted as including substituted and/or heteroatom-containing
hydrocarbyl and heteroatom-containing hydrocarbylene moieties,
respectively.
[0192] The term "heteroatom-containing" as in a
"heteroatom-containing hydrocarbyl group" refers to a hydrocarbon
molecule or a hydrocarbyl molecular fragment in which one or more
carbon atoms is replaced with an atom other than carbon, e.g.,
nitrogen, oxygen, sulfur, phosphorus, or silicon, typically
nitrogen, oxygen, or sulfur. Similarly, the term "heteroalkyl"
refers to an alkyl substituent that is heteroatom-containing, the
term "heterocyclic" refers to a cyclic substituent that is
heteroatom-containing, the terms "heteroaryl" and "heteroaromatic"
respectively refer to "aryl" and "aromatic" substituents that are
heteroatom-containing, and the like. It should be noted that a
"heterocyclic" group or compound may or may not be aromatic, and
further that "heterocycles" may be monocyclic, bicyclic, or
polycyclic as described above with respect to the term "aryl."
Examples of heteroalkyl groups include without limitation
alkoxyaryl, alkylsulfanyl-substituted alkyl, N-alkylated amino
alkyl, and the like. Examples of heteroaryl substituents include
without limitation pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl,
indolyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, tetrazolyl,
etc., and examples of heteroatom-containing alicyclic groups
include without limitation pyrrolidino, morpholino, piperazino,
piperidino, etc.
[0193] By "substituted" as in "substituted hydrocarbyl,"
"substituted alkyl," "substituted aryl," and the like, as alluded
to in some of the aforementioned definitions, is meant that in the
hydrocarbyl, alkyl, aryl, or other moiety, at least one hydrogen
atom bound to a carbon (or other) atom is replaced with one or more
non-hydrogen substituents. Examples of such substituents include,
without limitation: functional groups referred to herein as "Fn,"
such as halo, hydroxyl, sulfhydryl, C.sub.1-C.sub.24 alkoxy,
C.sub.2-C.sub.24 alkenyloxy, C.sub.2-C.sub.24 alkynyloxy,
C.sub.5-C.sub.24 aryloxy, C.sub.6-C.sub.24 aralkyloxy,
C.sub.6-C.sub.24 alkaryloxy, acyl (including C.sub.2-C.sub.24
alkylcarbonyl (--CO-alkyl) and C.sub.6-C.sub.24 arylcarbonyl
(--CO-aryl)), acyloxy (--O-acyl, including C.sub.2-C.sub.24
alkylcarbonyloxy (--O--CO-alkyl) and C.sub.6-C.sub.24
arylcarbonyloxy (--O--CO-aryl)), C.sub.2-C.sub.24 alkoxycarbonyl
(--(CO)--O-alkyl), C.sub.6-C.sub.24 aryloxycarbonyl
(--(CO)--O-aryl), halocarbonyl (--CO)--X where X is halo),
C.sub.2-C.sub.24 alkylcarbonato (--O--(CO)--O-alkyl),
C.sub.6-C.sub.24 arylcarbonato (--O--(CO)--O-aryl), carboxy
(--COOH), carboxylato (--COO.sup.-), carbamoyl (--(CO)--NH.sub.2),
mono-(C.sub.1-C.sub.24 alkyl)-substituted carbamoyl
(--(CO)--NH(C.sub.1-C.sub.24 alkyl)), di-(C.sub.1-C.sub.24
alkyl)-substituted carbamoyl (--(CO)--N(C.sub.1-C.sub.24
alkyl).sub.2), mono-(C.sub.1-C.sub.24 haloalkyl)-substituted
carbamoyl (--(CO)--NH(C.sub.1-C.sub.24 haloalkyl)),
di-(C.sub.1-C.sub.24 haloalkyl)-substituted carbamoyl
(--(CO)--N(C.sub.1-C.sub.24 haloalkyl).sub.2),
mono-(C.sub.5-C.sub.24 aryl)-substituted carbamoyl
(--(CO)--NH-aryl), di-(C.sub.5-C.sub.24 aryl)-substituted carbamoyl
(--(CO)--N(C.sub.5-C.sub.24 aryl).sub.2), di-N--(C.sub.1-C.sub.24
alkyl), N--(C.sub.5-C.sub.24 aryl)-substituted carbamoyl
(--(CO)--N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl),
thiocarbamoyl (--(CS)--NH.sub.2), mono-(C.sub.1-C.sub.24
alkyl)-substituted thiocarbamoyl (--(CS)--NH(C.sub.1-C.sub.24
alkyl)), di-(C.sub.1-C.sub.24 alkyl)-substituted thiocarbamoyl
(--(CS)--N(C.sub.1-C.sub.24 alkyl).sub.2), mono-(C.sub.5-C.sub.24
aryl)-substituted thiocarbamoyl (--(CS)--NH-aryl),
di-(C.sub.5-C.sub.24 aryl)-substituted thiocarbamoyl
(--(CS)--N(C.sub.5-C.sub.24 aryl).sub.2), di-N--(C.sub.1-C.sub.24
alkyl), N--(C.sub.5-C.sub.24 aryl)-substituted thiocarbamoyl
(--(CS)--N(C.sub.1-C.sub.24 alkyl)(C.sub.5-C.sub.24 aryl),
carbamido (--NH--(CO)--NH.sub.2), cyano (--CN), cyanato
(--O--C.ident.N), thiocyanato (--S--C.ident.N), isocyanate
(--N.dbd.C.dbd.O), thioisocyanate (--N.dbd.C.dbd.S), formyl
(--(CO)--H), thioformyl (--(CS)--H), amino (--NH.sub.2),
mono-(C.sub.1-C.sub.24 alkyl)-substituted amino
(--NH(C.sub.1-C.sub.24 alkyl), di-(C.sub.1-C.sub.24
alkyl)-substituted amino (--N(C.sub.1-C.sub.24 alkyl).sub.2),
mono-(C.sub.5-C.sub.24 aryl)-substituted amino
(--NH(C.sub.5-C.sub.24 aryl), di-(C.sub.5-C.sub.24
aryl)-substituted amino (--N(C.sub.5-C.sub.24 aryl).sub.2),
C.sub.2-C.sub.24 alkylamido (--NH--(CO)-alkyl), C.sub.6-C.sub.24
arylamido (--NH--(CO)-aryl), imino (--CR.dbd.NH where R includes
without limitation hydrogen, C.sub.1-C.sub.24 alkyl,
C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24
aralkyl, etc.), C.sub.2-C.sub.20 alkylimino (--CR.dbd.N(alkyl),
where R includes without limitation hydrogen, C.sub.1-C.sub.24
alkyl, C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl,
C.sub.6-C.sub.24 aralkyl, etc.), arylimino (--CR.dbd.N(aryl), where
R includes without limitation hydrogen, C.sub.1-C.sub.20 alkyl,
C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24
aralkyl, etc.), nitro (--NO.sub.2), nitroso (--NO), sulfo
(--SO.sub.2--OH), sulfonato (--SO.sub.2--O.sup.-), C.sub.1-C.sub.24
alkylsulfanyl (--S-alkyl; also termed "alkylthio"),
C.sub.5-C.sub.24 arylsulfanyl (--S-aryl; also termed "arylthio"),
C.sub.1-C.sub.24 alkylsulfinyl (--(SO)-alkyl), C.sub.5-C.sub.24
arylsulfinyl (--(SO)-aryl), C.sub.1-C.sub.24 alkylsulfonyl
(--SO.sub.2-alkyl), C.sub.1-C.sub.24 monoalkylaminosulfonyl
(--SO.sub.2--N(H)alkyl), C.sub.1-C.sub.24 dialkylaminosulfonyl
(--SO.sub.2--N(alkyl).sub.2), C.sub.5-C.sub.24 arylsulfonyl
(--SO.sub.2-aryl), boryl (--BH.sub.2), borono (--B(OH).sub.2),
boronato (--B(OR).sub.2 where R includes without limitation alkyl
or other hydrocarbyl), phosphono (--P(O)(OH).sub.2), phosphonato
(--P(O)(O.sup.-).sub.2), phosphinato (--P(O)(O.sup.-)), phospho
(--PO.sub.2), and phosphino (--PH.sub.2); and the hydrocarbyl
moieties C.sub.1-C.sub.24 alkyl (preferably C.sub.1-C.sub.12 alkyl,
more preferably C.sub.1-C.sub.6 alkyl), C.sub.2-C.sub.24 alkenyl
(preferably C.sub.2-C.sub.12 alkenyl, more preferably
C.sub.2-C.sub.6 alkenyl), C.sub.2-C.sub.24 alkynyl (preferably
C.sub.2-C.sub.12 alkynyl, more preferably C.sub.2-C.sub.6 alkynyl),
C.sub.5-C.sub.24 aryl (preferably C.sub.5-C.sub.14 aryl),
C.sub.6-C.sub.24 alkaryl (preferably C.sub.6-C.sub.16 alkaryl), and
C.sub.6-C.sub.24 aralkyl (preferably C.sub.6-C.sub.16 aralkyl).
[0194] By "functionalized" as in "functionalized hydrocarbyl,"
"functionalized alkyl," "functionalized olefin," "functionalized
cyclic olefin," and the like, is meant that in the hydrocarbyl,
alkyl, olefin, cyclic olefin, or other moiety, at least one
hydrogen atom bound to a carbon (or other) atom is replaced with
one or more functional groups such as those described hereinabove.
The term "functional group" is meant to include any functional
species that is suitable for the uses described herein. In
particular, as used herein, a functional group would necessarily
possess the ability to react with or bond to corresponding
functional groups on a substrate surface.
[0195] In addition, the aforementioned functional groups may, if a
particular group permits, be further substituted with one or more
additional functional groups or with one or more hydrocarbyl
moieties such as those specifically mentioned above. Analogously,
the above-mentioned hydrocarbyl moieties may be further substituted
with one or more functional groups or additional hydrocarbyl
moieties as noted above.
[0196] "Optional" or "optionally" means that the subsequently
described circumstance may or may not occur, so that the
description includes instances where the circumstance occurs and
instances where it does not. For example, the phrase "optionally
substituted" means that a non-hydrogen substituent may or may not
be present on a given atom, and, thus, the description includes
structures wherein a non-hydrogen substituent is present and
structures wherein a non-hydrogen substituent is not present.
[0197] The term "substrate material" as used herein, is intended to
generally mean any material that the resin compositions of the
invention may be contacted with, applied to, or have the substrate
material incorporated in to the resin. Without limitation, such
materials include reinforcing materials, such as filaments, fibers,
rovings, mats, weaves, fabrics, knitted material, cloth or other
known structures, glass fibers and fabrics, carbon fibers and
fabrics, aramid fibers and fabrics, and polyolefin or other polymer
fibers or fabrics. Other suitable substrate materials include
metallic density modulators, microparticulate density modulators,
such as microspheres, glass microspheres, ceramic microspheres,
microballons, cenospheres, and macroparticulate density modulators,
such as glass or ceramic beads. A ROMP polymer composite may be
comprised of one substrate material or a mixture of different
substrate materials.
[0198] The term "polymer backbone" is intended to mean the chains
of atoms in a polymer that comprise the main chain and any
crosslinks, if it is a crosslinked polymer.
[0199] The term "field joint" as used herein, is intended to
generally mean a connection between adjoining members or parts,
made at the time of installation (i.e. in the field). The term
"field joint" is a term of art often used to describe the welded
ends of individual lengths of pipe. For example, pipelines used to
transport oil and/or gas is most often formed from many individual
pieces of pipe, for example steel pipe. During the manufacturing of
individual pieces of pipe, an anti-corrosion coating is often
applied to the exterior surface of the pipe in such a manner that
the exterior surface of the pipe ends remains uncoated.
Furthermore, the pipe may be subsequently coated with an insulation
material; however, the exterior surface of the pipe ends still
remains uncoated. The pipeline is formed by connecting the
individual pieces of pipe by welding together the uncoated pipe
ends. At least part of this welding process may take place at an
onshore facility prior to loading the pipe on a lay barge or reel
ship, with the remainder of the connections made offshore prior to
the pipeline being deployed in offshore use. In the alternative,
during the manufacturing of individual pieces of pipe, an
anti-corrosion coating may be applied to the exterior surface of
the pipe in such a manner that the exterior surface of the pipe
ends are also coated. In this instance, the anti-corrosion coating
must be removed from the pipe ends prior to welding.
[0200] As used herein, the term "octyl norbornene" and/or the
abbreviation "ONB" refers to 5-octyl-2-norbornene including
endo/exo stereoisomers, and mixtures thereof. As used herein, the
term "tolyl norbornene" and/or the abbreviation "Tolyl-NB" refers
to 5-tolyl-2-norbornene including endo/exo stereoisomers, as well
as para, ortho, and/or meta structural isomers, and mixtures
thereof. As used herein, the term "decyl norbornene" and/or the
abbreviation "DNB" refers to 5-decyl-2-norbornene including
endo/exo stereoisomers, and mixtures thereof. As used herein, the
term "hexyl norbornene" and/or the abbreviation "HNB" refers to
5-hexyl-2-norbornene including endo/exo stereoisomers, and mixtures
thereof. As used herein, the term "phenyl norbornene" and/or the
abbreviation "Phenyl-NB" refers to 5-phenyl-2-norbornene including
endo/exo stereoisomers, and mixtures thereof.
[0201] As is known in the art, weight percent (wt %) can be
represented by gas chromatography (GC) percent area (area %).
Hence, GC area % obtained from the GC was reported as wt %. Weight
percent (wt %) and percent by weight are used interchangeably
herein. Mol percent (mol %) was calculated from the weight percent
(wt %) as is known in the art.
Thermal Insulation
[0202] The present invention is directed to addressing one or more
of the aforementioned concerns and relates to thermal insulation
materials and thermal insulation material compositions and methods
for thermally insulating pipelines and associated equipment,
structures, and objects used in offshore drilling. The present
invention is also relates to articles of manufacture comprising the
thermal insulation materials and/or thermal insulation material
compositions of the invention.
[0203] It was unexpected that thermal insulation materials and/or
thermal insulation material compositions and/or ROMP polymer and/or
ROMP polymer compositions of the present invention would possess
all of the desired characteristics and/or properties specified
above for thermal insulation materials, in particular thermal
insulation materials used in offshore drilling (e.g. subsea
applications). As such, the thermal insulation materials and/or
thermal insulation material compositions and/or ROMP polymer and/or
ROMP polymer compositions of the present invention disclosed herein
satisfy this need in the industry. where the ROMP polymer or ROMP
polymer composite are a reaction product of a resin composition
comprising a cyclic olefin composition and a catalyst composition
comprising at least one metal carbene olefin metathesis catalyst,
wherein the cyclic olefin composition comprises 10.0 mol % to 80.0
mol % of at least one cyclic olefin containing multiunsaturation,
and up to 90.0 mol % of at least one cyclic olefin containing
monounsaturation.
[0204] ROMP polymers and/or ROMP polymer composites where the ROMP
polymer or ROMP polymer composite are a reaction product of a resin
composition comprising a cyclic olefin composition and a catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst, wherein the cyclic olefin composition comprises 10.0 mol
% to 80.0 mol % of at least one cyclic olefin containing
multiunsaturation, and up to 90.0 mol % of at least one cyclic
olefin containing monounsaturation offer improved thermal stability
and/or improved hydrolytic stability over prior art thermal
insulation materials. In particular, thermal insulation materials
made from ROMP polymers where the ROMP polymer or is a reaction
product of a resin composition comprising a cyclic olefin
composition and a catalyst composition comprising at least one
metal carbene olefin metathesis catalyst, wherein the cyclic olefin
composition comprises 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation. offer an
advantage over prior art thermal insulation materials made from
polypropylene in such ROMP polymers possess improved thermal
stability.
[0205] Moreover, thermal insulation materials made from ROMP
polymers where the ROMP polymer is a reaction product of a resin
composition comprising a cyclic olefin composition and a catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst, wherein the cyclic olefin composition comprises 10.0 mol
% to 80.0 mol % of at least one cyclic olefin containing
multiunsaturation, and up to 90.0 mol % of at least one cyclic
olefin containing monounsaturation offer an advantage over prior
art thermal insulation materials made from polyurethane and epoxy
based materials, including elastomeric amine cured epoxy materials,
in that cyclic olefins (cyclic olefin monomers) used to make such
ROMP polymers may be selected so that the resultant ROMP polymers
do not contain carbon-heteroatom bonds in the polymer backbone.
Therefore, ROMP polymers where the ROMP polymer is a reaction
product of a resin composition comprising a cyclic olefin
composition and a catalyst composition comprising at least one
metal carbene olefin metathesis catalyst, wherein the cyclic olefin
composition comprises 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation are
generally more hydrolytically stable than polyurethanes and/or
epoxy based polymers, each of which possess carbon-heteroatom bonds
in the polymer backbone. Preferentially, ROMP polymers where the
ROMP polymer is a reaction product of a resin composition
comprising a cyclic olefin composition and a catalyst composition
comprising at least one metal carbene olefin metathesis catalyst,
wherein the cyclic olefin composition comprises 10.0 mol % to 80.0
mol % of at least one cyclic olefin containing multiunsaturation,
and up to 90.0 mol % of at least one cyclic olefin containing
monounsaturation, possess a polymer backbone containing only
carbon-carbon single bonds and carbon-carbon double bonds, where
the carbon atoms may be substituted or unsubstituted.
[0206] Moreover, ROMP compositions of the invention used to prepare
ROMP polymers and/or ROMP polymer composites, where the ROMP
polymers and/or ROMP polymer composites are a reaction product of a
ROMP composition, the ROMP composition comprising a resin
composition comprising a cyclic olefin composition and a catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst, wherein the cyclic olefin composition comprises 10.0 mol
% to 80.0 mol % of at least one cyclic olefin containing
multiunsaturation, and up to 90.0 mol % of at least one cyclic
olefin containing monounsaturation, are generally less sensitive to
air and/or moisture than resins used to prepare polyurethane and
epoxy based polymers and DCPD polymers prepared from molybendum and
tungsten catalyzed DCPD resins (e.g., Telene.RTM. DCPD Resin,
Metton.RTM. DCPD Resin, Pentam.RTM. DCPD Resin). Therefore ROMP
compositions comprising resin compositions comprising cyclic olefin
compositions, wherein the cyclic olefin composition comprises 10.0
mol % to 80.0 mol % of at least one cyclic olefin containing
multiunsaturation, and up to 90.0 mol % of at least one cyclic
olefin containing monounsaturation, and catalyst compositions
comprising at least one metal carbene olefin metathesis catalyst
are generally more robust to a wider array of environmental
conditions (e.g., temperature, humidity, etc.) Resin systems that
are less sensitive to air and/or moisture offer a benefit over more
sensitive resin systems, particularly if objects are to be coated
(thermally insulated) at on-site marine environments, such as on
boats, offshore oil rigs, offshore oil platforms, etc.
[0207] Furthermore, ROMP polymers of the invention, where the ROMP
polymer is a reaction product of a resin composition comprising a
cyclic olefin composition and a catalyst composition comprising at
least one metal carbene olefin metathesis catalyst, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation may be optionally hydrogenated by any known
method, to provide a hydrogenated ROMP polymer for use as thermal
insulation.
[0208] Furthermore, ROMP compositions of the invention, the ROMP
composition comprising a resin composition comprising a cyclic
olefin composition and a catalyst composition comprising at least
one metal carbene olefin metathesis catalyst, wherein the cyclic
olefin composition comprises 10.0 mol % to 80.0 mol % of at least
one cyclic olefin containing multiunsaturation, and up to 90.0 mol
% of at least one cyclic olefin containing monounsaturation, offer
improved ease of application over prior art resin compositions,
particularly polypropylene systems. Unlike polypropylene systems,
which are primarily limited to extrusion, ROMP compositions of the
invention, the ROMP composition comprising a resin composition
comprising a cyclic olefin composition and a catalyst composition
comprising at least one metal carbene olefin metathesis catalyst,
wherein the cyclic olefin composition comprises 10.0 mol % to 80.0
mol % of at least one cyclic olefin containing multiunsaturation,
and up to 90.0 mol % of at least one cyclic olefin containing
monounsaturation, can be applied to an object and/or object surface
by a variety of means including but not limited to pouring,
casting, infusing, injecting, molding, spraying, rotationally
molding, centrifugally casting, pultrusion, extrusion, etc.
Moreover, ROMP compositions of the invention, the ROMP composition
comprising a resin composition comprising a cyclic olefin
composition and a catalyst composition comprising at least one
metal carbene olefin metathesis catalyst, wherein the cyclic olefin
composition comprises 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation, also offer
improved ease of application over prior art resin compositions
based on epoxy resins (e.g., elastomeric amine cured epoxy
materials). Unlike epoxy based resin systems (e.g., elastomeric
amine cured epoxy materials), which are synthesized in at least two
steps, ROMP compositions of the invention, the ROMP composition
comprising a resin composition comprising a cyclic olefin
composition and a catalyst composition comprising at least one
metal carbene olefin metathesis catalyst, wherein the cyclic olefin
composition comprises 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation, simply
require a single mixing step (e.g. a resin composition comprising a
cyclic olefin composition is mixed with a catalyst composition
comprising at least one metal carbene olefin metathesis catalyst,
wherein the cyclic olefin composition comprises 10.0 mol % to 80.0
mol % of at least one cyclic olefin containing multiunsaturation,
and up to 90.0 mol % of at least one cyclic olefin containing
monounsaturation) prior to application to an object surface or
addition to a mold. Unlike DCPD resin systems containing molybdenum
or tungsten two-component catalyst systems (e.g., Telene.RTM. DCPD
Resin, Metton.RTM. DCPD Resin, Pentam.RTM. DCPD Resin), which
require specialized and expensive processing and handling
conditions and equipment, including specialized and expensive
molds, injection equipment, and storage tanks, cyclic olefin
compositions and/or resin compositions and/or ROMP compositions of
the invention the ROMP composition comprising a resin composition
comprising a cyclic olefin composition and a catalyst composition
comprising at least one metal carbene olefin metathesis catalyst,
wherein the cyclic olefin composition comprises 10.0 mol % to 80.0
mol % of at least one cyclic olefin containing multiunsaturation,
and up to 90.0 mol % of at least one cyclic olefin containing
monounsaturation can be applied to an object and/or object surface
by a variety of means including but not limited to simple
casting.
[0209] Furthermore, ROMP compositions of the invention the ROMP
composition comprising a resin composition comprising a cyclic
olefin composition and a catalyst composition comprising at least
one metal carbene olefin metathesis catalyst, wherein the cyclic
olefin composition comprises 10.0 mol % to 80.0 mol % of at least
one cyclic olefin containing multiunsaturation, and up to 90.0 mol
% of at least one cyclic olefin containing monounsaturation,
possess much lower viscosity over a broader range of temperatures
than epoxy based resin systems. The low viscosity of ROMP
compositions of the invention the ROMP composition comprising a
resin composition comprising a cyclic olefin composition and a
catalyst composition comprising at least one metal carbene olefin
metathesis catalyst, wherein the cyclic olefin composition
comprises 10.0 mol % to 80.0 mol % of at least one cyclic olefin
containing multiunsaturation, and up to 90.0 mol % of at least one
cyclic olefin containing monounsaturation, is particularly
advantageous as it promotes flow especially when filling complex
molds. Moreover, the low viscosity of cyclic olefin resin
compositions also allows for high loading of substrate materials
(e.g. glass or ceramic microspheres) which may enhance the
insulating capabilities of the resulting ROMP polymer. Suitable
resin compositions for use with this invention having a viscosity
at 25.degree. C. ranging from about 1 centipoise to about 200
centipoise (1 cP-200 cP). Viscosities typically range from 1-150
cP, 1-100 cP, 5-100 cP, 5-150 cP, 5-25 cP, 5-50 cP, 5-15 cP, 5-20
cP at 25.degree. C. At other temperatures -20.degree. C.,
-10.degree. C., 0.degree. C., 5.degree. C., 15.degree. C.,
25.degree. C., 30.degree. C., 40.degree. C., 50.degree. C.,
60.degree. C. viscosities may range from 1-150 cP, 1-100 cP, 5- 100
cP, 5-150 cP, 5-25 cP, 5-50 cP, 5-15 cP, 5-20 cP.
[0210] A particular benefit of the ROMP compositions of the
invention, the ROMP composition comprising a resin composition
comprising a cyclic olefin composition and a catalyst composition
comprising at least one metal carbene olefin metathesis catalyst,
wherein the cyclic olefin composition comprises 10.0 mol % to 80.0
mol % of at least one cyclic olefin containing multiunsaturation,
and up to 90.0 mol % of at least one cyclic olefin containing
monounsaturation, is that these compositions are easy to handle and
can be easily formulated such that the resultant ROMP polymer(s)
meet the needs/requirements of the application or service. For
example, ROMP compositions the ROMP composition comprising a resin
composition comprising a cyclic olefin composition and a catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst, wherein the cyclic olefin composition comprises 10.0 mol
% to 80.0 mol % of at least one cyclic olefin containing
multiunsaturation, and up to 90.0 mol % of at least one cyclic
olefin containing monounsaturation, used to prepare ROMP polymers
of the invention can be easily formulated such that the resultant
ROMP polymer(s) may exhibit a range of physical, mechanical and/or
thermal properties spanning the range from elastomeric behavior
and/or properties to rigid thermoset behavior and/or properties
depending on the needs/requirements of the application.
[0211] ROMP polymers and/or ROMP polymer composites of the present
invention where the ROMP polymer and/or ROMP polymer composite is a
reaction product of a resin composition comprising a cyclic olefin
composition and a catalyst composition comprising at least one
metal carbene olefin metathesis catalyst, wherein the cyclic olefin
composition comprises 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation can be used
to thermally insulate any object from a surrounding environment or
surrounding material, where the surrounding environment or
surrounding material may be a gas (e.g. air), a fluid (liquid)
(e.g., sea water, fresh water), or a solid (e.g. ice or
subterranean solids as in the case of a buried pipeline), or a
mixture thereof. In particular, ROMP polymers and/or ROMP polymer
composites of the present invention where the ROMP polymer and/or
ROMP polymer composite is a reaction product of a resin composition
comprising a cyclic olefin composition and a catalyst composition
comprising at least one metal carbene olefin metathesis catalyst,
wherein the cyclic olefin composition comprises 10.0 mol % to 80.0
mol % of at least one cyclic olefin containing multiunsaturation,
and up to 90.0 mol % of at least one cyclic olefin containing
monounsaturation are suitable for thermal insulation of objects,
such as oil pipelines in cold water (e.g. cold sea water, cold
fresh water) and for insulating wellhead equipment. The ROMP
polymers and/or ROMP polymer composites of the present invention
where the ROMP polymer and/or ROMP polymer composite is a reaction
product of a resin composition comprising a cyclic olefin
composition and a catalyst composition comprising at least one
metal carbene olefin metathesis catalyst, wherein the cyclic olefin
composition comprises 10.0 mol % to 80.0 mol % of at least one
cyclic olefin containing multiunsaturation, and up to 90.0 mol % of
at least one cyclic olefin containing monounsaturation, may also be
used for insulating other objects including but not limited to
pipes, pipelines, pipe fittings, hose, hose fitting, tanks,
containers, drums, manifolds, risers, field joints, configurations
designated as Christmas trees (oil field Christmas tree, subsea
Christmas tree), jumpers, spool pieces, configurations designated
as pipeline end termination (PLET), configurations designated as
pipeline end manifolds (PLEM), and other sub-sea architectures and
equipment. The ROMP polymers and/or ROMP polymer composites of the
present invention where the ROMP polymers and/or ROMP polymer
composites are a reaction product of a resin composition comprising
a cyclic olefin composition and a catalyst composition comprising
at least one metal carbene olefin metathesis catalyst, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation may also be used to coat other objects such as
robotic parts, devices and vehicles used in sub-sea applications.
Moreover, ROMP polymers and/or ROMP polymer composites of the
present invention where the ROMP polymers and/or ROMP polymer
composites are a reaction product of a resin composition comprising
a cyclic olefin composition and a catalyst composition comprising
at least one metal carbene olefin metathesis catalyst, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation may be used to construct thermal insulation
structures such as configurations designated as subsea dog
houses.
[0212] While ROMP polymers and/or ROMP polymer composites of the
invention where the ROMP polymers and/or ROMP polymer composites
are a reaction product of a resin composition comprising a cyclic
olefin composition and a catalyst composition comprising at least
one metal carbene olefin metathesis catalyst, wherein the cyclic
olefin composition comprises 10.0 mol % to 80.0 mol % of at least
one cyclic olefin containing multiunsaturation, and up to 90.0 mol
% of at least one cyclic olefin containing monounsaturation are
well suited for coating objects which are to be submerged in water
(e.g. fresh water, salt water, sea water, etc.) the ROMP polymers
and/or ROMP polymer composites may also be used to coat objects
which are not exposed to an aqueous environment.
[0213] ROMP polymers and/or ROMP polymer composites of the present
invention where the ROMP polymers and/or ROMP polymer composites
are a reaction product of a resin composition comprising a cyclic
olefin composition and a catalyst composition comprising at least
one metal carbene olefin metathesis catalyst, wherein the cyclic
olefin composition comprises 10.0 mol % to 80.0 mol % of at least
one cyclic olefin containing multiunsaturation, and up to 90.0 mol
% of at least one cyclic olefin containing monounsaturation may be
used for coating (insulating) objects (e.g., pipes and/or other
subsea structures) where the temperature of materials (e.g.,
hydrocarbons, oil, gas, etc.) transported by the objects (e.g.,
pipes and/or other structures) is greater than or equal to
160.degree. C. Therefore, by default, ROMP polymers and/or ROMP
polymer composites of the present invention where the ROMP polymers
and/or ROMP polymer composites are a reaction product of a resin
composition comprising a cyclic olefin composition and a catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst, wherein the cyclic olefin composition comprises 10.0 mol
% to 80.0 mol % of at least one cyclic olefin containing
multiunsaturation, and up to 90.0 mol % of at least one cyclic
olefin containing monounsaturation of the present invention may
also be used for coating (insulating) objects (e.g., pipes and/or
other subsea structures) where the temperature of materials (e.g.,
hydrocarbons, oil, gas, etc.) transported by the objects (e.g.,
pipes and/or other subsea structures) is less than 160.degree.
C.
[0214] ROMP polymers and/or ROMP polymer composites of the present
invention where the ROMP polymers and/or ROMP polymer composites
are a reaction product of a resin composition comprising a cyclic
olefin composition and a catalyst composition comprising at least
one metal carbene olefin metathesis catalyst, wherein the cyclic
olefin composition comprises 10.0 mol % to 80.0 mol % of at least
one cyclic olefin containing multiunsaturation, and up to 90.0 mol
% of at least one cyclic olefin containing monounsaturation of the
present invention have thermal conductivity values of less than
0.180 W/m*K, as determined by ASTM C518, as tested on heat flow
instrument (FOX-50, LaserComp). ROMP polymers and/or ROMP polymer
composites of the present invention where the ROMP polymers and/or
ROMP polymer composites are a reaction product of a resin
composition comprising a cyclic olefin composition and a catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst, wherein the cyclic olefin composition comprises 10.0 mol
% to 80.0 mol % of at least one cyclic olefin containing
multiunsaturation, and up to 90.0 mol % of at least one cyclic
olefin containing monounsaturation of the present invention may be
further reduced by the addition of glass microspheres. These and
other aspects and benefits of the invention will be apparent to the
skilled artesian in light of the following detailed description and
examples herein.
Adhesion Promoters
[0215] Adhesion promoters that may be used in the present invention
disclosed herein are generally compounds containing at least two
isocyanate groups (such as, for example, methylene diphenyl
diisocyanate and hexamethylene diisocyanate). The adhesion promoter
may be a diisocyanate, triisocyanate, or polyisocyanate (i.e.,
containing four or more isocyanate groups). The adhesion promoter
may be a mixture of at least one diisocyanate, triisocyanate, or
polyisocyanate. In a more particular aspect of the invention, the
adhesion promoter comprises, or is limited to, a diisocyanate
compound, or mixtures of diisocyanate compounds.
[0216] In general, adhesion promoters that may be used in the
present invention may be any compound having at least two
isocyanate groups. Suitable adhesion promoters include, without
limitation, isocyanate compounds comprising at least two isocyanate
groups, and wherein the compounds are selected from hydrocarbyl,
substituted hydrocarbyl, heteroatom-containing hydrocarbyl,
substituted heteroatom-containing hydrocarbyl, and functionalized
hydrocarbyl compounds. As described above, suitable hydrocarbyl
adhesion promoter compounds generally include alkyl, cycloalkyl,
alkylene, alkenyl, alkynyl, aryl, cycloalkyl, alkaryl, and aralkyl
compounds. Substituted heteroatom-containing, and functionalized
hydrocarbyl adhesion promoter compounds include the afore-mentioned
hydrocarbyl compounds, as well as the variations thereof noted
hereinabove.
[0217] Adhesion promoters that may be used in the present invention
may be an alkyl diisocyanate. An alkyl diisocyanate refers to a
linear, branched, or cyclic saturated or unsaturated hydrocarbon
group typically although not necessarily containing 1 to about 24
carbon atoms, preferably a diisocyanate containing 2 to about 12
carbon atoms, and more preferably a diisocyanate containing 6 to 12
carbon atoms such as hexamethylene diisocyanate (HDI),
octamethylene diisocyanate, decamethylene diisocyanate, and the
like. Cycloalkyl diisocyanates contain cyclic alkyl group,
typically having 4 to 16 carbon atoms. A preferred cycloalkyl
diisocyanate containing 6 to about 12 carbon atoms are cyclohexyl,
cyclooctyl, cyclodecyl, and the like. A more preferred cycloalkyl
diisocyanate originates as a condensation product of acetone called
5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethyl-cyclohexane,
commonly known as Isophorone diisocyanate (IPDI) and the isomers of
isocyanato-[(isocyanatocyclohexyl)methyl]cyclohexane (H.sub.12MDI).
H.sub.12MDI is derived from the hydrogenated form of the aryl
diisocyanate methylene diphenyl diisocyanate (MDI).
[0218] Adhesion promoters that may be used in the present invention
may be an aryl diisocyanate. Aryl diisocyanates refers to aromatic
diisocyanates containing a single aromatic ring or multiple
aromatic rings that are fused together, directly linked, or
indirectly linked (such that the different aromatic rings are bound
to a common group such as a methylene or ethylene moiety).
Preferred aryl diisocyanates contain 5 to 24 carbon atoms, and
particularly preferred aryl diisocyanates contain 5 to 14 carbon
atoms. Exemplary aryl diisocyanates contain one aromatic ring or
two fused or linked aromatic rings, e.g., phenyl, tolyl, xylyl,
naphthyl, biphenyl, diphenylether, benzophenone, and the like.
Preferred aromatic diisocyanates include toluene diisocyanates,
tetramethylxylene diisocyanate (TMXDI), and methylene diphenyl
diisocyanate (MDI), which may comprise any mixture of its three
isomers, 2.2'-MDI, 2,4'-MDI, and 4,4'-MDI.
[0219] Adhesion promoters that may be used in the present invention
may be a polymer-containing isocyanate, such as, for example,
diisocyanates. Polymer-containing isocyanates refers to a
polymer-containing two or more terminal and/or pendant alkyl or
aryl isocyanate groups. The polymer-containing isocyanates
generally have to have a minimal solubility in the resin to provide
improved mechanical properties. Preferred polymer-containing
isocyanates include, but are not limited to, PM200 (poly MDI),
Lupranate.RTM. (poly MDI from BASF), Krasol.RTM. isocyanate
terminated polybutadiene prepolymers, such as, for example,
Krasol.RTM. LBD2000 (TDI based), Krasol.RTM. LBD3000 (TDI based),
Krasol.RTM. NN-22 (MDI based), Krasol.RTM. NN-23 (MDI based),
Krasol.RTM. NN-25 (MDI based), and the like. Krasol.RTM. isocyanate
terminated polybutadiene prepolymers are available from Cray
Valley.
[0220] Adhesion promoters that may be used in the present invention
may be a trimer of alkyl diisocyanates and aryl diisocyanates. In
its simplest form, any combination of polyisocyanate compounds may
be trimerized to form an isocyanurate ring containing isocyanate
functional groups. Trimers of alkyl diisocyanate and aryl
diisocyanates may also be referred to as isocyanurates of alkyl
diisocyanate or aryl diisocyanate. Preferred alkyl diisocyanate and
aryl diisocyanate trimers include, but are not limited to,
hexamethylene diisocyanate trimer (HDIt), isophorone diisocyanate
trimer, toluene diisocyanate trimer, tetramethylxylene diisocyanate
trimer, methylene diphenyl diisocyanate trimers, and the like. More
preferred adhesion promoters are toluene diisocyanates,
tetramethylxylene diisocyanate (TMXDI), and methylene diphenyl
diisocyanate (MDI) including any mixture of its three isomers
2.2'-MDI, 2,4'-MDI and 4,4'-MDI; liquid MDI; solid MDI;
hexamethylenediisocyanatetrimer (HDIt); hexamethylenediisocyanate
(HDI); isophorone diisocyanate (IPDI); 4,4'-methylene
bis(cyclohexyl isocyanate) (H12MDI); polymeric MDI (PM200); MDI
prepolymer (Lupranate.RTM. 5080); liquid carbodiimide modified
4,4'-MDI (Lupranate.RTM. MM103); liquid MDI (Lupranate.RTM. MI);
liquid MDI (Mondur.RTM. ML); and liquid MDI (Mondur.RTM. MLQ). Even
more preferred adhesion promoters are methylene diphenyl
diisocyanate (MDI) including any mixture of its three isomers
2,2'-MDI, 2,4'-MDI and 4,4'-MDI; liquid MDI; solid MDI;
hexamethylenediisocyanatetrimer (HDIt); hexamethylene diisocyanate
(HDI); isophorone diisocyanate (IPDI); 4,4'-methylene
bis(cyclohexyl isocyanate) (H12MDI); polymeric MDI (PM200); MDI
prepolymer (Lupranate.RTM. 5080); liquid carbodiimide modified
4,4'-MDI (Lupranate.RTM. MM103); liquid MDI) (Lupranate.RTM. MI);
liquid MDI (Mondur.RTM. ML); liquid MDI (Mondur.RTM. MLQ).
[0221] Any concentration of adhesion promoter which improves the
mechanical properties of the olefin composite (e.g. ROMP polymer
composite) is sufficient for the invention. In general, suitable
amounts of adhesion promoter range from 0.001-50 phr, particularly
0.05-10 phr, more particularly 0.1-10 phr, or even more
particularly 0.5-4.0 phr. One or more adhesion promoters may be
used in the present invention.
[0222] Additional adhesion promoters suitable for use in the
present invention comprise functionalized silanes of the formula
Fn-(A).sub.n-Si(Y*).sub.3, wherein Y* is selected from halide
(preferably chloride) or OR; Fn is a functional group selected from
acrylate, methacrylate, allyl, vinyl, alkene, cycloalkene, or
norbornene; A is a divalent linking group selected from
hydrocarbylene, substituted hydrocarbylene, heteroatom-containing
hydrocarbylene, or substituted heteroatom-containing
hydrocarbylene; n is 0 or 1; and R is selected from hydrocarbyl,
substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or
substituted heteroatom-containing hydrocarbyl, preferably lower
alkyl, more preferably methyl, ethyl, or isopropyl; and a peroxide
selected from dialkyl and diaryl peroxides. Additional adhesion
promoters for use in the present invention and methods for their
use include those disclosed in International Pat. App. No.
PCT/US00/03002, the contents of which are incorporated herein by
reference.
Cyclic Olefins
[0223] Resin compositions and/or cyclic olefin compositions that
may be used with the present invention disclosed herein comprise
one or more cyclic olefins. In general, any cyclic olefin suitable
for the metathesis reactions disclosed herein may be used. Such
cyclic olefins may be optionally substituted, optionally
heteroatom-containing, mono-unsaturated, di-unsaturated, or
poly-unsaturated C.sub.5 to C.sub.24 hydrocarbons that may be
mono-, di-, or poly-cyclic. The cyclic olefin may generally be any
strained or unstrained cyclic olefin, provided the cyclic olefin is
able to participate in a ROMP reaction either individually or as
part of a ROMP cyclic olefin composition or as part of a resin
composition. While certain unstrained cyclic olefins such as
cyclohexene are generally understood to not undergo ROMP reactions
by themselves, under appropriate circumstances, such unstrained
cyclic olefins may nonetheless be ROMP active. For example, when
present as a co-monomer in a ROMP composition, unstrained cyclic
olefins may be ROMP active. Accordingly, as used herein and as
would be appreciated by the skilled artisan, the term "unstrained
cyclic olefin" is intended to refer to those unstrained cyclic
olefins that may undergo a ROMP reaction under any conditions, or
in any ROMP composition, provided the unstrained cyclic olefin is
ROMP active.
[0224] In general, the cyclic olefin may be represented by the
structure of formula (A)
##STR00001##
wherein J, R.sup.A1, and R.sup.A2 are as follows:
[0225] R.sup.A1 and R.sup.A2 is selected independently from the
group consisting of hydrogen, hydrocarbyl (e.g., C.sub.1-C.sub.20
alkyl, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.30 aralkyl, or
C.sub.5-C.sub.30 alkaryl), substituted hydrocarbyl (e.g.,
substituted C.sub.1-C.sub.20 alkyl, C.sub.5-C.sub.20 aryl,
C.sub.5-C.sub.30 aralkyl, or C.sub.5-C.sub.30 alkaryl),
heteroatom-containing hydrocarbyl (e.g., C.sub.1-C.sub.20
heteroalkyl, C.sub.5-C.sub.20 heteroaryl, heteroatom-containing
C.sub.5-C.sub.30 aralkyl, or heteroatom-containing C.sub.5-C.sub.30
alkaryl), and substituted heteroatom-containing hydrocarbyl (e.g.,
substituted C.sub.1-C.sub.20 heteroalkyl, C.sub.5-C.sub.20
heteroaryl, heteroatom-containing C.sub.5-C.sub.30 aralkyl, or
heteroatom-containing C.sub.5-C.sub.30 alkaryl) and, if substituted
hydrocarbyl or substituted heteroatom-containing hydrocarbyl,
wherein the substituents may be functional groups ("Fn") such as
phosphonato, phosphoryl, phosphanyl, phosphino, sulfonato,
C.sub.1-C.sub.20 alkylsulfanyl, C.sub.5-C.sub.20 arylsulfanyl,
C.sub.1-C.sub.20 alkylsulfonyl, C.sub.5-C.sub.20 arylsulfonyl,
C.sub.1-C.sub.20 alkylsulfinyl, C.sub.5-C.sub.20 arylsulfinyl,
sulfonamido, amino, amido, imino, nitro, nitroso, hydroxyl,
C.sub.1-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryloxy, C.sub.2-C.sub.20
alkoxycarbonyl, C.sub.5-C.sub.20 aryloxycarbonyl, carboxyl,
carboxylato, mercapto, formyl, C.sub.1-C.sub.20 thioester, cyano,
cyanato, thiocyanato, isocyanate, thioisocyanate, carbamoyl, epoxy,
styrenyl, silyl, silyloxy, silanyl, siloxazanyl, boronato, boryl,
or halogen, or a metal-containing or metalloid-containing group
(wherein the metal may be, for example, Sn or Ge). R.sup.A1 and
R.sup.A2 may itself be one of the aforementioned groups, such that
the Fn moiety is directly bound to the olefinic carbon atom
indicated in the structure. In the latter case, however, the
functional group will generally not be directly bound to the
olefinic carbon through a heteroatom containing one or more lone
pairs of electrons, e.g., an oxygen, sulfur, nitrogen, or
phosphorus atom, or through an electron-rich metal or metalloid
such as Ge, Sn, As, Sb, Se, Te, etc. With such functional groups,
there will normally be an intervening linkage Z*, such that
R.sup.A1 and/or R.sup.A2 then has the structure --(Z*).sub.n-Fn
wherein n is 1, Fn is the functional group, and Z* is a
hydrocarbylene linking group such as an alkylene, substituted
alkylene, heteroalkylene, substituted heteroalkene, arylene,
substituted arylene, heteroarylene, or substituted heteroarylene
linkage.
[0226] J is a saturated or unsaturated hydrocarbylene, substituted
hydrocarbylene, heteroatom-containing hydrocarbylene, or
substituted heteroatom-containing hydrocarbylene linkage, wherein
when J is substituted hydrocarbylene or substituted
heteroatom-containing hydrocarbylene, the substituents may include
one or more --(Z*).sub.n-Fn groups, wherein n is zero or 1, and Fn
and Z* are as defined previously. Additionally, two or more
substituents attached to ring carbon (or other) atoms within J may
be linked to form a bicyclic or polycyclic olefin. J will generally
contain in the range of approximately 5 to 14 ring atoms, typically
5 to 8 ring atoms, for a monocyclic olefin, and, for bicyclic and
polycyclic olefins, each ring will generally contain 4 to 8,
typically 5 to 7, ring atoms.
[0227] Mono-unsaturated cyclic olefins encompassed by structure (A)
may be represented by the structure (B)
##STR00002##
wherein b is an integer generally although not necessarily in the
range of 1 to 10, typically 1 to 5, R.sup.A1 and R.sup.A2 are as
defined above for structure (A), and R.sup.B1, R.sup.B2, R.sup.B3,
R.sup.B4, R.sup.B5, and R.sup.B6 are independently selected from
the group consisting of hydrogen, hydrocarbyl, substituted
hydrocarbyl, heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl and --(Z*).sub.n-Fn where n, Z*
and Fn are as defined previously, and wherein if any of the
R.sup.B1 through R.sup.B6 moieties is substituted hydrocarbyl or
substituted heteroatom-containing hydrocarbyl, the substituents may
include one or more --(Z*).sub.n-Fn groups. Accordingly, R.sup.B1,
R.sup.B2, R.sup.B3, R.sup.B4, R.sup.B5, and R.sup.B6 may be, for
example, hydrogen, hydroxyl, C.sub.1-C.sub.20 alkyl,
C.sub.5-C.sub.20 aryl, C.sub.1-C.sub.20 alkoxy, C.sub.5-C.sub.20
aryloxy, C.sub.2-C.sub.20 alkoxycarbonyl, C.sub.5-C.sub.20
aryloxycarbonyl, amino, amido, nitro, etc.
[0228] Furthermore, any of the R.sup.B1, R.sup.B2, R.sup.B3,
R.sup.B4, R.sup.B5, and R.sup.B6 moieties can be linked to any of
the other R.sup.B1, R.sup.B2, R.sup.B3, R.sup.B4, R.sup.B5, and
R.sup.B6 moieties to provide a substituted or unsubstituted
alicyclic group containing 4 to 30 ring carbon atoms or a
substituted or unsubstituted aryl group containing 6 to 18 ring
carbon atoms or combinations thereof and the linkage may include
heteroatoms or functional groups, e.g., the linkage may include
without limitation an ether, ester, thioether, amino, alkylamino,
imino, or anhydride moiety. The alicyclic group can be monocyclic,
bicyclic, or polycyclic. When unsaturated the cyclic group can
contain monounsaturation or multiunsaturation, with monounsaturated
cyclic groups being preferred. When substituted, the rings contain
monosubstitution or multisubstitution wherein the substituents are
independently selected from hydrogen, hydrocarbyl, substituted
hydrocarbyl, heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, --(Z*).sub.n-Fn where n is zero
or 1, Z* and Fn are as defined previously, and functional groups
(Fn) provided above.
[0229] Examples of monounsaturated, monocyclic olefins encompassed
by structure (B) include, without limitation, cyclopentene,
cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene,
cycloundecene, cyclododecene, tricyclodecene, tetracyclodecene,
octacyclodecene, and cycloeicosene, and substituted versions
thereof such as 1-methylcyclopentene, 1-ethylcyclopentene,
1-isopropylcyclohexene, l-chloropentene, 1-fluorocyclopentene,
4-methylcyclopentene, 4-methoxy-cyclopentene,
4-ethoxy-cyclopentene, cyclopent-3-ene-thiol, cyclopent-3-ene,
4-methylsulfanyl-cyclopentene, 3-methylcyclohexene,
1-methylcyclooctene, 1,5-dimethylcyclooctene, etc.
[0230] Monocyclic diene reactants encompassed by structure (A) may
be generally represented by the structure (C)
##STR00003##
wherein c and d are independently integers in the range of 1 to
about 8, typically 2 to 4, preferably 2 (such that the reactant is
a cyclooctadiene), R.sup.A1 and R.sup.A2 are as defined above for
structure (A), and R.sup.C1, R.sup.C2, R.sup.C3, R.sup.C4,
R.sup.C5, and R.sup.C6 are defined as for R.sup.B1 through
R.sup.B6. In this case, it is preferred that R.sup.C3 and R.sup.C4
be non-hydrogen substituents, in which case the second olefinic
moiety is tetrasubstituted. Examples of monocyclic diene reactants
include, without limitation, 1,3-cyclopentadiene,
1,3-cyclohexadiene, 1,4-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene,
1,3-cycloheptadiene, cyclohexadiene, 1,5-cyclooctadiene,
1,3-cyclooctadiene, and substituted analogs thereof. Triene
reactants are analogous to the diene structure (C), and will
generally contain at least one methylene linkage between any two
olefinic segments.
[0231] Bicyclic and polycyclic olefins encompassed by structure (A)
may be generally represented by the structure (D)
##STR00004##
wherein R.sup.A1 and R.sup.A2 are as defined above for structure
(A), R.sup.D1, R.sup.D2, R.sup.D3, and R.sup.D4 are as defined for
R.sup.B1 through R.sup.B6, e is an integer in the range of 1 to 8
(typically 2 to 4) f is generally 1 or 2; T is lower alkylene or
alkenylene (generally substituted or unsubstituted methyl or
ethyl), CHR.sup.G1, C(R.sup.G1).sub.2, O, S, N--R.sup.G1,
P--R.sup.G1, O.dbd.P--R.sup.G1, Si(R.sup.G1).sub.2, B--R.sup.G1, or
As--R.sup.G1 where R.sup.G1 is alkyl, alkenyl, cycloalkyl,
cycloalkenyl, aryl, alkaryl, aralkyl, or alkoxy. Furthermore, any
of the R.sup.D1, R.sup.D2, R.sup.D3, and R.sup.D4 moieties can be
linked to any of the other R.sup.D1, R.sup.D2, R.sup.D3, and
R.sup.D4 moieties to provide a substituted or unsubstituted
alicyclic group containing 4 to 30 ring carbon atoms or a
substituted or unsubstituted aryl group containing 6 to 18 ring
carbon atoms or combinations thereof and the linkage may include
heteroatoms or functional groups, e.g., the linkage may include
without limitation an ether, ester, thioether, amino, alkylamino,
imino, or anhydride moiety. The cyclic group can be monocyclic,
bicyclic, or polycyclic. When unsaturated the cyclic group can
contain monounsaturation or multiunsaturation, with monounsaturated
cyclic groups being preferred. When substituted, the rings contain
monosubstitution or multisubstitution wherein the substituents are
independently selected from hydrogen, hydrocarbyl, substituted
hydrocarbyl, heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, --(Z*).sub.n-Fn where n is zero
or 1, Z* and Fn are as defined previously, and functional groups
(Fn) provided above.
[0232] Cyclic olefins encompassed by structure (D) are in the
norbornene family. As used herein, norbornene means any compound
that includes at least one norbornene or substituted norbornene
moiety, including without limitation norbornene, substituted
norbornene(s), norbornadiene, substituted norbornadiene(s),
polycyclic norbornenes, and substituted polycyclic norbornene(s).
Norbornenes within this group may be generally represented by the
structure (E)
##STR00005##
wherein R.sup.A1 and R.sup.A2 are as defined above for structure
(A), T is as defined above for structure (D), R.sup.E1, R.sup.E2,
R.sup.E3, R.sup.E4, R.sup.E5, R.sup.E6, R.sup.E7, and R.sup.E8 are
as defined for R.sup.B1 through R.sup.B6, and "a" represents a
single bond or a double bond, f is generally 1 or 2, "g" is an
integer from 0 to 5, and when "a" is a double bond one of R.sup.E5,
R.sup.E6 and one of R.sup.E7, R.sup.E8 is not present.
[0233] Furthermore, any of the R.sup.E5, R.sup.E6, R.sup.E7, and
R.sup.E8 moieties can be linked to any of the other R.sup.E5,
R.sup.E6, R.sup.E7, and R.sup.E8 moieties to provide a substituted
or unsubstituted alicyclic group containing 4 to 30 ring carbon
atoms or a substituted or unsubstituted aryl group containing 6 to
18 ring carbon atoms or combinations thereof and the linkage may
include heteroatoms or functional groups, e.g., the linkage may
include without limitation an ether, ester, thioether, amino,
alkylamino, imino, or anhydride moiety. The cyclic group can be
monocyclic, bicyclic, or polycyclic. When unsaturated the cyclic
group can contain monounsaturation or multiunsaturation, with
monounsaturated cyclic groups being preferred. When substituted,
the rings contain monosubstitution or multisubstitution wherein the
substituents are independently selected from hydrogen, hydrocarbyl,
substituted hydrocarbyl, heteroatom-containing hydrocarbyl,
substituted heteroatom-containing hydrocarbyl, --(Z*).sub.n-Fn
where n is zero or 1, Z* and Fn are as defined previously, and
functional groups (Fn) provided above.
[0234] More preferred cyclic olefins possessing at least one
norbornene moiety have the structure (F):
##STR00006##
wherein, R.sup.F1, R.sup.F2, R.sup.F3, and R.sup.F4, are as defined
for R.sup.B1 through R.sup.B6, and "a" represents a single bond or
a double bond, "g" is an integer from 0 to 5, and when "a" is a
double bond one of R.sup.F1, R.sup.F2 and one of R.sup.F3, R.sup.F4
is not present.
[0235] Furthermore, any of the R.sup.F1, R.sup.F2, R.sup.F3, and
R.sup.F4 moieties can be linked to any of the other R.sup.F1,
R.sup.F2, R.sup.F3, and R.sup.F4 moieties to provide a substituted
or unsubstituted alicyclic group containing 4 to 30 ring carbon
atoms or a substituted or unsubstituted aryl group containing 6 to
18 ring carbon atoms or combinations thereof and the linkage may
include heteroatoms or functional groups, e.g., the linkage may
include without limitation an ether, ester, thioether, amino,
alkylamino, imino, or anhydride moiety. The alicyclic group can be
monocyclic, bicyclic, or polycyclic. When unsaturated the cyclic
group can contain monounsaturation or multiunsaturation, with
monounsaturated cyclic groups being preferred. When substituted,
the rings contain monosubstitution or multisubstitution wherein the
substituents are independently selected from hydrogen, hydrocarbyl,
substituted hydrocarbyl, heteroatom-containing hydrocarbyl,
substituted heteroatom-containing hydrocarbyl, --(Z*).sub.n-Fn
where n is zero or 1, Z* and Fn are as defined previously, and
functional groups (Fn) provided above.
[0236] One route for the preparation of hydrocarbyl substituted and
functionally substituted norbornenes employs the Diels-Alder
cycloaddition reaction in which cyclopentadiene or substituted
cyclopentadiene is reacted with a suitable dienophile at elevated
temperatures to form the substituted norbornene adduct generally
shown by the following reaction Scheme 1:
##STR00007##
wherein R.sup.F1 to R.sup.F4 are as previously defined for
structure (F).
[0237] Other norbornene adducts can be prepared by the thermal
pyrolysis of dicyclopentadiene in the presence of a suitable
dienophile. The reaction proceeds by the initial pyrolysis of
dicyclopentadiene to cyclopentadiene followed by the Diels-Alder
cycloaddition of cyclopentadiene and the dienophile to give the
adduct shown below in Scheme 2:
##STR00008##
wherein "g" is an integer from 0 to 5, and R.sup.F1 to R.sup.F4 are
as previously defined for structure (F).
[0238] Norbornadiene and higher Diels-Alder adducts thereof
similarly can be prepared by the thermal reaction of
cyclopentadiene and dicyclopentadiene in the presence of an
acetylenic reactant as shown below in Scheme 3:
##STR00009##
wherein "g" is an integer from 0 to 5, R.sup.F1 and R.sup.F4 are as
previously defined for structure (F)
[0239] Examples of bicyclic and polycyclic olefins thus include,
without limitation, dicyclopentadiene (DCPD); trimer and other
higher order oligomers of cyclopentadiene including without
limitation tricyclopentadiene (cyclopentadiene trimer),
cyclopentadiene tetramer, and cyclopentadiene pentamer;
ethylidenenorbornene; dicyclohexadiene; norbornene;
5-methyl-2-norbornene; 5-ethyl-2-norbornene;
5-isobutyl-2-norbornene; 5,6-dimethyl-2-norbornene;
5-phenylnorbornene; 5-benzylnorbornene; 5-acetylnorbornene;
5-methoxycarbonylnorbornene; 5-ethyoxycarbonyl-1-norbornene;
5-methyl-5-methoxy-carbonylnorbornene; 5-cyanonorbornene;
5,5,6-trimethyl-2-norbornene; cyclo-hexenylnorbornene; endo,
exo-5,6-dimethoxynorbornene; endo, endo-5,6-dimethoxynorbornene;
endo, exo-5,6-dimethoxycarbonylnorbornene;
endo,endo-5,6-dimethoxycarbonylnorbornene; 2,3-dimethoxynorbornene;
norbornadiene; tricycloundecene; tetracyclododecene;
8-methyltetracyclododecene; 8-ethyltetracyclododecene;
8-methoxycarbonyltetracyclododecene; 8-methyl-8-tetracyclododecene;
8-cyanotetracyclododecene; pentacyclopentadecene;
pentacyclohexadecene; and the like, and their structural isomers,
stereoisomers, and mixtures thereof. Additional examples of
bicyclic and polycyclic olefins include, without limitation,
C.sub.2-C.sub.12 hydrocarbyl substituted norbornenes such as
5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene,
5-decyl-2-norbornene, 5-dodecyl-2-norbornene, 5-vinyl-2-norbornene,
5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene,
5-propenyl-2-norbornene, and 5-butenyl-2-norbornene, and the like.
It is well understood by one in the art that bicyclic and
polycyclic olefins as disclosed herein may consist of a variety of
structural isomers and/or stereoisomers, any and all of which are
suitable for use in the present invention. Any reference herein to
such bicyclic and polycyclic olefins unless specifically stated
includes mixtures of any and all such structural isomers and/or
stereoisomers.
[0240] Preferred cyclic olefins include C.sub.5 to C.sub.24
unsaturated hydrocarbons. Also preferred are C.sub.5 to C.sub.24
cyclic hydrocarbons that contain one or more (typically 2 to 12)
heteroatoms such as O, N, S, or P. For example, crown ether cyclic
olefins may include numerous O heteroatoms throughout the cycle,
and these are within the scope of the invention. In addition,
preferred cyclic olefins are C.sub.5 to C.sub.24 hydrocarbons that
contain one or more (typically 2 or 3) olefins. For example, the
cyclic olefin may be mono-, di-, or tri-unsaturated. Examples of
cyclic olefins include without limitation cyclooctene,
cyclododecene, and (c,t,t)-1,5,9-cyclododecatriene.
[0241] The cyclic olefins may also comprise multiple (typically 2
or 3) rings. For example, the cyclic olefin may be mono-, di-, or
tri-cyclic. When the cyclic olefin comprises more than one ring,
the rings may or may not be fused. Preferred examples of cyclic
olefins that comprise multiple rings include norbornene,
dicyclopentadiene, tricyclopentadiene, and
5-ethylidene-2-norbornene.
[0242] The cyclic olefin may also be substituted, for example, a
C.sub.5 to C.sub.24 cyclic hydrocarbon wherein one or more
(typically 2, 3, 4, or 5) of the hydrogens are replaced with
non-hydrogen substituents. Suitable non-hydrogen substituents may
be chosen from the substituents described hereinabove. For example,
functionalized cyclic olefins, i.e., C.sub.5 to C.sub.24 cyclic
hydrocarbons wherein one or more (typically 2, 3, 4, or 5) of the
hydrogens are replaced with functional groups, are within the scope
of the invention. Suitable functional groups may be chosen from the
functional groups described hereinabove. For example, a cyclic
olefin functionalized with an alcohol group may be used to prepare
a telechelic polymer comprising pendent alcohol groups. Functional
groups on the cyclic olefin may be protected in cases where the
functional group interferes with the metathesis catalyst, and any
of the protecting groups commonly used in the art may be employed.
Acceptable protecting groups may be found, for example, in Greene
et al., Protective Groups in Organic Synthesis, 3rd Ed. (New York:
Wiley, 1999). Examples of functionalized cyclic olefins include
without limitation 2-hydroxymethyl-5-norbornene,
2-[(2-hydroxyethyl)carboxylate]-5-norbornene, cydecanol,
5-n-hexyl-2-norbornene, 5-n-butyl-2-norbornene.
[0243] Cyclic olefins incorporating any combination of the
abovementioned features (i.e., heteroatoms, substituents, multiple
olefins, multiple rings) are suitable for the methods disclosed
herein. Additionally, cyclic olefins incorporating any combination
of the abovementioned features (i.e., heteroatoms, substituents,
multiple olefins, multiple rings) are suitable for the invention
disclosed herein.
[0244] The cyclic olefins useful in the methods disclosed herein
may be strained or unstrained. It will be appreciated that the
amount of ring strain varies for each cyclic olefin compound, and
depends upon a number of factors including the size of the ring,
the presence and identity of substituents, and the presence of
multiple rings. Ring strain is one factor in determining the
reactivity of a molecule towards ring-opening olefin metathesis
reactions. Highly strained cyclic olefins, such as certain bicyclic
compounds, readily undergo ring opening reactions with olefin
metathesis catalysts. Less strained cyclic olefins, such as certain
unsubstituted hydrocarbon monocyclic olefins, are generally less
reactive. In some cases, ring opening reactions of relatively
unstrained (and therefore relatively unreactive) cyclic olefins may
become possible when performed in the presence of the olefinic
compounds disclosed herein. Additionally, cyclic olefins useful in
the invention disclosed herein may be strained or unstrained.
[0245] The resin compositions and/or cyclic olefin compositions of
the present invention may comprise a plurality of cyclic olefins. A
plurality of cyclic olefins may be used to prepare metathesis
polymers from the olefinic compound. For example, two cyclic
olefins selected from the cyclic olefins described hereinabove may
be employed in order to form metathesis products that incorporate
both cyclic olefins. Where two or more cyclic olefins are used, one
example of a second cyclic olefin is a cyclic alkenol, i.e., a
C.sub.5-C.sub.2 cyclic hydrocarbon wherein at least one of the
hydrogen substituents is replaced with an alcohol or protected
alcohol moiety to yield a functionalized cyclic olefin.
[0246] The use of a plurality of cyclic olefins, and in particular
when at least one of the cyclic olefins is functionalized, allows
for further control over the positioning of functional groups
within the products. For example, the density of cross-linking
points can be controlled in polymers and macromonomers prepared
using the methods disclosed herein. Control over the quantity and
density of substituents and functional groups also allows for
control over the physical properties (e.g., melting point, tensile
strength, glass transition temperature, etc.) of the products.
Control over these and other properties is possible for reactions
using only a single cyclic olefin, but it will be appreciated that
the use of a plurality of cyclic olefins further enhances the range
of possible metathesis products and polymers formed.
[0247] More preferred cyclic olefins include dicyclopentadiene;
tricyclopentadiene; dicyclohexadiene; norbornene;
5-methyl-2-norbornene; 5-ethyl-2-norbornene;
5-isobutyl-2-norbornene; 5,6-dimethyl-2-norbornene;
5-phenylnorbornene; 5-benzylnorbornene; 5-acetylnorbornene;
5-methoxycarbonylnorbornene; 5-ethoxycarbonyl-1-norbornene;
5-methyl-5-methoxy-carbonylnorbornene; 5-cyanonorbornene;
5,5,6-trimethyl-2-norbornene; cyclo-hexenylnorbornene; endo,
exo-5,6-dimethoxynorbornene; endo, endo-5,6-dimethoxynorbornene;
endo, exo-5-6-dimethoxycarbonylnorbornene; endo,
endo-5,6-dimethoxycarbonylnorbornene; 2,3-dimethoxynorbornene;
norbornadiene; tricycloundecene; tetracyclododecene;
8-methyltetracyclododecene; 8-ethyl-tetracyclododecene;
8-methoxycarbonyltetracyclododecene;
8-methyl-8-tetracyclo-dodecene; 8-cyanotetracyclododecene;
pentacyclopentadecene; pentacyclohexadecene; higher order oligomers
of cyclopentadiene such as cyclopentadiene tetramer,
cyclopentadiene pentamer, and the like; and C.sub.2-C.sub.12
hydrocarbyl substituted norbornenes such as 5-butyl-2-norbornene;
5-hexyl-2-norbornene; 5-octyl-2-norbornene; 5-decyl-2-norbornene;
5-dodecyl-2-norbornene; 5-vinyl-2-norbornene;
5-ethylidene-2-norbornene; 5-isopropenyl-2-norbornene;
5-propenyl-2-norbornene; and 5-butenyl-2-norbornene, and the like.
Even more preferred cyclic olefins include dicyclopentadiene,
tricyclopentadiene, and higher order oligomers of cyclopentadiene,
such as cyclopentadiene tetramer, cyclopentadiene pentamer, and the
like, tetracyclododecene, norbornene, and C.sub.2-C.sub.12
hydrocarbyl substituted norbornenes, such as 5-butyl-2-norbornene,
5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene,
5-dodecyl-2-norbornene, 5-vinyl-2-norbornene,
5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene,
5-propenyl-2-norbornene, 5-butenyl-2-norbornene, and the like.
[0248] Cyclic olefins include dicyclopentadiene,
tricyclopentadiene, and higher order oligomers of cyclopentadiene,
such as cyclopentadiene tetramer, cyclopentadiene pentamer, and the
like, 5-tolyl-2-norbornene, 5-phenyl-2-norbornene, C.sub.2-C.sub.12
hydrocarbyl substituted norbornenes, such as 5-hexyl-2-norbornene,
5-octyl-2-norbornene, 5-decyl-2-norbornene, 5-dodecyl-2-norbornene,
and the like.
[0249] Cyclic olefins that contain multiunsaturation include
dicyclopentadiene, tricyclopentadiene, and higher order oligomers
of cyclopentadiene, such as cyclopentadiene tetramer,
cyclopentadiene pentamer, and the like, and 5-vinyl-2-norbornene,
5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene,
5-propenyl-2-norbornene, 5-butenyl-2-norbornene, and the like.
[0250] Cyclic olefins that contain multiunsaturation include
dicyclopentadiene, tricyclopentadiene, and higher order oligomers
of cyclopentadiene, such as cyclopentadiene tetramer,
cyclopentadiene pentamer, and the like
[0251] Cyclic olefins that contain monounsaturation include
5-tolyl-2-norbornene, 5-phenyl-2-norbornene, 5-butyl-2-norbornene,
5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene,
5-dodecyl-2-norbornene.
[0252] Cyclic olefins that contain monounsaturation include
5-tolyl-2-norbornene, 5-phenyl-2-norbornene.
[0253] Cyclic olefins that contain monounsaturation include
5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene,
5-decyl-2-norbornene, 5-dodecyl-2-norbornene
[0254] Cyclic olefins that contain monounsaturation include
5-hexyl-2-norbornene, 5-octyl-2-norbornene,
5-decyl-2-norbornene.
[0255] Cyclic olefins that contain monounsaturation include
5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene,
and 5-tolyl-2-norbornene.
[0256] Cyclic olefins that contain monounsaturation include
5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene,
5-tolyl-2-norbornene, and 5-phenyl-2-norbornene.
Metal Carbene Olefin Metathesis Catalysts
[0257] A metal carbene olefin metathesis catalyst that may be used
in the invention disclosed herein, is preferably a Group 8
transition metal complex having the structure of formula (I)
##STR00010##
in which:
[0258] M is a Group 8 transition metal;
[0259] L.sup.1, L.sup.2, and L.sup.3 are neutral electron donor
ligands;
[0260] n is 0 or 1, such that L.sup.3 may or may not be
present;
[0261] m is 0, 1, or 2;
[0262] k is 0 or 1;
[0263] X.sup.1 and X.sup.2 are anionic ligands; and
[0264] R.sup.1 and R.sup.2 are independently selected from
hydrogen, hydrocarbyl, substituted hydrocarbyl,
heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, and functional groups, [0265]
wherein any two or more of X.sup.1, X.sup.2, L.sup.1, L.sup.2,
L.sup.3, R.sup.1, and R.sup.2 can be taken together to form one or
more cyclic groups, and further wherein any one or more of X.sup.1,
X.sup.2, L.sup.1, L.sup.2, L.sup.3, R.sup.1, and R.sup.2 may be
attached to a support.
[0266] Additionally, in formula (I), one or both of R.sup.1 and
R.sup.2 may have the structure --(W).sub.n--U.sup.+V.sup.-, in
which W is selected from hydrocarbylene, substituted
hydrocarbylene, heteroatom-containing hydrocarbylene, or
substituted heteroatom-containing hydrocarbylene; U is a positively
charged Group 15 or Group 16 element substituted with hydrogen,
hydrocarbyl, substituted hydrocarbyl, heteroatom-containing
hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; V is
a negatively charged counterion; and n is zero or 1. Furthermore,
R.sup.1 and R.sup.2 may be taken together to form an indenylidene
moiety.
[0267] Preferred catalysts contain Ru or Os as the Group 8
transition metal, with Ru particularly preferred.
[0268] Numerous embodiments of the catalysts useful in the
reactions disclosed herein are described in more detail infra. For
the sake of convenience, the catalysts are described in groups, but
it should be emphasized that these groups are not meant to be
limiting in any way. That is, any of the catalysts useful in the
invention may fit the description of more than one of the groups
described herein.
[0269] A first group of catalysts, then, are commonly referred to
as First Generation Grubbs-type catalysts, and have the structure
of formula (I). For the first group of catalysts, M is a Group 8
transition metal, m is 0, 1, or 2, and n, X.sup.1, X.sup.2,
L.sup.1, L.sup.2, L.sup.3, R.sup.1, and R.sup.2 are described as
follows.
[0270] For the first group of catalysts, n is 0, and L.sup.1 and
L.sup.2 are independently selected from phosphine, sulfonated
phosphine, phosphite, phosphinite, phosphonite, arsine, stibine,
ether, (including cyclic ethers), amine, amide, imine, sulfoxide,
carboxyl, nitrosyl, pyridine, substituted pyridine, imidazole,
substituted imidazole, pyrazine, substituted pyrazine and
thioether. Exemplary ligands are trisubstituted phosphines.
Preferred trisubstituted phosphines are of the formula
PR.sup.H1R.sup.H2R.sup.H3, where R.sup.H1, R.sup.H2, and R.sup.H3
are each independently substituted or unsubstituted aryl or
C.sub.1-C.sub.10 alkyl, particularly primary alkyl, secondary
alkyl, or cycloalkyl. In the most preferred, L.sup.1 and L.sup.2
are independently selected from the group consisting of
trimethylphosphine (PMe.sub.3), triethylphosphine (PEt.sub.3),
tri-n-butylphosphine (PBu.sub.3), tri(ortho-tolyl)phosphine
(P-o-tolyl.sub.3), tri-tert-butylphosphine (P-tert-Bu.sub.3),
tricyclopentylphosphine (PCyclopentyl.sub.3),
tricyclohexylphosphine (PCy.sub.3), triisopropylphosphine
(P-i-Pr.sub.3), trioctylphosphine (POct.sub.3),
triisobutylphosphine, (P-i-Bu.sub.3), triphenylphosphine
(PPh.sub.3), tri(pentafluorophenyl)phosphine
(P(C.sub.6F.sub.5).sub.3), methyldiphenylphosphine (PMePh.sub.2),
dimethylphenylphosphine (PMe.sub.2Ph), and diethylphenylphosphine
(PEt.sub.2Ph). Alternatively, L.sup.1 and L.sup.2 may be
independently selected from phosphabicycloalkane (e.g.,
monosubstituted 9-phosphabicyclo-[3.3.1]nonane, or monosubstituted
9-phosphabicyclo[4.2.1]nonane] such as cyclohexylphoban,
isopropylphoban, ethylphoban, methylphoban, butylphoban,
pentylphoban and the like).
[0271] X.sup.1 and X.sup.2 are anionic ligands, and may be the same
or different, or are linked together to form a cyclic group,
typically although not necessarily a five- to eight-membered ring.
In preferred embodiments, X.sup.1 and X.sup.2 are each
independently hydrogen, halide, or one of the following groups:
C.sub.1-C.sub.20 alkyl, C.sub.5-C.sub.24 aryl, C.sub.1-C.sub.20
alkoxy, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.20 alkoxycarbonyl,
C.sub.6-C.sub.24 aryloxycarbonyl, C.sub.2-C.sub.24 acyl,
C.sub.2-C.sub.24 acyloxy, C.sub.1-C.sub.20 alkylsulfonato,
C.sub.5-C.sub.24 arylsulfonato, C.sub.1-C.sub.20 alkylsulfanyl,
C.sub.5-C.sub.24 arylsulfanyl, C.sub.1-C.sub.20 alkylsulfinyl,
NO.sub.3, --N.dbd.C.dbd.O, --N.dbd.C.dbd.S, or C.sub.5-C.sub.24
arylsulfinyl. Optionally, X.sup.1 and X.sup.2 may be substituted
with one or more moieties selected from C.sub.1-C.sub.12 alkyl,
C.sub.1-C.sub.12 alkoxy, C.sub.5-C.sub.24 aryl, and halide, which
may, in turn, with the exception of halide, be further substituted
with one or more groups selected from halide, C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6 alkoxy, and phenyl. In more preferred
embodiments, X.sup.1 and X.sup.2 are halide, benzoate,
C.sub.2-C.sub.6 acyl, C.sub.2-C.sub.6 alkoxycarbonyl,
C.sub.1-C.sub.6 alkyl, phenoxy, C.sub.1-C.sub.6 alkoxy,
C.sub.1-C.sub.6 alkylsulfanyl, aryl, or C.sub.1-C.sub.6
alkylsulfonyl. In even more preferred embodiments, X.sup.1 and
X.sup.2 are each halide, CF.sub.3CO.sub.2, CH.sub.3CO.sub.2,
CFH.sub.2CO.sub.2, (CH.sub.3).sub.3CO,
(CF.sub.3).sub.2(CH.sub.3)CO, (CF.sub.3)(CH.sub.3).sub.2CO, PhO,
MeO, EtO, tosylate, mesylate, or trifluoromethane-sulfonate. In the
most preferred embodiments, X.sup.1 and X.sup.2 are each
chloride.
[0272] R.sup.1 and R.sup.2 are independently selected from
hydrogen, hydrocarbyl (e.g., C.sub.1-C.sub.20 alkyl,
C.sub.2-C.sub.20 alkenyl, C.sub.2-C.sub.20 alkynyl,
C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24
aralkyl, etc.), substituted hydrocarbyl (e.g., substituted
C.sub.1-C.sub.20 alkyl, C.sub.2-C.sub.20 alkenyl, C.sub.2-C.sub.20
alkynyl, C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl,
C.sub.6-C.sub.24 aralkyl, etc.), heteroatom-containing hydrocarbyl
(e.g., heteroatom-containing C.sub.1-C.sub.20 alkyl,
C.sub.2-C.sub.20 alkenyl, C.sub.2-C.sub.20 alkynyl,
C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24
aralkyl, etc.), and substituted heteroatom-containing hydrocarbyl
(e.g., substituted heteroatom-containing C.sub.1-C.sub.20 alkyl,
C.sub.2-C.sub.20 alkenyl, C.sub.2-C.sub.20 alkynyl,
C.sub.5-C.sub.24 aryl, C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24
aralkyl, etc.), and functional groups. R.sup.1 and R.sup.2 may also
be linked to form a cyclic group, which may be aliphatic or
aromatic, and may contain substituents and/or heteroatoms.
Generally, such a cyclic group will contain 4 to 12, preferably 5,
6, 7, or 8 ring atoms.
[0273] In preferred catalysts, R.sup.1 is hydrogen and R.sup.2 is
selected from C.sub.1-C.sub.20 alkyl, C.sub.2-C.sub.20 alkenyl, and
C.sub.5-C.sub.24 aryl, more preferably C.sub.1-C.sub.6 alkyl,
C.sub.2-C.sub.6 alkenyl, and C.sub.5-C.sub.14 aryl. Still more
preferably, R.sup.2 is phenyl, vinyl, methyl, isopropyl, or
t-butyl, optionally substituted with one or more moieties selected
from C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, phenyl, and a
functional group Fn as defined earlier herein. Most preferably,
R.sup.2 is phenyl or vinyl substituted with one or more moieties
selected from methyl, ethyl, chloro, bromo, iodo, fluoro, nitro,
dimethylamino, methyl, methoxy, and phenyl. Optimally, R.sup.2 is
phenyl or --CH.dbd.C(CH.sub.3).sub.2.
[0274] Any two or more (typically two, three, or four) of X.sup.1,
X.sup.2, L.sup.1, L.sup.2, L.sup.3, R.sup.1, and R.sup.2 can be
taken together to form a cyclic group, including bidentate or
multidentate ligands, as disclosed, for example, in U.S. Pat. No.
5,312,940, the disclosure of which is incorporated herein by
reference. When any of X.sup.1, X.sup.2, L.sup.1, L.sup.2, L.sup.3,
R.sup.1, and R.sup.2 are linked to form cyclic groups, those cyclic
groups may contain 4 to 12, preferably 4, 5, 6, 7 or 8 atoms, or
may comprise two or three of such rings, which may be either fused
or linked. The cyclic groups may be aliphatic or aromatic, and may
be heteroatom-containing and/or substituted. The cyclic group may,
in some cases, form a bidentate ligand or a tridentate ligand.
Examples of bidentate ligands include, but are not limited to,
bisphosphines, dialkoxides, alkyldiketonates, and
aryldiketonates.
[0275] A second group of catalysts, commonly referred to as Second
Generation Grubbs-type catalysts, have the structure of formula
(I), wherein L.sup.1 is a carbene ligand having the structure of
formula (II)
##STR00011##
such that the complex may have the structure of formula (III)
##STR00012##
wherein M, m, n, X.sup.1, X.sup.2, L.sup.2, L.sup.3, R.sup.1, and
R.sup.2 are as defined for the first group of catalysts, and the
remaining substituents are as follows;
[0276] X and Y are heteroatoms typically selected from N, O, S, and
P. Since O and S are divalent, p is necessarily zero when X is O or
S, q is necessarily zero when Y is O or S, and k is zero or 1.
However, when X is N or P, then p is 1, and when Y is N or P, then
q is 1. In a preferred embodiment, both X and Y are N;
[0277] Q.sup.1, Q.sup.2, Q.sup.3, and Q.sup.4 are linkers, e.g.,
hydrocarbylene (including substituted hydrocarbylene,
heteroatom-containing hydrocarbylene, and substituted
heteroatom-containing hydrocarbylene, such as substituted and/or
heteroatom-containing alkylene) or --(CO)--, and w, x, y, and z are
independently zero or 1, meaning that each linker is optional.
Preferably, w, x, y, and z are all zero. Further, two or more
substituents on adjacent atoms within Q.sup.1, Q.sup.2, Q.sup.3,
and Q.sup.4 may be linked to form an additional cyclic group;
and
[0278] R.sup.3, R.sup.3A, R.sup.4, and R.sup.4A are independently
selected from hydrogen, hydrocarbyl, substituted hydrocarbyl,
heteroatom-containing hydrocarbyl, and substituted
heteroatom-containing hydrocarbyl. In addition, X and Y may be
independently selected from carbon and one of the heteroatoms
mentioned above, preferably no more than one of X or Y is carbon.
Also, L.sup.2 and L.sup.3 may be taken together to form a single
bindentate electron-donating heterocyclic ligand. Furthermore,
R.sup.1 and R.sup.2 may be taken together to form an indenylidene
moiety. Moreover, X.sup.1, X.sup.2, L.sup.2, L.sup.3, X and Y may
be further coordinated to boron or to a carboxylate.
[0279] In addition, any two or more of X.sup.1, X.sup.2, L.sup.1,
L.sup.2, L.sup.3, R.sup.1, R.sup.2, R.sup.3, R.sup.3A, R.sup.4,
R.sup.4A, Q.sup.1, Q.sup.2, Q.sup.3 and Q.sup.4 can be taken
together to form a cyclic group, and any one or more of X R.sup.3,
R.sup.3A, R.sup.4, and R.sup.4A may be attached to a support. Any
two or more of X.sup.1, X.sup.2, L.sup.1, L.sup.2, L.sup.3,
R.sup.1, R.sup.2, R.sup.3, R.sup.3A, R.sup.4, and R.sup.4A can also
be taken to be -A-Fn, wherein "A" is a divalent hydrocarbon moiety
selected from alkylene and arylalkylene, wherein the alkyl portion
of the alkylene and arylalkylene groups can be linear or branched,
saturated or unsaturated, cyclic or acyclic, and substituted or
unsubstituted, wherein the aryl portion of the of arylalkylene can
be substituted or unsubstituted, and wherein hetero atoms and/or
functional groups may be present in either the aryl or the alkyl
portions of the alkylene and arylalkylene groups, and Fn is a
functional group, or together to form a cyclic group, and any one
or more of X.sup.1, X.sup.2, L.sup.2, L.sup.3, Q.sup.1, Q.sup.2,
Q.sup.3, Q.sup.4, R.sup.1, R.sup.2, R.sup.3, R.sup.3A, R.sup.4, and
R.sup.4A may be attached to a support.
[0280] A particular class of carbene ligands having the structure
of formula (II), where R.sup.3A and R.sup.4A are linked to form a
cyclic group and at least one of X or Y is a nitrogen, or at least
one of Q.sup.3 or Q.sup.4 is a heteroatom-containing hydrocarbylene
or substituted heteroatom-containing hydrocarbylene, where at least
one heteroatom is a nitrogen, are commonly referred to as
N-heterocyclic carbene (NHC) ligands.
[0281] Preferably, R.sup.3A and R.sup.4A are linked to form a
cyclic group so that the carbene ligand has the structure of
formula (IV)
##STR00013##
wherein R.sup.3 and R.sup.4 are as defined for the second group of
catalysts above, with preferably at least one of R.sup.3 and
R.sup.4, and more preferably both R.sup.3 and R.sup.4, being
alicyclic or aromatic of one to about five rings, and optionally
containing one or more heteroatoms and/or substituents. Q is a
linker, typically a hydrocarbylene linker, including substituted
hydrocarbylene, heteroatom-containing hydrocarbylene, and
substituted heteroatom-containing hydrocarbylene linkers, wherein
two or more substituents on adjacent atoms within Q may also be
linked to form an additional cyclic structure, which may be
similarly substituted to provide a fused polycyclic structure of
two to about five cyclic groups. Q is often, although not
necessarily, a two-atom linkage or a three-atom linkage.
[0282] Examples of N-heterocyclic carbene (NHC) ligands and acyclic
diaminocarbene ligands suitable as L.sup.1 thus include, but are
not limited to, the following where DIPP or DiPP is
diisopropylphenyl and Mes is 2,4,6-trimethylphenyl:
##STR00014##
[0283] Additional examples of N-heterocyclic carbene (NHC) ligands
and acyclic diaminocarbene ligands suitable as L.sup.1 thus
include, but are not limited to the following:
##STR00015##
wherein R.sup.W1, R.sup.W2, R.sup.W3, R.sup.W4 are independently
hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, or
heteroatom containing hydrocarbyl, and where one or both of
R.sup.W3 and R.sup.W4 may be in independently selected from
halogen, nitro, amido, carboxyl, alkoxy, aryloxy, sulfonyl,
carbonyl, thio, or nitroso groups.
[0284] Additional examples of N-heterocyclic carbene (NHC) ligands
suitable as L.sup.1 are further described in U.S. Pat. Nos.
7,378,528; 7,652,145; 7,294,717; 6,787,620; 6,635,768; and
6,552,139, the contents of each are incorporated herein by
reference.
[0285] Additionally, thermally activated N-Heterocyclic Carbene
Precursors as disclosed in U.S. Pat. No. 6,838,489, the contents of
which are incorporated herein by reference, may also be used with
the present invention.
[0286] When M is ruthenium, then, the preferred complexes have the
structure of formula (V)
##STR00016##
[0287] In a more preferred embodiment, Q is a two-atom linkage
having the structure --CR.sup.11R.sup.12--CR.sup.13R.sup.14-- or
--CR.sup.11.dbd.CR.sup.13--, preferably
--CR.sup.11R.sup.12--CR.sup.13R.sup.14--, wherein R.sup.11,
R.sup.12, R.sup.13, and R.sup.14 are independently selected from
hydrogen, hydrocarbyl, substituted hydrocarbyl,
heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, and functional groups. Examples
of functional groups here include without limitation carboxyl,
C.sub.1-C.sub.20 alkoxy, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.20
alkoxycarbonyl, C.sub.5-C.sub.24 alkoxycarbonyl, C.sub.2-C.sub.24
acyloxy, C.sub.1-C.sub.20 alkylthio, C.sub.5-C.sub.24 arylthio,
C.sub.1-C.sub.20 alkylsulfonyl, and C.sub.1-C.sub.20 alkylsulfinyl,
optionally substituted with one or more moieties selected from
C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 alkoxy, C.sub.5-C.sub.14
aryl, hydroxyl, sulfhydryl, formyl, and halide. R.sup.11, R.sup.12,
R.sup.13, and R.sup.14 are preferably independently selected from
hydrogen, C.sub.1-C.sub.12 alkyl, substituted C.sub.1-C.sub.12
alkyl, C.sub.1-C.sub.12 heteroalkyl, substituted C.sub.1-C.sub.12
heteroalkyl, phenyl, and substituted phenyl. Alternatively, any two
of R.sup.11, R.sup.12, R.sup.13, and R.sup.14 may be linked
together to form a substituted or unsubstituted, saturated or
unsaturated ring structure, e.g., a C.sub.4-C.sub.12 alicyclic
group or a C.sub.5 or C.sub.6 aryl group, which may itself be
substituted, e.g., with linked or fused alicyclic or aromatic
groups, or with other substituents. In one further aspect, any one
or more of R.sup.11, R.sup.12, R.sup.13, and R.sup.14 comprises one
or more of the linkers. Additionally, R.sup.3 and R.sup.4 may be
unsubstituted phenyl or phenyl substituted with one or more
substituents selected from C.sub.1-C.sub.20 alkyl, substituted
C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 heteroalkyl, substituted
C.sub.1-C.sub.20 heteroalkyl, C.sub.5-C.sub.24 aryl substituted
C.sub.5-C.sub.24 aryl, C.sub.5-C.sub.24 heteroaryl,
C.sub.6-C.sub.24 aralkyl, C.sub.6-C.sub.24 alkaryl, or halide.
Furthermore, X.sup.1 and X.sup.2 may be halogen.
[0288] When R.sup.3 and R.sup.4 are aromatic, they are typically
although not necessarily composed of one or two aromatic rings,
which may or may not be substituted, e.g., R.sup.3 and R.sup.4 may
be phenyl, substituted phenyl, biphenyl, substituted biphenyl, or
the like. In one preferred embodiment, R.sup.3 and R.sup.4 are the
same and are each unsubstituted phenyl or phenyl substituted with
up to three substituents selected from C.sub.1-C.sub.20 alkyl,
substituted C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 heteroalkyl,
substituted C.sub.1-C.sub.20 heteroalkyl, C.sub.5-C.sub.24 aryl,
substituted C.sub.5-C.sub.24 aryl, C.sub.5-C.sub.24 heteroaryl,
C.sub.6-C.sub.24 aralkyl, C.sub.6-C.sub.24 alkaryl, or halide.
Preferably, any substituents present are hydrogen, C.sub.1-C.sub.12
alkyl, C.sub.1-C.sub.12 alkoxy, C.sub.5-C.sub.14 aryl, substituted
C.sub.5-C.sub.14 aryl, or halide. As an example, R.sup.3 and
R.sup.4 are mesityl (i.e., Mes as defined herein).
[0289] In a third group of catalysts having the structure of
formula (I), M, m, n, X.sup.1, X.sup.2, R.sup.1, and R.sup.2 are as
defined for the first group of catalysts, L.sup.1 is a strongly
coordinating neutral electron donor ligand such as any of those
described for the first and second group of catalysts, and L.sup.2
and L.sup.3 are weakly coordinating neutral electron donor ligands
in the form of optionally substituted heterocyclic groups. Again, n
is zero or 1, such that L.sup.3 may or may not be present.
Generally, in the third group of catalysts, L.sup.2 and L.sup.3 are
optionally substituted five- or six-membered monocyclic groups
containing 1 to 4, preferably 1 to 3, most preferably 1 to 2
heteroatoms, or are optionally substituted bicyclic or polycyclic
structures composed of 2 to 5 such five- or six-membered monocyclic
groups. If the heterocyclic group is substituted, it should not be
substituted on a coordinating heteroatom, and any one cyclic moiety
within a heterocyclic group will generally not be substituted with
more than 3 substituents.
[0290] For the third group of catalysts, examples of L.sup.2 and
L.sup.3 include, without limitation, heterocycles containing
nitrogen, sulfur, oxygen, or a mixture thereof.
[0291] Examples of nitrogen-containing heterocycles appropriate for
L.sup.2 and L.sup.3 include pyridine, bipyridine, pyridazine,
pyrimidine, bipyridamine, pyrazine, 1,3,5-triazine, 1,2,4-triazine,
1,2,3-triazine, pyrrole, 2H-pyrrole, 3H-pyrrole, pyrazole,
2H-imidazole, 1,2,3-triazole, 1,2,4-triazole, indole, 3H-indole,
1H-isoindole, cyclopenta(b)pyridine, indazole, quinoline,
bisquinoline, isoquinoline, bisisoquinoline, cinnoline,
quinazoline, naphthyridine, piperidine, piperazine, pyrrolidine,
pyrazolidine, quinuclidine, imidazolidine, picolylimine, purine,
benzimidazole, bisimidazole, phenazine, acridine, and carbazole.
Additionally, the nitrogen-containing heterocycles may be
optionally substituted on a non-coordinating heteroatom with a
non-hydrogen substitutent.
[0292] Examples of sulfur-containing heterocycles appropriate for
L.sup.2 and L.sup.3 include thiophene, 1,2-dithiole, 1,3-dithiole,
thiepin, benzo(b)thiophene, benzo(c)thiophene, thionaphthene,
dibenzothiophene, 2H-thiopyran, 4H-thiopyran, and thioanthrene.
[0293] Examples of oxygen-containing heterocycles appropriate for
L.sup.2 and L.sup.3 include 2H-pyran, 4H-pyran, 2-pyrone, 4-pyrone,
1,2-dioxin, 1,3-dioxin, oxepin, furan, 2H-1-benzopyran, coumarin,
coumarone, chromene, chroman-4-one, isochromen-1-one,
isochromen-3-one, xanthene, tetrahydrofuran, 1,4-dioxan, and
dibenzofuran.
[0294] Examples of mixed heterocycles appropriate for L.sup.2 and
L.sup.3 include isoxazole, oxazole, thiazole, isothiazole,
1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole,
1,2,3,4-oxatriazole, 1,2,3,5-oxatriazole, 3H-1,2,3-dioxazole,
3H-1,2-oxathiole, 1,3-oxathiole, 4H-1,2-oxazine, 2H-1,3-oxazine,
1,4-oxazine, 1,2,5-oxathiazine, o-isooxazine, phenoxazine,
phenothiazine, pyrano[3,4-b]pyrrole, indoxazine, benzoxazole,
anthranil, and morpholine.
[0295] Preferred L.sup.2 and L.sup.3 ligands are aromatic
nitrogen-containing and oxygen-containing heterocycles, and
particularly preferred L.sup.2 and L.sup.3 ligands are monocyclic
N-heteroaryl ligands that are optionally substituted with 1 to 3,
preferably 1 or 2, substituents. Specific examples of particularly
preferred L.sup.2 and L.sup.3 ligands are pyridine and substituted
pyridines, such as 3-bromopyridine, 4-bromopyridine,
3,5-dibromopyridine, 2,4,6-tribromopyridine, 2,6-dibromopyridine,
3-chloropyridine, 4-chloropyridine, 3,5-dichloropyridine,
2,4,6-trichloropyridine, 2,6-dichloropyridine, 4-iodopyridine,
3,5-diiodopyridine, 3,5-dibromo-4-methylpyridine,
3,5-dichloro-4-methylpyridine, 3,5-dimethyl-4-bromopyridine,
3,5-dimethylpyridine, 4-methylpyridine, 3,5-diisopropylpyridine,
2,4,6-trimethylpyridine, 2,4,6-triisopropylpyridine,
4-(tert-butyl)pyridine, 4-phenylpyridine, 3,5-diphenylpyridine,
3,5-dichloro-4-phenylpyridine, and the like.
[0296] In general, any substituents present on L.sup.2 and/or
L.sup.3 are selected from halo, C.sub.1-C.sub.20 alkyl, substituted
C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 heteroalkyl, substituted
C.sub.1-C.sub.20 heteroalkyl, C.sub.5-C.sub.24 aryl, substituted
C.sub.5-C.sub.24 aryl, C.sub.5-C.sub.24 heteroaryl, substituted
C.sub.5-C.sub.24 heteroaryl, C.sub.6-C.sub.24 alkaryl, substituted
C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24 heteroalkaryl,
substituted C.sub.6-C.sub.24 heteroalkaryl, C.sub.6-C.sub.24
aralkyl, substituted C.sub.6-C.sub.24 aralkyl, C.sub.6-C.sub.24
heteroaralkyl, substituted C.sub.6-C.sub.24 heteroaralkyl, and
functional groups, with suitable functional groups including,
without limitation, C.sub.1-C.sub.20 alkoxy, C.sub.5-C.sub.24
aryloxy, C.sub.2-C.sub.20 alkylcarbonyl, C.sub.6-C.sub.24
arylcarbonyl, C.sub.2-C.sub.20 alkylcarbonyloxy, C.sub.6-C.sub.24
arylcarbonyloxy, C.sub.2-C.sub.20 alkoxycarbonyl, C.sub.6-C.sub.24
aryloxycarbonyl, halocarbonyl, C.sub.2-C.sub.20 alkylcarbonato,
C.sub.6-C.sub.24 arylcarbonato, carboxy, carboxylato, carbamoyl,
mono-(C.sub.1-C.sub.20 alkyl)-substituted carbamoyl,
di-(C.sub.1-C.sub.20 alkyl)-substituted carbamoyl,
di-N--(C.sub.1-C.sub.20 alkyl), N--(C.sub.5-C.sub.24
aryl)-substituted carbamoyl, mono-(C.sub.5-C.sub.24
aryl)-substituted carbamoyl, di-(C.sub.6-C.sub.24 aryl)-substituted
carbamoyl, thiocarbamoyl, mono-(C.sub.1-C.sub.20 alkyl)-substituted
thiocarbamoyl, di-(C.sub.1-C.sub.20 alkyl)-substituted
thiocarbamoyl, di-N--(C.sub.1-C.sub.20 alkyl)-N--(C.sub.6-C.sub.24
aryl)-substituted thiocarbamoyl, mono-(C.sub.6-C.sub.24
aryl)-substituted thiocarbamoyl, di-(C.sub.6-C.sub.24
aryl)-substituted thiocarbamoyl, carbamido, formyl, thioformyl,
amino, mono-(C.sub.1-C.sub.20 alkyl)-substituted amino,
di-(C.sub.1-C.sub.20 alkyl)-substituted amino,
mono-(C.sub.5-C.sub.24 aryl)-substituted amino,
di-(C.sub.5-C.sub.24 aryl)-substituted amino,
di-N--(C.sub.1-C.sub.20 alkyl), N--(C.sub.5-C.sub.24
aryl)-substituted amino, C.sub.2-C.sub.20 alkylamido,
C.sub.6-C.sub.24 arylamido, imino, C.sub.1-C.sub.20 alkylimino,
C.sub.5-C.sub.24 arylimino, nitro, and nitroso. In addition, two
adjacent substituents may be taken together to form a ring,
generally a five- or six-membered alicyclic or aryl ring,
optionally containing 1 to 3 heteroatoms and 1 to 3 substituents as
above.
[0297] Preferred substituents on L.sup.2 and L.sup.3 include,
without limitation, halo, C.sub.1-C.sub.12 alkyl, substituted
C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 heteroalkyl, substituted
C.sub.1-C.sub.12 heteroalkyl, C.sub.5-C.sub.14 aryl, substituted
C.sub.5-C.sub.14 aryl, C.sub.5-C.sub.14 heteroaryl, substituted
C.sub.5-C.sub.14 heteroaryl, C.sub.6-C.sub.16 alkaryl, substituted
C.sub.6-C.sub.16 alkaryl, C.sub.6-C.sub.16 heteroalkaryl,
substituted C.sub.6-C.sub.16 heteroalkaryl, C.sub.6-C.sub.16
aralkyl, substituted C.sub.6-C.sub.16 aralkyl, C.sub.6-C.sub.16
heteroaralkyl, substituted C.sub.6-C.sub.16 heteroaralkyl,
C.sub.1-C.sub.12 alkoxy, C.sub.5-C.sub.14 aryloxy, C.sub.2-C.sub.12
alkylcarbonyl, C.sub.6-C.sub.14 arylcarbonyl, C.sub.2-C.sub.12
alkylcarbonyloxy, C.sub.6-C.sub.14 arylcarbonyloxy,
C.sub.2-C.sub.12 alkoxycarbonyl, C.sub.6-C.sub.14 aryloxycarbonyl,
halocarbonyl, formyl, amino, mono-(C.sub.1-C.sub.12
alkyl)-substituted amino, di-(C.sub.1-C.sub.12 alkyl)-substituted
amino, mono-(C.sub.5-C.sub.14 aryl)-substituted amino,
di-(C.sub.5-C.sub.14 aryl)-substituted amino, and nitro.
[0298] Of the foregoing, the most preferred substituents are halo,
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6
alkoxy, phenyl, substituted phenyl, formyl, N,N-di(C.sub.1-C.sub.6
alkyl)amino, nitro, and nitrogen heterocycles as described above
(including, for example, pyrrolidine, piperidine, piperazine,
pyrazine, pyrimidine, pyridine, pyridazine, etc.).
[0299] In certain embodiments, L.sup.2 and L.sup.3 may also be
taken together to form a bidentate or multidentate ligand
containing two or more, generally two, coordinating heteroatoms
such as N, O, S, or P, with preferred such ligands being diimine
ligands of the Brookhart type. One representative bidentate ligand
has the structure of formula (VI)
##STR00017##
wherein R.sup.15, R.sup.16, R.sup.17, and R.sup.18 hydrocarbyl
(e.g., C.sub.1-C.sub.20 alkyl, C.sub.2-C.sub.20 alkenyl,
C.sub.2-C.sub.20 alkynyl, C.sub.5-C.sub.2 aryl, C.sub.6-C.sub.24
alkaryl, or C.sub.6-C.sub.24 aralkyl), substituted hydrocarbyl
(e.g., substituted C.sub.1-C.sub.20 alkyl, C.sub.2-C.sub.20
alkenyl, C.sub.2-C.sub.20 alkynyl, C.sub.5-C.sub.2 aryl,
C.sub.6-C.sub.24 alkaryl, or C.sub.6-C.sub.24 aralkyl),
heteroatom-containing hydrocarbyl (e.g., C.sub.1-C.sub.20
heteroalkyl, C.sub.5-C.sub.2 heteroaryl, heteroatom-containing
C.sub.6-C.sub.24 aralkyl, or heteroatom-containing C.sub.6-C.sub.24
alkaryl), or substituted heteroatom-containing hydrocarbyl (e.g.,
substituted C.sub.1-C.sub.20 heteroalkyl, C.sub.5-C.sub.24
heteroaryl, heteroatom-containing C.sub.6-C.sub.24 aralkyl, or
heteroatom-containing C.sub.6-C.sub.24 alkaryl), or (1) R.sup.15
and R.sup.16, (2) R.sup.17 and R.sup.18, (3) R.sup.16 and R.sup.17,
or (4) both R.sup.15 and R.sup.16, and R.sup.17 and R.sup.18, may
be taken together to form a ring, i.e., an N-heterocycle. Preferred
cyclic groups in such a case are five- and six-membered rings,
typically aromatic rings.
[0300] In a fourth group of catalysts that have the structure of
formula (I), two of the substituents are taken together to form a
bidentate ligand or a tridentate ligand. Examples of bidentate
ligands include, but are not limited to, bisphosphines,
dialkoxides, alkyldiketonates, and aryldiketonates. Specific
examples include --P(Ph).sub.2CH.sub.2CH.sub.2P(Ph).sub.2-,
--As(Ph).sub.2CH.sub.2CH.sub.2As(Ph.sub.2)-,
--P(Ph).sub.2CH.sub.2CH.sub.2C(CF.sub.3).sub.2O--, binaphtholate
dianions, pinacolate dianions,
--P(CH.sub.3).sub.2(CH.sub.2).sub.2P(CH.sub.3).sub.2--, and
--OC(CH.sub.3).sub.2(CH.sub.3).sub.2CO--. Preferred bidentate
ligands are --P(Ph).sub.2CH.sub.2CH.sub.2P(Ph).sub.2- and
--P(CH.sub.3).sub.2(CH.sub.2).sub.2P(CH.sub.3).sub.2--. Tridentate
ligands include, but are not limited to,
(CH.sub.3).sub.2NCH.sub.2CH.sub.2P(Ph)CH.sub.2CH.sub.2N(CH.sub.3).sub.2.
Other preferred tridentate ligands are those in which any three of
X.sup.1, X.sup.2, L.sup.1, L.sup.2, L.sup.3, R.sup.1, and R.sup.2
(e.g., X.sup.1, L.sup.1, and L.sup.2) are taken together to be
cyclopentadienyl, indenyl, or fluorenyl, each optionally
substituted with C.sub.2-C.sub.20 alkenyl, C.sub.2-C.sub.20
alkynyl, C.sub.1-C.sub.20 alkyl, C.sub.5-C.sub.20 aryl,
C.sub.1-C.sub.20 alkoxy, C.sub.2-C.sub.20 alkenyloxy,
C.sub.2-C.sub.20 alkynyloxy, C.sub.6-C.sub.20 aryloxy,
C.sub.2-C.sub.20 alkoxycarbonyl, C.sub.1-C.sub.20 alkylthio,
C.sub.1-C.sub.20 alkylsulfonyl, or C.sub.1-C.sub.20 alkylsulfinyl,
each of which may be further substituted with C.sub.1-C.sub.6
alkyl, halide, C.sub.1-C.sub.6 alkoxy or with a phenyl group
optionally substituted with halide, C.sub.1-C.sub.6 alkyl, or
C.sub.1-C.sub.6 alkoxy. More preferably, in compounds of this type,
X, L.sup.1, and L.sup.2 are taken together to be cyclopentadienyl
or indenyl, each optionally substituted with vinyl,
C.sub.1-C.sub.10 alkyl, C.sub.5-C.sub.20 aryl, C.sub.1-C.sub.10
carboxylate, C.sub.2-C.sub.10 alkoxycarbonyl, C.sub.1-C.sub.10
alkoxy, or C.sub.5-C.sub.20 aryloxy, each optionally substituted
with C.sub.1-C.sub.6 alkyl, halide, C.sub.1-C.sub.6 alkoxy or with
a phenyl group optionally substituted with halide, C.sub.1-C.sub.6
alkyl or C.sub.1-C.sub.6 alkoxy. Most preferably, X, L.sup.1 and
L.sup.2 may be taken together to be cyclopentadienyl, optionally
substituted with vinyl, hydrogen, methyl, or phenyl. Tetradentate
ligands include, but are not limited to
O.sub.2C(CH.sub.2).sub.2P(Ph)(CH.sub.2).sub.2P(Ph)(CH.sub.2).sub.2CO.sub.-
2, phthalocyanines, and porphyrins.
[0301] Complexes wherein Y is coordinated to the metal are examples
of a fifth group of catalysts, and are commonly called
"Grubbs-Hoveyda" catalysts. Grubbs-Hoveyda metathesis-active metal
carbene complexes may be described by the formula (VII)
##STR00018##
wherein,
[0302] M is a Group 8 transition metal, particularly Ru or Os, or,
more particularly, Ru;
[0303] X.sup.1, X.sup.2, and L.sup.1 are as previously defined
herein for the first and second groups of catalysts;
[0304] Y is a heteroatom selected from N, O, S, and P; preferably Y
is O or N;
[0305] R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are each,
independently, selected from the group consisting of hydrogen,
halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom
containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy,
aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio,
aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl,
alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl,
perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano,
isocyanate, hydroxyl, ester, ether, amine, imine, amide,
halogen-substituted amide, trifluoroamide, sulfide, disulfide,
sulfonate, carbamate, silane, siloxane, phosphine, phosphate,
borate, or -A-Fn, wherein "A" and Fn have been defined above; and
any combination of Y, Z, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 can
be linked to form one or more cyclic groups;
[0306] n is 0, 1, or 2, such that n is 1 for the divalent
heteroatoms 0 or S, and n is 2 for the trivalent heteroatoms N or
P; and
[0307] Z is a group selected from hydrogen, alkyl, aryl,
functionalized alkyl, functionalized aryl where the functional
group(s) may independently be one or more or the following: alkoxy,
aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate,
cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide,
trifluoroamide, sulfide, disulfide, carbamate, silane, siloxane,
phosphine, phosphate, or borate; methyl, isopropyl, sec-butyl,
t-butyl, neopentyl, benzyl, phenyl and trimethylsilyl; and wherein
any combination or combinations of X.sup.1, X.sup.2, L.sup.1, Y, Z,
R.sup.5, R.sup.6, R.sup.7, and R.sup.8 may be linked to a support.
Additionally, R.sup.5, R.sup.6, R.sup.7, R.sup.8, and Z may
independently be thioisocyanate, cyanato, or thiocyanato.
[0308] Examples of complexes comprising Grubbs-Hoveyda ligands
suitable in the invention include:
##STR00019##
wherein, L.sup.1, X.sup.1, X.sup.2, and M are as described for any
of the other groups of catalysts. Suitable chelating carbenes and
carbene precursors are further described by Pederson et al. (U.S.
Pat. Nos. 7,026,495 and 6,620,955, the disclosures of both of which
are incorporated herein by reference) and Hoveyda et al. (U.S. Pat.
No. 6,921,735 and WO0214376, the disclosures of both of which are
incorporated herein by reference).
[0309] Other useful complexes include structures wherein L.sup.2
and R.sup.2 according to formulae (I), (III), or (V) are linked,
such as styrenic compounds that also include a functional group for
attachment to a support. Examples in which the functional group is
a trialkoxysilyl functionalized moiety include, but are not limited
to, the following:
##STR00020## ##STR00021##
[0310] Further examples of complexes having linked ligands include
those having linkages between a neutral NHC ligand and an anionic
ligand, a neutral NHC ligand and an alkylidine ligand, a neutral
NHC ligand and an L.sup.2 ligand, a neutral NHC ligand and an
L.sup.3 ligand, an anionic ligand and an alkylidine ligand, and any
combination thereof. While the possible structures are too numerous
to list herein, some suitable structures based on formula (III)
include:
##STR00022## ##STR00023##
[0311] In addition to the catalysts that have the structure of
formula (I), as described above, other transition metal carbene
complexes include, but are not limited to:
[0312] neutral ruthenium or osmium metal carbene complexes
containing metal centers that are formally in the +2 oxidation
state, have an electron count of 16, are penta-coordinated, and are
of the general formula (IX);
[0313] neutral ruthenium or osmium metal carbene complexes
containing metal centers that are formally in the +2 oxidation
state, have an electron count of 18, are hexa-coordinated, and are
of the general formula (X);
[0314] cationic ruthenium or osmium metal carbene complexes
containing metal centers that are formally in the +2 oxidation
state, have an electron count of 14, are tetra-coordinated, and are
of the general formula (XI); and
[0315] cationic ruthenium or osmium metal carbene complexes
containing metal centers that are formally in the +2 oxidation
state, have an electron count of 14 or 16, are tetra-coordinated or
penta-coordinated, respectively, and are of the general formula
(XII)
##STR00024##
wherein:
[0316] M, X.sup.1, X.sup.2, L.sup.1, L.sup.2, L.sup.3, R.sup.1, and
R.sup.2 are as defined for any of the previously defined four
groups of catalysts;
[0317] r and s are independently zero or 1;
[0318] t is an integer in the range of zero to 5;
[0319] k is an integer in the range of zero to 1;
[0320] Y is any non-coordinating anion (e.g., a halide ion,
BF.sub.4.sup.-, etc.);
[0321] Z.sup.1 and Z.sup.2 are independently selected from --O--,
--S--, --NR.sup.2--, --PR.sup.2--, --P(.dbd.O)R.sup.2--,
--P(OR.sup.2)--, --P(.dbd.O)(OR.sup.2)--, --C(.dbd.O)--,
--C(.dbd.O)O--, --OC(.dbd.O)--, --OC(.dbd.O)O--, --S(.dbd.O)--,
--S(.dbd.O).sub.2--, -, and an optionally substituted and/or
optionally heteroatom-containing C.sub.1-C.sub.20 hydrocarbylene
linkage;
[0322] Z.sup.3 is any cationic moiety such as
--P(R.sup.2).sub.3.sup.+ or --N(R.sup.2).sub.3.sup.+; and
[0323] any two or more of X.sup.1, X.sup.2, L.sup.1, L.sup.2,
L.sup.3, Z.sup.1, Z.sup.2, Z.sup.3, R.sup.1, and R.sup.2 may be
taken together to form a cyclic group, e.g., a multidentate ligand,
and wherein any one or more of X.sup.1, X.sup.2, L.sup.1, L.sup.2,
L.sup.3, Z.sup.1, Z.sup.2, Z.sup.3, R.sup.1, and R.sup.2 may be
attached to a support.
[0324] Additionally, another group of metal carbene olefin
metathesis catalysts that may be used in the invention disclosed
herein, is a Group 8 transition metal complex having the structure
of formula (XIII):
##STR00025##
wherein M is a Group 8 transition metal, particularly ruthenium or
osmium, or more particularly, ruthenium;
[0325] X.sup.1, X.sup.2, L.sup.1 and L.sup.2 are as defined for the
first and second groups of catalysts defined above; and
[0326] R.sup.G1, R.sup.G2, R.sup.G3, R.sup.G4, R.sup.G5, and
R.sup.G6 are each independently selected from the group consisting
of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl,
heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy,
alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino,
alkylthio, aminosulfonyl, monoalkylaminosulfonyl,
dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl,
trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde,
nitrate, cyano, isocyanate, thioisocyanate, cyanato, thiocyanato,
hydroxyl, ester, ether, thioether, amine, alkylamine, imine, amide,
halogen-substituted amide, trifluoroamide, sulfide, disulfide,
sulfonate, carbamate, silane, siloxane, phosphine, phosphate,
borate, or -A-Fn, wherein "A" is a divalent hydrocarbon moiety
selected from alkylene and arylalkylene, wherein the alkyl portion
of the alkylene and arylalkylene groups can be linear or branched,
saturated or unsaturated, cyclic or acyclic, and substituted or
unsubstituted, wherein the aryl portion of the arylalkylene can be
substituted or unsubstituted, and wherein hetero atoms and/or
functional groups may be present in either the aryl or the alkyl
portions of the alkylene and arylalkylene groups, and Fn is a
functional group, or any one or more of the R.sup.G1, R.sup.G2,
R.sup.G3, R.sup.G4, R.sup.G5, and R.sup.G6 may be linked together
to form a cyclic group, or any one or more of the R.sup.G1,
R.sup.G2, R.sup.G3, R.sup.G4, R.sup.G5, and R.sup.G6 may be
attached to a support.
[0327] Additionally, one preferred embodiment of the Group 8
transition metal complex of formula XIII is a Group 8 transition
metal complex of formula (XIV):
##STR00026##
wherein M, X.sup.1, X.sup.2, L.sup.1, L.sup.2, are as defined above
for Group 8 transition metal complex of formula XIII; and
[0328] R.sup.G7, R.sup.G8, R.sup.G9, R.sup.G10, R.sup.G11,
R.sup.G12, R.sup.G13, R.sup.G14, R.sup.G15 and R.sup.G16 are as
defined above for R.sup.G1, R.sup.G2, R.sup.G3, R.sup.G4, R.sup.G5,
and R.sup.G6 for Group 8 transition metal complex of formula XIII
or any one or more of the R.sup.G7, R.sup.G8, R.sup.G9, R.sup.G10,
R.sup.G11, R.sup.G12, R.sup.G13, R.sup.G14, R.sup.G15 and R.sup.G16
may be linked together to form a cyclic group, or any one or more
of the R.sup.G7, R.sup.G8, R.sup.G9, R.sup.G10, R.sup.G11,
R.sup.G12, R.sup.G13, R.sup.G14, R.sup.G15 and R.sup.G16 may be
attached to a support.
[0329] Additionally, another preferred embodiment of the Group 8
transition metal complex of formula XIII is a Group 8 transition
metal complex of formula (XV):
##STR00027##
wherein M, X.sup.1, X.sup.2, L.sup.1, L.sup.2, are as defined above
for Group 8 transition metal complex of formula XIII.
[0330] Additionally, another group of olefin metathesis catalysts
that may be used in the invention disclosed herein, is a Group 8
transition metal complex comprising a Schiff base ligand having the
structure of formula (XVI):
##STR00028##
wherein M is a Group 8 transition metal, particularly ruthenium or
osmium, or more particularly, ruthenium;
[0331] X.sup.1, and L.sup.1 are as defined for the first and second
groups of catalysts defined above;
[0332] Z is selected from the group consisting of oxygen, sulfur,
selenium, NR.sup.J11, PR.sup.J11, AsR.sup.J11, and SbR.sup.J11;
and
[0333] R.sup.J1, R.sup.J2, R.sup.J3, R.sup.J4, R.sup.J5, R.sup.J6,
R.sup.J7, R.sup.J8, R.sup.J9, R.sup.J10, and R.sup.J11 are each
independently selected from the group consisting of hydrogen,
halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom
containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy,
aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio,
aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl,
alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl,
perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano,
isocyanate, thioisocyanate, cyanato, thiocyanato, hydroxyl, ester,
ether, thioether, amine, alkylamine, imine, amide,
halogen-substituted amide, trifluoroamide, sulfide, disulfide,
sulfonate, carbamate, silane, siloxane, phosphine, phosphate,
borate, or -A-Fn, wherein "A" is a divalent hydrocarbon moiety
selected from alkylene and arylalkylene, wherein the alkyl portion
of the alkylene and arylalkylene groups can be linear or branched,
saturated or unsaturated, cyclic or acyclic, and substituted or
unsubstituted, wherein the aryl portion of the arylalkylene can be
substituted or unsubstituted, and wherein hetero atoms and/or
functional groups may be present in either the aryl or the alkyl
portions of the alkylene and arylalkylene groups, and Fn is a
functional group, or any one or more of the R.sup.J1, R.sup.J2,
R.sup.J3, R.sup.J4, R.sup.J5, R.sup.J6, R.sup.J7, R.sup.J8,
R.sup.J9, R.sup.J10, and R.sup.J11 may be linked together to form a
cyclic group, or any one or more of the R.sup.J1, R.sup.J2,
R.sup.J3, R.sup.J4, R.sup.J5, R.sup.J6, R.sup.J7, R.sup.J8,
R.sup.J9, R.sup.J10, and R.sup.J11 may be attached to a
support.
[0334] Additionally, one preferred embodiment of the Group 8
transition metal complex of formula (XVI) is a Group 8 transition
metal complex comprising a Schiff base ligand having the structure
of formula (XVII):
##STR00029##
[0335] wherein M, X.sup.1, L.sup.1, Z, R.sup.J7, R.sup.J8,
R.sup.J9, R.sup.J10, and R.sup.J11 are as defined above for Group 8
transition metal complex of formula XVI; and
[0336] R.sup.J12, R.sup.J13, R.sup.J14, R.sup.J15, R.sup.J16,
R.sup.J17, R.sup.J18, R.sup.J19, R.sup.J20, and R.sup.J21 are as
defined above for R.sup.J1, R.sup.J2, R.sup.J3, R.sup.J4, R.sup.J5,
and R.sup.J6 for Group 8 transition metal complex of formula XVI,
or any one or more of the R.sup.J7, R.sup.J8, R.sup.J9, R.sup.J10,
R.sup.J11, R.sup.J12, R.sup.J13, R.sup.J14, R.sup.J15, R.sup.J16,
R.sup.J17, R.sup.J18, R.sup.J19, R.sup.J20, and R.sup.J21 may be
linked together to form a cyclic group, or any one or more of the
R.sup.J7, R.sup.J8, R.sup.J9, R.sup.J10, R.sup.J11, R.sup.J12,
R.sup.J13, R.sup.J14, R.sup.J15, R.sup.J16, R.sup.J17, R.sup.J18,
R.sup.J19, R.sup.J20, and R.sup.J21 may be attached to a
support.
[0337] Additionally, another preferred embodiment of the Group 8
transition metal complex of formula (XVI) is a Group 8 transition
metal complex comprising a Schiff base ligand having the structure
of formula (XVIII):
##STR00030##
wherein M, X.sup.1, L.sup.1, Z, R.sup.J7, R.sup.J8, R.sup.J9,
R.sup.J10, R.sup.J11, are as defined above for Group 8 transition
metal complex of formula (XVI).
[0338] Additionally, another group of olefin metathesis catalysts
that may be used in the invention disclosed herein, is a Group 8
transition metal complex comprising a Schiff base ligand having the
structure of formula (XIX):
##STR00031##
wherein M is a Group 8 transition metal, particularly ruthenium or
osmium, or more particularly, ruthenium;
[0339] X.sup.1, L.sup.1, R.sup.1, and R.sup.2 are as defined for
the first and second groups of catalysts defined above;
[0340] Z is selected from the group consisting of oxygen, sulfur,
selenium, NR.sup.K5, PR.sup.K5, AsR.sup.K5, and SbR.sup.K5; [0341]
m is 0, 1, or 2; and
[0342] R.sup.K1, R.sup.K2, R.sup.K3, R.sup.K4, and R.sup.K5 are
each independently selected from the group consisting of hydrogen,
halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom
containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy,
aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio,
aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl,
alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl,
perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano,
isocyanate, thioisocyanate, cyanato, thiocyanato, hydroxyl, ester,
ether, thioether, amine, alkylamine, imine, amide,
halogen-substituted amide, trifluoroamide, sulfide, disulfide,
sulfonate, carbamate, silane, siloxane, phosphine, phosphate,
borate, or -A-Fn, wherein "A" is a divalent hydrocarbon moiety
selected from alkylene and arylalkylene, wherein the alkyl portion
of the alkylene and arylalkylene groups can be linear or branched,
saturated or unsaturated, cyclic or acyclic, and substituted or
unsubstituted, wherein the aryl portion of the arylalkylene can be
substituted or unsubstituted, and wherein hetero atoms and/or
functional groups may be present in either the aryl or the alkyl
portions of the alkylene and arylalkylene groups, and Fn is a
functional group, or any one or more of the R.sup.K1, R.sup.K2,
R.sup.K3, R.sup.K4, and R.sup.K5 may be linked together to form a
cyclic group, or any one or more of the R.sup.K1, R.sup.K2,
R.sup.K3, R.sup.K4, and R.sup.K5 may be attached to a support.
[0343] In addition, catalysts of formulas (XVI) to (XIX) may be
optionally contacted with an activating compound, where at least
partial cleavage of a bond between the Group 8 transition metal and
at least one Schiff base ligand occurs, wherein the activating
compound is either a metal or silicon compound selected from the
group consisting of copper (I) halides; zinc compounds of the
formula Zn(R.sup.Y1).sub.2, wherein R.sup.Y1 is halogen,
C.sub.1-C.sub.7 alkyl or aryl; tin compounds represented by the
formula SnR.sup.Y2R.sup.Y3R.sup.Y4R.sup.Y5 wherein each of
R.sup.Y2, R.sup.Y3, R.sup.Y4 and R.sup.Y5 is independently selected
from the group consisting of halogen, C.sub.1-C.sub.20 alkyl,
C.sub.3-C.sub.10 cycloalkyl, aryl, benzyl and C.sub.2-C.sub.7
alkenyl; and silicon compounds represented by the formula
SiR.sup.Y6R.sup.Y7R.sup.Y8R.sup.Y9 wherein each of R.sup.Y6,
R.sup.Y7, R.sup.Y8, R.sup.Y9 is independently selected from the
group consisting of hydrogen, halogen, C.sub.1-C.sub.20 alkyl,
halo, C.sub.1-C.sub.7 alkyl, aryl, heteroaryl, and vinyl. In
addition, catalysts of formulas (XVI) to (XIX) may be optionally
contacted with an activating compound where at least partial
cleavage of a bond between the Group 8 transition metal and at
least one Schiff base ligand occurs, wherein the activating
compound is an inorganic acid such as hydrogen iodide, hydrogen
bromide, hydrogen chloride, hydrogen fluoride, sulfuric acid,
nitric acid, iodic acid, periodic acid, perchloric acid, HOClO,
HOClO.sub.2 and HOIO.sub.3. In addition, catalysts of formulas
(XVI) to (XIX) may be optionally contacted with an activating
compound where at least partial cleavage of a bond between the
Group 8 transition metal and at least one Schiff base ligand
occurs, wherein the activating compound is an organic acid such as
sulfonic acids including but not limited to methanesulfonic acid,
aminobenzenesulfonic acid, benzenesulfonic acid, napthalenesulfonic
acid, sulfanilic acid and trifluoromethanesulfonic acid;
monocarboxylic acids including but not limited to acetoacetic acid,
barbituric acid, bromoacetic acid, bromobenzoic acid, chloroacetic
acid, chlorobenzoic acid, chlorophenoxyacetic acid, chloropropionic
acid, cis-cinnamic acid, cyanoacetic acid, cyanobutyric acid,
cyanophenoxyacetic acid, cyanopropionic acid, dichloroacetic acid,
dichloroacetylacetic acid, dihydroxybenzoic acid, dihydroxymalic
acid, dihydroxytartaric acid, dinicotinic acid, diphenylacetic
acid, fluorobenzoic acid, formic acid, furancarboxylic acid, furoic
acid, glycolic acid, hippuric acid, iodoacetic acid, iodobenzoic
acid, lactic acid, lutidinic acid, mandelic acid, .alpha.-naphtoic
acid, nitrobenzoic acid, nitrophenylacetic acid, o-phenylbenzoic
acid, thioacetic acid, thiophene-carboxylic acid, trichloroacetic
acid, and trihydroxybenzoic acid; and other acidic substances such
as but not limited to picric acid and uric acid.
[0344] In addition, other examples of catalysts that may be used
with the present invention are located in the following
disclosures, each of which is incorporated herein by reference,
U.S. Pat. Nos. 7,687,635; 7,671,224; 6,284,852; 6,486,279; and
5,977,393; International Publication Number WO2010/037550; and U.S.
patent application Ser. Nos. 12/303,615; 10/590,380; 11/465,651
(Publication No.: US 2007/0043188); and Ser. No. 11/465,651
(Publication No.: US 2008/0293905 Corrected Publication); and
European Pat. Nos. EP1757613B1 and EP1577282B1.
[0345] Non-limiting examples of catalysts that may be used to
prepare supported complexes and in the reactions disclosed herein
include the following, some of which for convenience are identified
throughout this disclosure by reference to their molecular
weight:
##STR00032## ##STR00033## ##STR00034## ##STR00035## ##STR00036##
##STR00037## ##STR00038## ##STR00039## ##STR00040## ##STR00041##
##STR00042## ##STR00043## ##STR00044##
[0346] In the foregoing molecular structures and formulae, Ph
represents phenyl, Cy represents cyclohexyl, Cp represents
cyclopentyl, Me represents methyl, Bu represents n-butyl, t-Bu
represents tert-butyl, i-Pr represents isopropyl, py represents
pyridine (coordinated through the N atom), Mes represents mesityl
(i.e., 2,4,6-trimethylphenyl), DiPP and DIPP represents
2,6-diisopropylphenyl, and MiPP represents 2-isopropylphenyl.
[0347] Further examples of catalysts useful to prepare supported
complexes and in the reactions disclosed herein include the
following: ruthenium (II)
dichloro(3-methyl-2-butenylidene)bis(tricyclopentylphosphine)
(C716); ruthenium (II)
dichloro(3-methyl-2-butenylidene)bis(tricyclohexylphosphine)
(C801); ruthenium (II)
dichloro(phenylmethylene)bis(tricyclohexylphosphine) (C823);
ruthenium (II)
(1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmet-
hylene)(triphenylphosphine) (C830); ruthenium (II)
dichloro(phenylvinylidene)bis(tricyclohexylphosphine) (C835);
ruthenium (II)
dichloro(tricyclohexylphosphine)(o-isopropoxyphenylmethylene)
(C601); ruthenium (II) (1,3-bis-(2,
4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)bis(3-
-bromopyridine) (C884);
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(o-isoprop-
oxyphenylmethylene)ruthenium(II) (C627);
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(benzylide-
ne)(triphenylphosphine)ruthenium(II) (C831);
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(benzylide-
ne)(methyldiphenylphosphine)ruthenium(II) (C769);
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(benzylide-
ne)(tricyclohexylphosphine)ruthenium(II) (C848);
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(benzylide-
ne)(diethylphenylphosphine)ruthenium(II) (C735);
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(benzylide-
ne)(tri-n-butylphosphine)ruthenium(II) (C771);
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl--
2-butenylidene)(triphenylphosphine)ruthenium(II) (C809);
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl--
2-butenylidene)(methyldiphenylphosphine)ruthenium(II) (C747);
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl--
2-butenylidene) (tricyclohexylphosphine)ruthenium(II) (C827);
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl--
2-butenylidene)(diethylphenylphosphine)ruthenium(II) (C713);
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl--
2-butenylidene)(tri-n-butylphosphine)ruthenium(II) (C749);
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylind-
enylidene)(triphenylphosphine)ruthenium(II) (C931);
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylind-
enylidene)(methylphenylphosphine)ruthenium(II) (C869);
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylind-
enylidene)(tricyclohexylphosphine)ruthenium(II) (C949);
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylind-
enylidene)(diethylphenylphosphine)ruthenium(II) (C835); and
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylind-
enylidene)(tri-n-butylphosphine)ruthenium(II) (C871).
[0348] Still further catalysts useful in ROMP reactions, and/or in
other metathesis reactions, such as ring-closing metathesis, cross
metathesis, ring-opening cross metathesis, self-metathesis,
ethenolysis, alkenolysis, acyclic diene metathesis polymerization,
and combinations thereof, include the following structures:
##STR00045## ##STR00046## ##STR00047##
[0349] In general, the transition metal complexes used as catalysts
herein can be prepared by several different methods, such as those
described by Schwab et al. (1996) J. Am. Chem. Soc. 118:100-110,
Scholl et al. (1999) Org. Lett. 6:953-956, Sanford et al. (2001) J.
Am. Chem. Soc. 123:749-750, U.S. Pat. No. 5,312,940, and U.S. Pat.
No. 5,342,909, the disclosures of each of which are incorporated
herein by reference. Also see U.S. Pat. Pub. No. 2003/0055262 to
Grubbs et al., WO 02/079208, and U.S. Pat. No. 6,613,910 to Grubbs
et al., the disclosures of each of which are incorporated herein by
reference. Preferred synthetic methods are described in WO
03/11455A1 to Grubbs et al., the disclosure of which is
incorporated herein by reference.
[0350] Preferred metal carbene olefin metathesis catalysts are
Group 8 transition metal complexes having the structure of formula
(I) commonly called "First Generation Grubbs" catalysts, formula
(III) commonly called "Second Generation Grubbs" catalysts, or
formula (VII) commonly called "Grubbs-Hoveyda" catalysts.
[0351] More preferred metal carbene olefin metathesis catalysts
have the structure of formula (I)
##STR00048##
in which:
[0352] M is a Group 8 transition metal;
[0353] L.sup.1, L.sup.2, and L.sup.3 are neutral electron donor
ligands;
[0354] n is 0 or 1;
[0355] m is 0, 1, or 2;
[0356] k is 0 or 1;
[0357] X.sup.1 and X.sup.2 are anionic ligands;
[0358] R.sup.1 and R.sup.2 are independently selected from
hydrogen, hydrocarbyl, substituted hydrocarbyl,
heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, and functional groups,
[0359] wherein any two or more of X.sup.1, X.sup.2, L.sup.1,
L.sup.2, L.sup.3, R.sup.1, and R.sup.2 can be taken together to
form one or more cyclic groups, and further wherein any one or more
of X.sup.1, X.sup.2, L.sup.1, L.sup.2, L.sup.3, R.sup.1, and
R.sup.2 may be attached to a support;
and formula (VII)
##STR00049##
wherein,
[0360] M is a Group 8 transition metal;
[0361] L.sup.1 is a neutral electron donor ligand;
[0362] X.sup.1 and X.sup.2 are anionic ligands;
[0363] Y is a heteroatom selected from 0 or N;
[0364] R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are independently
selected from hydrogen, hydrocarbyl, substituted hydrocarbyl,
heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, and functional groups;
[0365] n is 0, 1, or 2; and
[0366] Z is selected from hydrogen, hydrocarbyl, substituted
hydrocarbyl, heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, and functional groups,
[0367] wherein any combination of Y, Z, R.sup.5, R.sup.6, R.sup.7,
and R.sup.8 can be linked to form one or more cyclic groups, and
further wherein any combination of X.sup.1, X.sup.2, L.sup.1, Y, Z,
R.sup.5, R.sup.6, R.sup.7, and R.sup.8 may be attached to a
support.
[0368] Most preferred metal carbene olefin metathesis catalysts
have the structure of formula (I)
##STR00050##
in which:
[0369] M is ruthenium;
[0370] n is 0;
[0371] m is 0;
[0372] k is 1;
[0373] L.sup.1 and L.sup.2 are trisubstituted phosphines
independently selected from the group consisting of
tri-n-butylphosphine (Pn-Bu.sub.3), tricyclopentylphosphine
(PCp.sub.3), tricyclohexylphosphine (PCy.sub.3),
triisopropylphosphine (P-i-Pr.sub.3), triphenylphosphine
(PPh.sub.3), methyldiphenylphosphine (PMePh.sub.2),
dimethylphenylphosphine (PMe.sub.2Ph), and diethylphenylphosphine
(PEt.sub.2Ph); or L.sup.1 is an N-heterocyclic carbene selected
from the group consisting of
1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene,
1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene,
1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and
1,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene and L.sup.2 is a
trisubstituted phosphine selected from the group consisting of
tri-n-butylphosphine (Pn-Bu.sub.3), tricyclopentylphosphine
(PCp.sub.3), tricyclohexylphosphine (PCy.sub.3),
triisopropylphosphine (P-i-Pr.sub.3), triphenylphosphine
(PPh.sub.3), methyldiphenylphosphine (PMePh.sub.2),
dimethylphenylphosphine (PMe.sub.2Ph), and diethylphenylphosphine
(PEt.sub.2Ph);
[0374] X.sup.1 and X.sup.2 are chloride;
[0375] R.sup.1 is hydrogen and R.sup.2 is phenyl or
--CH.dbd.C(CH.sub.3).sub.2 or thienyl; or R.sup.1 and R.sup.2 are
taken together to form 3-phenyl-1H-indene;
and formula (VII)
##STR00051##
wherein,
[0376] M is ruthenium;
[0377] L.sup.1 is a trisubstituted phosphine selected from the
group consisting of tri-n-butylphosphine (Pn-Bu.sub.3),
tricyclopentylphosphine (PCp.sub.3), tricyclohexylphosphine
(PCy.sub.3), triisopropylphosphine (P-i-Pr.sub.3),
triphenylphosphine (PPh.sub.3), methyldiphenylphosphine
(PMePh.sub.2), dimethylphenylphosphine (PMe.sub.2Ph), and
diethylphenylphosphine (PEt.sub.2Ph); or L.sup.1 is an
N-heterocyclic carbene selected from the group consisting of
1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene,
1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene,
1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and
1,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene;
[0378] X.sup.1 and X.sup.2 are chloride;
[0379] Y is oxygen;
[0380] R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are each
hydrogen;
[0381] n is 1; and
[0382] Z is isopropyl.
[0383] Suitable supports for any of the catalysts described herein
may be of synthetic, semi-synthetic, or naturally occurring
materials, which may be organic or inorganic, e.g., polymeric,
ceramic, or metallic. Attachment to the support will generally,
although not necessarily, be covalent, and the covalent linkage may
be direct or indirect. Indirect covalent linkages are typically,
though not necessarily, through a functional group on a support
surface. Ionic attachments are also suitable, including
combinations of one or more anionic groups on the metal complexes
coupled with supports containing cationic groups, or combinations
of one or more cationic groups on the metal complexes coupled with
supports containing anionic groups.
[0384] When utilized, suitable supports may be selected from
silicas, silicates, aluminas, aluminum oxides, silica-aluminas,
aluminosilicates, zeolites, titanias, titanium dioxide, magnetite,
magnesium oxides, boron oxides, clays, zirconias, zirconium
dioxide, carbon, polymers, cellulose, cellulosic polymers amylose,
amylosic polymers, or a combination thereof. The support preferably
comprises silica, a silicate, or a combination thereof.
[0385] In certain embodiments, it is also possible to use a support
that has been treated to include functional groups, inert moieties,
and/or excess ligands. Any of the functional groups described
herein are suitable for incorporation on the support, and may be
generally accomplished through techniques known in the art. Inert
moieties may also be incorporated on the support to generally
reduce the available attachment sites on the support, e.g., in
order to control the placement, or amount, of a complex linked to
the support.
[0386] The catalyst compositions comprising at least one metal
carbene olefin metathesis catalyst may be utilized in olefin
metathesis reactions according to techniques known in the art. The
catalyst compositions comprising at least one metal carbene olefin
metathesis catalyst are typically added to the resin composition as
a solid, a solution, or as a suspension. When the catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst is added to the resin composition as a suspension, the at
least one metal carbene olefin metathesis catalyst is suspended in
a dispersing carrier such as mineral oil, paraffin oil, soybean
oil, tri-isopropylbenzene, or any hydrophobic liquid which has a
sufficiently high viscosity so as to permit effective dispersion of
the catalyst(s), and which is sufficiently inert and which has a
sufficiently high boiling point so that is does not act as a
low-boiling impurity in the olefin metathesis reaction. It will be
appreciated that the amount of catalyst that is used (i.e., the
"catalyst loading") in the reaction is dependent upon a variety of
factors such as the identity of the reactants and the reaction
conditions that are employed. It is therefore understood that
catalyst loading may be optimally and independently chosen for each
reaction. In general, however, the catalyst will be present in an
amount that ranges from a low of about 0.1 ppm, 1 ppm, or 5 ppm, to
a high of about 10 ppm, 15 ppm, 25 ppm, 50 ppm, 100 ppm, 200 ppm,
500 ppm, or 1000 ppm relative to the amount of an olefinic
substrate.
[0387] The catalyst will generally be present in an amount that
ranges from a low of about 0.00001 mol %, 0.0001 mol %, or 0.0005
mol %, to a high of about 0.001 mol %, 0.0015 mol %, 0.0025 mol %,
0.005 mol %, 0.01 mol %, 0.02 mol %, 0.05 mol %, or 0.1 mol %
relative to the olefinic substrate.
[0388] When expressed as the molar ratio of monomer to catalyst,
the catalyst (the "monomer to catalyst ratio"), loading will
generally be present in an amount that ranges from a low of about
10,000,000:1, 1,000,000:1, or 200,00:1, to a high of about
100,000:1 66,667:1, 40,000:1, 20,000:1, 10,000:1, 5,000:1, or
1,000:1.
Cyclic Olefin (Resin) Compositions, Articles, and Insulated
Objects
[0389] Resin compositions of the present invention comprise a
cyclic olefin composition. For example, in one embodiment a resin
composition according to the present invention comprises a cyclic
olefin composition, wherein the cyclic olefin composition comprise
10.0 mol % to 80.0 mol % of at least one cyclic olefin containing
multiunsaturation, and up to 90.0 mol % of at least one cyclic
olefin containing monounsaturation, wherein the at least one cyclic
olefin containing multiunsaturation may be substituted or
unsubstituted, and wherein the at least one cyclic olefin
containing monounsaturation may be substituted or unsubstituted,
and wherein the substituents are independently selected from
hydrogen, hydrocarbyl, substituted hydrocarbyl,
heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, --(Z*).sub.n-Fn where n is zero
or 1, Z* and Fn, and functional groups (Fn). Other embodiments of
cyclic olefin resin compositions may be used to in resin
compositions of the invention herein as well. Additionally, resin
compositions of the invention may also comprise at least one
substrate material. Additionally, resin compositions according to
the invention may also comprise at least one adhesion promoter,
where the resin composition is combined with a catalyst composition
comprising at least one olefin metathesis catalyst to form a ROMP
composition, and the resulting ROMP composition is applied to at
least one substrate material. Additionally, resin compositions
according to the invention may also comprise a cyclic olefin
composition and at least one adhesion promoter comprising at least
one compound containing at least two isocyanate groups, where the
resin composition is combined with at least one olefin metathesis
catalyst, and the resulting ROMP composition is applied to at least
one substrate material, wherein the substrate material may be
functionalized substrate material, such as, for example, a
heteroatom-functionalized substrate, such as, for example, an
amino-functionalized substrate. Additionally, resin compositions
according to the invention may also comprise at least one adhesion
promoter comprising at least one compound containing at least two
isocyanate groups, where the resin composition is combined with at
least olefin metathesis catalyst, and the resulting resin
composition is applied to at least one substrate material, such as,
for example, a glass substrate material or carbon substrate
material. In another embodiment, resin compositions, particularly
ROMP compositions according to the invention comprise at a cyclic
olefin composition, at least one olefin metathesis catalyst, at
least one adhesion promoter comprising at least one compound
containing at least two isocyanate groups, and at least one
heteroatom-functionalized substrate material.
[0390] The amounts of the adhesion promoter in the resin
composition may vary over a wide range and may vary depending on
the manufacturing operation or the particular end-use application.
Generally, any level of adhesion promoter which produces a desired
increase in mechanical properties is of particular interest. When
formulated or combined with a resin composition, the concentration
of the adhesion promoter typically ranges from 0.001-50 phr,
particularly 0.05-10 phr, more particularly 0.1-10 phr, or even
more particularly 0.5-4.0 phr.
[0391] In particular aspects of the present invention, substrate
materials may advantageously comprise an aminosilane-treated
substrate.
[0392] In another embodiment, resin compositions according to the
invention may additionally comprise an exogenous inhibitor.
Exogenous inhibitors or "gel modification additives", for use in
the present invention are disclosed in U.S. Pat. No. 5,939,504, the
contents of which are incorporated herein by reference. In another
embodiment, resin compositions according to the invention may
additionally comprise a hydroperoxide gel modifier. Hydroperoxide
gel modifiers (e.g. cumene hydroperoxide) for use in the present
invention are disclosed in International Pat. App. No.
PCT/US2012/042850.
[0393] In another embodiment, the resin compositions according to
the invention may additionally comprise an adhesion promoter.
Adhesion promoters for use in the present invention are disclosed
in International Pat. App. No. PCT/US2012/042850.
[0394] Resin compositions of the invention may be optionally
formulated with additives. Suitable additives include, but are not
limited to, gel modifiers, hardness modulators, antioxidants,
antiozonants, stabilizers, crosslinkers, fillers, binders, coupling
agents, thixotropes, wetting agents, biocides, plasticizers,
pigments, flame retardants, dyes, fibers and reinforcement
materials, including sized reinforcements and substrates, such as
those treated with finishes, coatings, coupling agents, film
formers and/or lubricants. Furthermore, the amount of additives
present in the resin compositions may vary depending on the
particular type of additive used. The concentration of the
additives in the resin compositions typically ranges from, for
example, 0.001-85 percent by weight, particularly, from 0.1-75
percent by weight, or even more particularly, from 2-60 percent by
weight.
[0395] Resin compositions of the invention may be optionally
formulated with or without a crosslinker, for example, a
crosslinker selected from dialkyl peroxides, diacyl peroxides, and
peroxyacids.
[0396] Additionally, suitable impact modifiers or elastomers
include without limitation natural rubber, butyl rubber,
polyisoprene, polybutadiene, polyisobutylene, ethylene-propylene
copolymer, styrene-butadiene-styrene triblock rubber, random
styrene-butadiene rubber, styrene-isoprene-styrene triblock rubber,
styrene-ethylene/butylene-styrene copolymer,
styrene-ethylene/propylene-styrene copolymer,
ethylene-propylene-diene terpolymers, ethylene-vinyl acetate, and
nitrile rubbers. Preferred impact modifiers or elastomers are
polybutadiene Diene 55AC10 (Firestone), polybutadiene Diene 55AM5
(Firestone), EPDM Royalene 301T, EPDM Buna T9650 (Bayer),
styrene-ethylene/butylene-styrene copolymer Kraton G1651H, Polysar
Butyl 301 (Bayer), polybutadiene Taktene 710 (Bayer),
styrene-ethylene/butylene-styrene Kraton G1726M, Ethylene-Octene
Engage 8150 (DuPont-Dow), styrene-butadiene Kraton D1184, EPDM
Nordel 1070 (DuPont-Dow), and polyisobutylene Vistanex MML-140
(Exxon). Such materials are normally employed in the resin
composition at levels of about 0.10 phr to 10 phr, but more
preferably at levels of about 0.1 phr to 5 phr. Various polar
impact modifiers or elastomers can also be used.
[0397] Antioxidants and antiozonants include any antioxidant or
antiozonant used in the rubber or plastics industry. An "Index of
Commercial Antioxidants and Antiozonants, Fourth Edition" is
available from Goodyear Chemicals, The Goodyear Tire and Rubber
Company, Akron, Ohio 44316. Suitable stabilizers (i.e.,
antioxidants or antiozonants) include without limitation:
2,6-di-tert-butyl-4-methylphenol (BHT); styrenated phenol, such as
Wingstay.RTM. S (Goodyear); 2- and 3-tert-butyl-4-methoxyphenol;
alkylated hindered phenols, such as Wingstay C (Goodyear);
4-hydroxymethyl-2,6-di-tert-butylphenol;
2,6-di-tert-butyl-4-sec-butylphenol;
2,2'-methylenebis(4-methyl-6-tert-butylphenol);
2,2'-methylenebis(4-ethyl-6-tert-butylphenol);
4,4'-methylenebis(2,6-di-tert-butylphenol); miscellaneous
bisphenols, such as Cyanox.RTM. 53 (Cytec Industries Inc.) and
Permanax WSO; 2,2'-ethylidenebis(4,6-di-tert-butylphenol);
2,2'-methylenebis(4-methyl-6-(1-methylcyclohexyl)phenol);
4,4'-butylidenebis(6-tert-butyl-3-methylphenol); polybutylated
Bisphenol A; 4,4'-thiobis(6-tert-butyl-3-methylphenol);
4,4'-methylenebis(2,6-dimethylphenol); 1,1'-thiobis(2-naphthol);
methylene bridged polyaklylphenol, such as Ethyl antioxidant 738;
2,2'-thiobis(4-methyl-6-tert-butylphenol);
2,2'-isobutylidenebis(4,6-dimethylphenol);
2,2'-methylenebis(4-methyl-6-cyclohexylphenol); butylated reaction
product of p-cresol and dicyclopentadiene, such as Wingstay L;
tetrakis(methylene-3,5-di-tert-butyl-4-hydroxyhydrocinnamate)
methane, i.e., Irganox.RTM. 1010 (BASF);
1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,
e.g., Ethanox.RTM. 330 (Albemarle Corporation);
4,4'-methylenebis(2,6-di-tertiary-butylphenol), e.g., Ethanox 4702
or Ethanox 4710;
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, i.e.,
Good-rite.RTM. 3114 (Emerald Performance Materials),
2,5-di-tert-amylhydroquinone, tert-butylhydroquinone,
tris(nonylphenylphosphite),
bis(2,4-di-tert-butyl)pentaerythritol)diphosphite, distearyl
pentaerythritol diphosphite, phosphited phenols and bisphenols,
such as Naugard.RTM. 492 (Chemtura Corporation), phosphite/phenolic
antioxidant blends, such as Irganox B215;
di-n-octadecyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate, such
as Irganox 1093; 1,6-hexamethylene
bis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionate), such as
Irganox 259, and
octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate, i.e., Irganox
1076, tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylylenediphosp
honite, diphenylamine, and 4,4'-diemthoxydiphenylamine. Such
materials are normally employed in the resin composition at levels
of about 0.10 phr to 10 phr, but more preferably at levels of about
0.1 phr to 5 phr.
[0398] Suitable reinforcing materials include those that add to the
strength or stiffness of a polymer composite when incorporated with
the polymer. Reinforcing materials can be in the form of filaments,
fibers, rovings, mats, weaves, fabrics, knitted material, cloth, or
other known structures. Suitable reinforcement materials include
glass fibers and fabrics, carbon fibers and fabrics, aramid fibers
and fabrics, polyolefin fibers or fabrics (including ultrahigh
molecular weight polyethylene fabrics such as those produced by
Honeywell under the Spectra.RTM. trade name), and polyoxazole
fibers or fabrics (such as those produced by the Toyobo Corporation
under the Zylon.RTM. trade name). Reinforcing materials containing
surface finishes, sizings, or coatings are particularly suitable
for the described invention including Ahlstrom glass roving
(R338-2400), Johns Manville glass roving (Star ROV.RTM.-086), Owens
Corning rovings (OCV 366-AG-207, R25H-X14-2400, SE1200-207,
SE1500-2400, SE2350-250), PPG glass rovings (Hybon.RTM. 2002,
Hybon.RTM. 2026), Toho Tenax.RTM. carbon fiber tow (HTR-40), and
Zoltek carbon fiber tow (Panex.RTM. 35). Furthermore, any fabrics
prepared using reinforcing materials containing surface finishes,
sizings or coatings are suitable for the invention. Advantageously,
the invention does not require the expensive process of removing of
surface finishes, sizings, or coatings from the reinforcing
materials. Additionally, glass fibers or fabrics may include
without limitation A-glass, E-glass or S-glass, S-2 glass, C-glass,
R-glass, ECR-glass, M-glass, D-glass, and quartz, and
silica/quartz. Preferred glass fiber reinforcements are those with
finishes formulated for use with epoxy, vinyl ester, and/or
polyurethane resins. When formulated for use with a combination of
these resin types, the reinforcements are sometimes described as
"multi-compatible." Such reinforcements are generally treated
during their manufacture with organosilane coupling agents
comprising vinyl, amino, glycidoxy, or methacryloxy functional
groups (or various combinations thereof) and are coated with a
finish to protect the fiber surface and facilitate handling and
processing (e.g., spooling and weaving). Finishes typically
comprise a mixture of chemical and polymeric compounds such as film
formers, surfactants, and lubricants. Especially preferred glass
reinforcements are those containing some amount of
amino-functionalized silane coupling agent. Especially preferred
finishes are those comprising and epoxy-based and/or
polyurethane-based film formers. Examples of preferred glass-fiber
reinforcements are those based on Hybon.RTM. 2026, 2002, and 2001
(PPG) multi-compatible rovings; Ahlstrom R338 epoxysilane-sized
rovings; StarRov.RTM. 086 (Johns Manville) soft silane sized
multi-compatible rovings; OCV.TM. 366, SE 1200, and R25H (Owens
Corning) multi-compatible rovings; OCV.TM. SE 1500 and 2350 (Owens
Corning) epoxy-compatible rovings; and Jushi Group multi-compatible
glass rovings (752 type, 396 type, 312 type, 386 type). Additional
suitable polymer fibers and fabrics may include without limitation
one or more of polyester, polyamide (for example, NYLON polamide
available from E.I. DuPont, aromatic polyamide (such as KEVLAR
aromatic polyamide available from E.I. DuPont, or P84 aromatic
polyamide available from Lenzing Aktiengesellschaft), polyimide
(for example KAPTON polyimide available from E.I. DuPont,
polyethylene (for example, DYNEEMA polyethylene from Toyobo Co.,
Ltd.). Additional suitable carbon fibers may include without
limitation AS2C, AS4, AS4C, AS4D, AS7, IM6, IM7, IM9, and PV42/850
from Hexcel Corporation; TORAYCA T300, T300J, T400H, T600S, T700S,
T700G, T800H, T800S, T1000G, M35J, M40J, M46J, M50J, M55J, M60J,
M30S, M30G and M40 from Toray Industries, Inc.; HTS12K/24K, G30-500
3k/6K/12K, G30-500 12K, G30-700 12K, G30-7000 24K F402, G40-800
24K, STS 24K, HTR 40 F22 24K 1550tex from Toho Tenax, Inc.; 34-700,
34-700WD, 34-600, 34-600WD, and 34-600 unsized from Grafil Inc.;
T-300, T-650/35, T-300C, and T-650/35C from Cytec Industries.
Additionally suitable carbon fibers may include without limitation
AKSACA (A42/D011), AKSACA (A42/D012), Blue Star Starafil
(10253512-90), Blue Star Starafil (10254061-130), SGL Carbon (C30
T050 1.80), SGL Carbon (C50 T024 1.82), Grafil (347R1200U), Grafil
(THR 6014A), Grafil (THR 6014K), Hexcel Carbon (AS4C/EXP 12K),
Mitsubishi (Pyrofil TR 505 12L AF), Mitsubishi (Pyrofil TR 505 12L
AF), Toho Tenax (T700SC 12000-50C), Toray (T700SC 12000-90C),
Zoltek (Panex 35 50K, sizing 11), Zoltek (Panex 35 50K, sizing 13).
Additional suitable carbon fabrics may include without limitation
Carbon fabrics by Vectorply (C-L 1800) and Zoltek (Panex 35 UD
Fabic-PX35UD0500-1220). Additionally suitable glass fabrics may
include without limitation glass fabrics as supplied by Vectorply
(E-LT 3500-10) based on PPG Hybon.RTM. 2026; Saertex
(U14EU970-01190-T2525-125000) based on PPG Hybon.RTM. 2002;
Chongqing Polycomp Internation Corp. (CPIC.RTM. Fiberglass) (EKU
1150(0)/50-600); and Owens Corning (L1020/07A06 Xweft 200tex).
[0399] Other suitable fillers include, for example, metallic
density modulators, microparticulate density modulators, such as,
for example, microspheres, and macroparticulate density modulators,
such as, for example, glass or ceramic beads. Metallic density
modulators include, but are not limited to, powdered, sintered,
shaved, flaked, filed, particulated, or granulated metals, metal
oxides, metal nitrides, and/or metal carbides, and the like.
Preferred metallic density modulators include, among others,
tungsten, tungsten carbide, aluminum, titanium, iron, lead, silicon
oxide, aluminum oxide, boron carbide, and silicon carbide.
Microparticulate density modulators include, but are not limited
to, glass, metal, thermoplastic (either expandable or pre-expanded)
or thermoset, and/or ceramic/silicate microspheres.
Macroparticulate density modulators include, but are not limited
to, glass, plastic, or ceramic beads; metal rods, chunks, pieces,
or shot; hollow glass, ceramic, plastic, or metallic spheres,
balls, or tubes; and the like.
[0400] The invention is also directed to articles manufactured from
a resin composition comprising at least one cyclic olefin, at least
one metal carbene olefin metathesis catalyst, wherein the article
is a thermal insulation material. The invention is also directed to
articles manufactured from a resin composition comprising at least
one cyclic olefin, at least one olefin metathesis catalyst, at
least one adhesion promoter comprising at least one compound
containing at least two isocyanate groups, and at least one
substrate material, wherein the article is a thermal insulation
material. Additionally, the invention is directed to articles
manufactured from a resin composition comprising at least one
cyclic olefin, at least one olefin metathesis catalyst, and at
least one adhesion promoter comprising at least one compound
containing at least two isocyanate groups, where the resin
composition is combined with at least one olefin metathesis
catalyst, and the resulting ROMP composition is applied to at least
one substrate material, which may be, for example, a functionalized
substrate, such as, for example, a heteroatom-functionalized
substrate, such as, for example, an amino-functionalized substrate,
wherein the article is a thermal insulation material.
[0401] The invention is also directed to articles manufactured from
a resin composition comprising a cyclic olefin composition, at
least one metal carbene olefin metathesis catalyst, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation, wherein the at least one cyclic olefin containing
multiunsaturation may be substituted or unsubstituted, and wherein
the at least one cyclic olefin containing monounsaturation may be
substituted or unsubstituted, and wherein the substituents are
independently selected from hydrogen, hydrocarbyl, substituted
hydrocarbyl, heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, --(Z*).sub.n-Fn where n is zero
or 1, Z* and Fn, and functional groups (Fn), wherein the article is
a thermal insulation material. The invention is also directed to
articles manufactured from a resin composition comprising a cyclic
olefin composition, at least one olefin metathesis catalyst, at
least one adhesion promoter comprising at least one compound
containing at least two isocyanate groups, and at least one
substrate material, wherein the cyclic olefin composition comprises
10.0 mol % to 80.0 mol % of at least one cyclic olefin containing
multiunsaturation, and up to 90.0 mol % of at least one cyclic
olefin containing monounsaturation, wherein the at least one cyclic
olefin containing multiunsaturation may be substituted or
unsubstituted, and wherein the at least one cyclic olefin
containing monounsaturation may be substituted or unsubstituted,
and wherein the substituents are independently selected from
hydrogen, hydrocarbyl, substituted hydrocarbyl,
heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, --(Z*).sub.n-Fn where n is zero
or 1, Z* and Fn, and functional groups (Fn), wherein the article is
a thermal insulation material. Additionally, the invention is
directed to articles manufactured from a resin composition
comprising a cyclic olefin composition, at least one olefin
metathesis catalyst, and at least one adhesion promoter comprising
at least one compound containing at least two isocyanate groups,
wherein the cyclic olefin composition comprises 10.0 mol % to 80.0
mol % of at least one cyclic olefin containing multiunsaturation,
and up to 90.0 mol % of at least one cyclic olefin containing
monounsaturation, wherein the at least one cyclic olefin containing
multiunsaturation may be substituted or unsubstituted, and wherein
the at least one cyclic olefin containing monounsaturation may be
substituted or unsubstituted, and wherein the substituents are
independently selected from hydrogen, hydrocarbyl, substituted
hydrocarbyl, heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, --(Z*).sub.n-Fn where n is zero
or 1, Z* and Fn, and functional groups (Fn), where the resin
composition is combined with at least one olefin metathesis
catalyst, and the resulting ROMP composition is applied to at least
one substrate material, which may be, for example, a functionalized
substrate, such as, for example, a heteroatom-functionalized
substrate, such as, for example, an amino-functionalized substrate,
wherein the article is a thermal insulation material.
[0402] Additionally, the invention is directed to objects at least
partially coated with a thermal insulation material, wherein the
thermal insulation material is a ROMP polymer. Additionally, the
invention is directed to objects at least partially coated with a
thermal insulation material, wherein the thermal insulation
material is a ROMP polymer composite.
[0403] Additionally, the invention is directed to objects at least
partially coated with a thermal insulation material, wherein the
thermal insulation material is a ROMP polymer, wherein the ROMP
polymer is a reaction product of a resin composition comprising a
cyclic olefin composition and a catalyst composition comprising at
least one metal carbene olefin metathesis catalyst, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation, wherein the at least one cyclic olefin containing
multiunsaturation may be substituted or unsubstituted, and wherein
the at least one cyclic olefin containing monounsaturation may be
substituted or unsubstituted, and wherein the substituents are
independently selected from hydrogen, hydrocarbyl, substituted
hydrocarbyl, heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, --(Z*).sub.n-Fn where n is zero
or 1, Z* and Fn, and functional groups (Fn). Additionally, the
invention is directed to objects at least partially coated with a
thermal insulation material, wherein the thermal insulation
material is a ROMP polymer composite, wherein the ROMP polymer
composite is a reaction product of a resin composition comprising a
cyclic olefin composition and a catalyst composition comprising at
least one metal carbene olefin metathesis catalyst, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation, wherein the at least one cyclic olefin containing
multiunsaturation may be substituted or unsubstituted, and wherein
the at least one cyclic olefin containing monounsaturation may be
substituted or unsubstituted, and wherein the substituents are
independently selected from hydrogen, hydrocarbyl, substituted
hydrocarbyl, heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, --(Z*).sub.n-Fn where n is zero
or 1, Z* and Fn, and functional groups (Fn).
[0404] Additionally, the invention is directed to objects at least
partially encased by a thermal insulation material, wherein the
thermal insulation material is a ROMP polymer. Additionally, the
invention is directed to objects at least partially encased by a
thermal insulation material, wherein the thermal insulation
material is a ROMP polymer composite.
[0405] Additionally, the invention is directed to objects at least
partially encased by a thermal insulation material, wherein the
thermal insulation material is a ROMP polymer, wherein the ROMP
polymer is a reaction product of a resin composition comprising a
cyclic olefin composition and a catalyst composition comprising at
least one metal carbene olefin metathesis catalyst, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation, wherein the at least one cyclic olefin containing
multiunsaturation may be substituted or unsubstituted, and wherein
the at least one cyclic olefin containing monounsaturation may be
substituted or unsubstituted, and wherein the substituents are
independently selected from hydrogen, hydrocarbyl, substituted
hydrocarbyl, heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, --(Z*).sub.n-Fn where n is zero
or 1, Z* and Fn, and functional groups (Fn). Additionally, the
invention is directed to objects at least partially encased by a
thermal insulation material, wherein the thermal insulation
material is a ROMP polymer composite, wherein the ROMP polymer
composite is a reaction product of a resin composition comprising a
cyclic olefin composition and a catalyst composition comprising at
least one metal carbene olefin metathesis catalyst, wherein the
cyclic olefin composition comprises 10.0 mol % to 80.0 mol % of at
least one cyclic olefin containing multiunsaturation, and up to
90.0 mol % of at least one cyclic olefin containing
monounsaturation, wherein the at least one cyclic olefin containing
multiunsaturation may be substituted or unsubstituted, and wherein
the at least one cyclic olefin containing monounsaturation may be
substituted or unsubstituted, and wherein the substituents are
independently selected from hydrogen, hydrocarbyl, substituted
hydrocarbyl, heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, --(Z*).sub.n-Fn where n is zero
or 1, Z* and Fn, and functional groups (Fn).
[0406] Additionally, the invention is directed to a process for a
ROMP polymer coating for offshore applications, the process
comprising, providing an object surface to be at least partially
coated, providing a resin composition comprising at least one
cyclic olefin, providing a catalyst composition comprising at least
one metal carbene olefin metathesis catalyst, combining the resin
composition comprising at least one cyclic olefin and catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst to form a ROMP composition, contacting the object surface
with the ROMP composition, and subjecting the ROMP composition to
conditions effective to polymerize the ROMP composition.
[0407] Additionally, the invention is directed to a process for a
ROMP polymer coating for offshore applications, the process
comprising, providing an object surface to be at least partially
coated, providing a resin composition comprising a cyclic olefin
composition, wherein the cyclic olefin composition comprises 10.0
mol % to 80.0 mol % of at least one cyclic olefin containing
multiunsaturation, and up to 90.0 mol % of at least one cyclic
olefin containing monounsaturation, wherein the at least one cyclic
olefin containing multiunsaturation may be substituted or
unsubstituted, and wherein the at least one cyclic olefin
containing monounsaturation may be substituted or unsubstituted,
and wherein the substituents are independently selected from
hydrogen, hydrocarbyl, substituted hydrocarbyl,
heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, --(Z*).sub.n-Fn where n is zero
or 1, Z* and Fn, and functional groups (Fn), providing a catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst, combining the resin composition comprising a cyclic
olefin composition and catalyst composition comprising at least one
metal carbene olefin metathesis catalyst to form a ROMP
composition, contacting the object surface with the ROMP
composition, and subjecting the ROMP composition to conditions
effective to polymerize the ROMP composition.
[0408] Additionally, the invention is directed to a process for a
ROMP polymer coating for offshore applications, the process
comprising, providing an object surface to be at least partially
coated, providing a resin composition comprising at least one
cyclic olefin, providing a catalyst composition comprising at least
one metal carbene olefin metathesis catalyst, combining the resin
composition comprising at least one cyclic olefin and catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst to form a ROMP composition, applying the ROMP composition
to the object surface, and subjecting the ROMP composition to
conditions effective to polymerize the ROMP composition.
[0409] Additionally, the invention is directed to a process for a
ROMP polymer coating for offshore applications, the process
comprising, providing an object surface to be at least partially
coated, providing a resin composition comprising a cyclic olefin
composition, wherein the cyclic olefin composition comprises 10.0
mol % to 80.0 mol % of at least one cyclic olefin containing
multiunsaturation, and up to 90.0 mol % of at least one cyclic
olefin containing monounsaturation, wherein the at least one cyclic
olefin containing multiunsaturation may be substituted or
unsubstituted, and wherein the at least one cyclic olefin
containing monounsaturation may be substituted or unsubstituted,
and wherein the substituents are independently selected from
hydrogen, hydrocarbyl, substituted hydrocarbyl,
heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, --(Z*).sub.n-Fn where n is zero
or 1, Z* and Fn, and functional groups (Fn), providing a catalyst
composition comprising at least one metal carbene olefin metathesis
catalyst, combining the resin composition comprising a cyclic
olefin composition and catalyst composition comprising at least one
metal carbene olefin metathesis catalyst to form a ROMP
composition, applying the ROMP composition to the object surface,
and subjecting the ROMP composition to conditions effective to
polymerize the ROMP composition.
[0410] The ROMP polymers and/or ROMP polymer composites of the
invention may be applied to an object using a variety of methods
known in the art. In one method, a form or mold is placed or
constructed around the object to be insulated. The resin
composition comprising at least one cyclic olefin and the catalyst
composition comprising at least one cyclic olefin are combined to
form a ROMP composition and the ROMP composition is the applied
between the object and the mold and the ROMP composition is then
subjected to conditions effective to cure the ROMP composition.
Once the ROMP composition has cured, the mold is removed.
[0411] The application of the ROMP composition to the object
surface to be at least partially coated is carried out by methods
known in the art, examples include, but are not limited to casting,
centrifugal casting, pultrusion, molding, rotational molding, open
molding, reaction injection molding (RIM), resin transfer molding
(RTM), pouring, vacuum impregnation, surface coating, filament
winding, cell casting, dip casting, continuous casting, embedding,
potting, encapsulation, film casting or solvent casting, gated
casting, mold casting, slush casting, extrusion, mechanical
foaming, chemical foaming, physical foaming, compression molding or
matched die molding, spray up, spraying, Vacuum Assisted Resin
Transfer Molding (VARTM), Seeman's Composite Resin Infusion Molding
Process (SCRIMP), blow molding, in mold coating, in-mold painting
or injection, vacuum forming, Reinforced Reaction Injection Molding
(RRIM), Structural Reaction Injection Molding (SRIM), thermal
expansion transfer molding (TERM), resin injection recirculation
molding (RICM), controlled atmospheric pressure resin infusion
(CAPRI), hand-layup. For manufacturing techniques requiring the use
of a RIM or impingement style mixhead, including without limitation
RIM, SRIM, and RRIM, articles of manufacture may be molded using a
single mixhead or a plurality of mixheads as well as a plurality of
material injection streams (e.g., two resin streams and one
catalyst stream).
[0412] The ROMP polymer and/or ROMP polymer composite thermal
insulation materials of the invention need not necessarily be
molded around an object to be insulated. In the alternative, a ROMP
polymer article and/or ROMP polymer composite article may be
independently prepared by a variety of methods known in the art and
then subsequently affixed to or placed around an object to
thermally insulate the object from the surrounding environment.
Moreover, the means for affixing a ROMP polymer article and/or ROMP
polymer composite article to an object may be by any known means
including an adhesive means and/or mechanical means such as
fasteners, bolts, screws, etc. For example, a ROMP polymer thermal
insulation material and/or a ROMP polymer composite thermal
insulation material can be pre-made into sections which are shaped
to complement the object to be insulated. The pre-made sections may
then be secured or affixed to the object using any known means.
[0413] Additionally, the object to be insulated may be pretreated
with any known tie coat or primer, which is suitable to improve
and/or enhance the adhesion of the ROMP polymer and/or ROMP polymer
composite thermal insulation material to the object. For example,
the tie coat or primer may be first applied to the object to be
insulated, then a ROMP composition may be applied to the object,
and the ROMP composition is subsequently subjected to conditions
effective to polymerize the ROMP composition. Furthermore, the tie
coat or primer may be applied to the object to be insulated, and a
pre-made ROMP polymer thermal insulation material and/or pre-made
ROMP polymer composite thermal insulation material may be
subsequently affixed to the object.
[0414] The thermal insulation and/or thermal insulation coating may
be of any configuration, weight, size, thickness, or geometric
shape. Furthermore, the thermal insulation and/or thermal
insulation coating is not limited to a single polymer layer, but
also include multiple polymer layers, where each polymer layer may
comprise the same or different composition.
[0415] The objects to be encased, coated and/or insulated may be of
any configuration, weight, size, thickness, or geometric shape.
Furthermore, the objects to be encased, coated and/or insulated may
be constructed of any material including but not limited to metal,
metal alloys, plastic, rubber, polymer, wood, ceramic, glass,
carbon, cement, concrete, etc.
[0416] The objects to be encased, coated and/or insulated may be
partially or fully encased, coated, and/or insulated.
[0417] In particular, ROMP polymers and/or ROMP polymer composites
of the present invention are suitable for thermal insulation of
objects, such as oil pipelines in cold water (e.g. cold sea water,
cold fresh water) and for insulating wellhead equipment. The ROMP
polymers and/or ROMP polymer composites of the present invention
may also be used for insulating other objects including but not
limited to pipes, pipelines, pipe fittings, hose, hose fitting,
tanks, containers, drums, manifolds, risers, field joints,
configurations designated as Christmas tree (oil field Christmas
tree, subsea Christmas tree), jumpers, spool pieces, configurations
designated as pipeline end termination (PLET), configurations
designated as pipeline end manifolds (PLEM), and other sub-sea
architectures and equipment. The ROMP polymers and/or ROMP polymer
composites of the present invention may also be used to coat other
objects such as robotic parts, devices and vehicles used in sub-sea
applications. Moreover, ROMP polymers and/or ROMP polymer
composites of the present invention may be used to construct
thermal insulation structures such as configurations designated as
subsea dog houses.
[0418] Pipe coated with the ROMP polymer and/or ROMP polymer
composite of the invention can have any outer diameter, inner
diameter, and length.
[0419] While ROMP polymers and/or ROMP polymer composites of the
invention are well suited for coating objects or thermally
insulating objects which are to be submerged in water (e.g. fresh
water, salt water, sea water, etc.) the ROMP polymers and/or ROMP
polymer composites may also be used to coat objects or thermally
insulate objects which are which are not exposed to an aqueous
environment.
[0420] Resin compositions according to the invention may further
comprise a sizing composition, or be used to provide improved
adhesion to substrate materials that are sized with certain
commercial silanes commonly used in the industry. As is known in
the art, glass fibers are typically treated with a chemical
solution (e.g., a sizing composition) soon after their formation to
reinforce the glass fibers and protect the strands' mechanical
integrity during processing and composite manufacture. Sizing
treatments compatible with olefin metathesis catalysts and
polydicyclopentadiene composites have been described in U.S. Pat.
Nos. 6,890,650 and 6,436,476, the disclosures of both of which are
incorporated herein by reference. However, these disclosures are
based on the use of specialty silane treatments that are not
commonly used in industrial glass manufacture. By comparison, the
current invention may provide improved mechanical properties for
polymer-glass composites that are sized with silanes commonly used
in the industry.
[0421] Glass sizing formulations typically comprise at least one
film former (typically a film forming polymer), at least one
silane, and at least one lubricant. Any components of a sizing
formulation that do not interfere with or substantially decrease
the effectiveness of the metathesis catalyst or olefin
polymerization reaction are considered to be compatible with the
current invention and may generally be used herein.
[0422] Film formers that are compatible with ROMP catalysts include
epoxies, polyesters, polyurethanes, polyolefins, and/or polyvinyl
acetates. Other common film formers that do not adversely affect
the performance of the olefin metathesis catalyst may also be used.
Film formers are typically used as nonionic, aqueous emulsions.
More than one film former may be used in a given sizing
formulation, to achieve a desired balance of glass processability
and composite mechanical properties.
[0423] More particularly, the film former may comprise a low
molecular weight epoxy emulsion, defined as an epoxy monomer or
oligomer with an average molecular weight per epoxide group (EEW)
of less than 500, and/or a high molecular weight epoxy emulsion,
defined as an epoxy monomer or oligomer with an average molecular
weight per epoxide group (EEW) of greater than 500. Examples of
suitable low molecular weight products include aqueous epoxy
emulsions produced by Franklin International, including Franklin
K8-0203 (EEW 190) and Franklin E-102 (EEW 225-275). Other examples
of low molecular weight epoxy emulsions are available from Hexion,
including EPI-REZ.TM. 3510-W-60 (EEW 185-215), and EPI-REZ.TM.
3515-W-60 (EEW 225-275). Further examples of low molecular weight
epoxy emulsions are available from COIM, including Filco 309 (EEW
270) and Filco 306 (EEW 330). Further examples of low molecular
weight epoxy emulsions are available from DSM, including
Neoxil.RTM. 965 (EEW 220-280) and Neoxil.RTM. 4555 (EEW 220-260).
Examples of suitable high molecular weight epoxy emulsion products
include epoxy emulsions produced by Hexion, including EPI-REZ.TM.
3522-W-60 (EEW 615-715).
[0424] Aqueous emulsions of modified epoxies, polyesters, and
polyurethanes may also be used in the film former. Examples of
suitable modified epoxy products include emulsions produced by DSM,
including Neoxil.RTM. 2626 (a plasticized epoxy with an EEW of
500-620), Neoxil.RTM. 962/D (an epoxy-ester with an EEW of
470-550), Neoxil.RTM. 3613 (an epoxy-ester with an EEW of 500-800),
Neoxil.RTM. 5716 (an epoxy-novolac with an EEW of 210-290),
Neoxil.RTM. 0035 (a plasticized epoxy-ester with an EEW of 2500),
and Neoxil.RTM. 729 (a lubricated epoxy with an EEW of 200-800).
Further examples of modified epoxy emulsions are available from
COIM, including Filco 339 (an unsaturated polyester-epoxy with an
EEW of 2000) and Filco 362 (an epoxy-ester with an EEW of 530).
Examples of suitable polyester products include emulsions produced
by DSM, including Neoxil.RTM. 954/D, Neoxil.RTM. 2635, and
Neoxil.RTM. 4759 (unsaturated bisphenolic polyesters). Additional
suitable products from DSM include Neoxil.RTM. 9166 and Neoxil.RTM.
968/60 (adipate polyesters). Further examples of suitable products
include emulsions produced by COIM, including Filco 354/N
(unsaturated bisphenolic polyester), Filco 350 (unsaturated
polyester), and Filco 368 (saturated polyester). Examples of
suitable polyurethane products include emulsions produced by Bayer
Material Science, including Baybond.RTM. 330 and Baybond.RTM.
401.
[0425] The film former may also comprise polyolefins or
polyolefin-acrylic copolymers, polyvinylacetates, modified
polyvinylacetates, or polyolefin-acetate copolymers. Suitable
polyolefins include, but are not limited to, polyethylenes,
polypropylenes, polybutylenes, and copolymers thereof, and the
polyolefins may be oxidized, maleated, or otherwise treated for
effective film former use. Examples of suitable products include
emulsions produced by Michelman, including Michem.RTM. Emulsion
91735, Michem.RTM. Emulsion 35160, Michem.RTM. Emulsion 42540,
Michem.RTM. Emulsion 69230, Michem.RTM. Emulsion 34040M1,
Michem.RTM. Prime 4983R, and Michem.RTM. Prime 4982SC. Examples of
suitable products include emulsions produced by HB Fuller,
including PD 708H, PD 707, and PD 0166. Additional suitable
products include emulsions produced by Franklin International,
including Duracet.RTM. 637. Additional suitable products include
emulsions produced by Celanese, including Vinamul.RTM. 8823
(plasticized polyvinylacetate), Dur-O-Set.RTM. E-200
(ethylene-vinyl acetate copolymer), Dur-O-Set.RTM. TX840
(ethylene-vinyl acetate copolymer), and Resyn.RTM. 1971
(epoxy-modified polyvinylacetate).
[0426] While not limited thereto, preferred film formers include
low- and high-molecular weight epoxies, saturated and unsaturated
polyesters, and polyolefins, such as Franklin K80-203, Franklin
E-102, Hexion 3510-W-60, Hexion 3515-W-60, and Michelman 35160.
[0427] Nonionic lubricants may also be added to the sizing
composition. Suitable nonionic lubricants that are compatible with
ROMP compositions include esters of polyethylene glycols and block
copolymers of ethylene oxide and propylene oxide. More than one
nonionic lubricant may be used in a given sizing formulation if
desired, e.g., to achieve a desired balance of glass processability
and composite mechanical properties.
[0428] Suitable lubricants may contain polyethylene glycol (PEG)
units with an average molecular weight between 200 and 2000,
preferably between 200-600. These PEG units can be esterified with
one or more fatty acids, including oleate, tallate, laurate,
stearate, and others. Particularly preferred lubricants include PEG
400 dilaurate, PEG 600 dilaurate, PEG 400 distearate, PEG 600
distearate, PEG 400 dioleate, and PEG 600 dioleate. Examples of
suitable products include compounds produced by BASF, including
MAPEG.RTM. 400 DO, MAPEG.RTM. 400 DOT, MAPEG.RTM. 600 DO,
MAPEG.RTM. 600 DOT, and MAPEG.RTM. 600 DS. Additional suitable
products include compounds produced by Zschimmer & Schwarz,
including Mulsifan 200 DO, Mulsifan 400 DO, Mulsifan 600 DO,
Mulsifan 200 DL, Mulsifan 400 DL, Mulsifan 600 DL, Mulsifan 200 DS,
Mulsifan 400 DS, and Mulsifan 600 DS. Additional suitable products
include compounds produced by Cognis, including Agnique.RTM. PEG
300 DO, Agnique.RTM. PEG 400 DO, and Agnique.RTM. PEG 600 DO.
[0429] Suitable nonionic lubricants also include block copolymers
of ethylene oxide and propylene oxide. Examples of suitable
products include compounds produced by BASF, including
Pluronic.RTM. L62, Pluronic.RTM. L101, Pluronic.RTM. P 103, and
Pluronic.RTM. P 105.
[0430] Cationic lubricants may also be added to the sizing
composition. Cationic lubricants that are compatible with ROMP
include modified polyethyleneimines, such as Emery 6760L produced
by Pulcra Chemicals.
[0431] Silane coupling agent may optionally be added to the sizing
composition, non-limiting examples including, methacrylate,
acrylate, amino, or epoxy functionalized silanes along with alkyl,
alkenyl, and norbornenyl silanes.
[0432] Optionally, the sizing composition may contain one or more
additives for modifying the pH of the sizing resin. One preferred
pH modifier is acetic acid.
[0433] The sizing composition may optionally contain other
additives useful in glass sizing compositions. Such additives may
include emulsifiers, defoamers, cosolvents, biocides, antioxidants,
and additives designed to improve the effectiveness of the sizing
composition. The sizing composition can be prepared by any method
and applied to substrate materials for use herein, such as glass
fibers or fabric, by any technique or method.
[0434] In a preferred embodiment, the metathesis reactions
disclosed herein are carried out under a dry, inert atmosphere.
Such an atmosphere may be created using any inert gas, including
such gases as nitrogen and argon. The use of an inert atmosphere is
optimal in terms of promoting catalyst activity, and reactions
performed under an inert atmosphere typically are performed with
relatively low catalyst loading. The reactions disclosed herein may
also be carried out in an oxygen-containing and/or a
water-containing atmosphere, and in one embodiment, the reactions
are carried out under ambient conditions. The presence of oxygen or
water in the reaction may, however, necessitate the use of higher
catalyst loadings as compared with reactions performed under an
inert atmosphere. Where the vapor pressure of the reactants allows,
the reactions disclosed herein may also be carried out under
reduced pressure.
[0435] The reactions disclosed herein may be carried out in a
solvent, and any solvent that is inert towards cross-metathesis may
be employed. Generally, solvents that may be used in the metathesis
reactions include organic, protic, or aqueous solvents, such as
aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic
hydrocarbons, alcohols, water, or mixtures thereof. Example
solvents include benzene, toluene, p-xylene, methylene chloride,
1,2-dichloroethane, dichlorobenzene, chlorobenzene,
tetrahydrofuran, diethyl ether, pentane, methanol, ethanol, water,
or mixtures thereof. In a preferred embodiment, the reactions
disclosed herein are carried out neat, i.e., without the use of a
solvent.
[0436] It will be appreciated that the temperature at which a
metathesis reaction according to methods disclosed herein is
conducted can be adjusted as needed, and may be at least about
-78.degree. C., -40.degree. C., -10.degree. C., 0.degree. C.,
10.degree. C., 20.degree. C., 25.degree. C., 35.degree. C.,
50.degree. C., 70.degree. C., 100.degree. C., or 150.degree. C., or
the temperature may be in a range that has any of these values as
the upper or lower bounds. In a preferred embodiment, the reactions
are carried out at a temperature of at least about 35.degree. C.,
and in another preferred embodiment, the reactions are carried out
at a temperature of at least about 50.degree. C.
[0437] It is to be understood that while the invention has been
described in conjunction with specific embodiments thereof, the
description above as well as the examples that follow are intended
to illustrate and not limit the scope of the invention. Other
aspects, advantages, and modifications within the scope of the
invention will be apparent to those skilled in the art to which the
invention pertains.
EXPERIMENTAL
[0438] In the following examples, efforts have been made to ensure
accuracy with respect to numbers used (e.g., amounts, temperature,
etc.) but some experimental error and deviation should be accounted
for. Unless indicated otherwise, temperature is in degrees Celsius
(.degree. C.), pressure is at or near atmospheric, viscosity is in
centipoise (cP). Additives added to the cyclic olefin compositions
to form resin compositions are reported as ppm, which is defined as
the weight in grams of additive per million grams of cyclic olefin
composition, or as phr, which is defined as the weight in grams of
the additive per hundred grams of cyclic olefin composition.
[0439] The following examples are to be considered as not being
limiting of the invention as described herein, and are instead
provided as representative examples of compositions of the
invention and methods for their use, and articles made from such
compositions and methods.
Examples
Materials and Methods
[0440] All glassware was oven dried and reactions were performed
under ambient conditions unless otherwise noted. All solvents and
reagents were purchased from commercial suppliers and used as
received unless otherwise noted.
[0441] Mol percent (mol %) of dicyclopentadiene (DCPD),
tricyclopentadiene (TCPD), tetracyclopentadiene (TeCPD), decyl
norbornene (DNB), hexyl norbornene (HNB), tolyl norbornene
(Tolyl-NB), or octyl norbornene (ONB) present in the cyclic olefin
compositions were calculated from the weight percent (wt %) values
obtained by gas chromatography (GC).
[0442] DCPD (Ultrene.RTM. 99) was obtained from Cymetech
Corporation. A representative lot of Ultrene.RTM. 99 comprised DCPD
(99.83 weight percent) and TCPD (0.17 weight percent) as measured
by GC. A modified DCPD base resin (DCPD-HT) containing 20-25 wt %
TCPD (and small amounts of higher cyclopentadiene (CPD) homologs)
was prepared by heat treatment of Ultrene.RTM. 99 generally as
described in U.S. Pat. No. 4,899,005. A modified DCPD base resin
(DCPD-6T) containing 5-7 wt % TCPD (and small amounts of higher CPD
homologs) was prepared by heat treatment of Ultrene.RTM. 99
generally as described in U.S. Pat. No. 4,899,005.
[0443] Tricyclopentadiene (TCPD) was prepared as generally
described in European Pat. No. EP0271007B2 and purified to greater
than 95% by vacuum distillation.
[0444] Preparation of a Representative ONB/TCPD Resin Mixture:
1-Decene (3 equivalents) and modified DCPD containing 20-25%
tricyclopentadiene (1 equivalent) were combined in a 3-neck flask
and heated to 160.degree. C. on a heating mantle under an argon
atmosphere for 12 hours. The temperature was increased to
170.degree. C. for an additional 24 hours. After completion of the
reaction, residual 1-decene and DCPD were removed from the reaction
mixture by vacuum distillation at 70-80.degree. C. Following
removal of 1-decene and DCPD, the remaining mixture was heated to
100.degree. C. and a 3:1 mixture of octyl
norborene:tricyclopentadiene was distilled overhead and collected
as a homogeneous liquid. The collected octyl
norbornene/tricyclopentadiene liquid mixture was treated with a
small amount of butylated hydroxytoluene and stored under an argon
atmosphere. A representative lot of ONB/TCPD mixture comprised ONB
(71.7 wt %) and TCPD (28.2 wt %) and small amounts of higher CPD
homologs as measured by GC.
[0445] 5-Tolyl-2-norbornene (Tolyl-NB)/TCPD mixture was prepared as
generally described in U.S. Pat. No. 5,138,003. A representative
lot of Tolyl-NB/TCPD mixture comprised Tolyl-NB (70.5 wt %) and
TCPD (28.6 wt %) and DCPD (0.147 wt %) and small amounts of higher
CPD homologs as measured by GC.
[0446] 5-Hexyl-2-norbornene (HNB) was prepared by Diels-Alder
reaction of CPD with 1-octene as generally known in the art. A
representative lot of HNB comprised HNB (99.9 wt %) and small
amounts of higher CPD homologs as measured by GC.
[0447] 5-Decyl-2-norbornene (DNB)/TCPD mixture was prepared by
Diels-Alder reaction of CPD with 1-dodecene as generally known in
the art. A representative lot of DNB/TCPD mixture comprised DNB
(913 wt %) and TCPD (8.4 wt %) and small amounts of higher CPD
homologs as measured by GC.
[0448] Irganox.RTM. 1076 antioxidant (BASF) was used where
indicated.
[0449] Cumene hydroperoxide (CHP) was used as received unless
otherwise indicated from Sigma Aldrich (88% purity), Syrgis
Performance Initiators (Norox.RTM. CHP, 85%), or Trigonox
K-90.RTM., Akzo Nobel, 88%). CHP was used as a 1,000 ppm or 10,000
ppm concentration stock solution in DCPD, or as received.
[0450] Butylated hydroxytoluene (BHT) was used where indicated.
[0451] Triphenylphosphine (TPP) was used as received from
Arkema.
[0452] 1-Decene was used as received from CP Chem.
[0453] K-20 glass microspheres were purchased from 3M and used
where indicated.
[0454] Metal carbene olefin metathesis catalysts were prepared by
standard methods and include
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl--
2-butenylidene) (tricyclohexylphosphine)ruthenium(II) (C827);
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(benzylide-
ne)(tricyclohexylphosphine)ruthenium(II) (C848);
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl--
2-butenylidene)(methyldiphenylphosphine)ruthenium(II) (C747);
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(benzylide-
ne)(tri-n-butylphosphine)ruthenium(II) (C771); ruthenium (II)
dichloro (3-methyl-2-butenylidene)bis(tricyclohexylphosphine)
(C801);
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(o-isoprop-
oxyphenylmethylene)ruthenium(II) (C627);
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylind-
enylidene)(diethylphenylphosphine)ruthenium(II) (C835); and
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylind-
enylidene)(tricyclohexylphosphine)ruthenium(II) (C949).
[0455] Cyclic Olefin Composition (A): ONB/TCPD mixture was combined
with DCPD-HT. Cyclic olefin composition (A) comprised ONB (43.1 mol
%), DCPD (35.5 mol %), TCPD from ONB mixture (13.5 mol %), and TCPD
from DCPD mixture (7.7 mol %).
[0456] Cyclic Olefin Composition (B): ONB/TCPD mixture was combined
with DCPD-HT. Cyclic olefin composition (B) comprised ONB (40.9 mol
%), DCPD (39.6 mol %), and TCPD (19.5 mol %).
[0457] Cyclic Olefin Composition (C): ONB/TCPD mixture (910 grams)
was combined with DCPD-HT (490 grams). Cyclic olefin composition
(C) comprised ONB (42.99 mol %), DCPD (35.79 mol %), TCPD (21.17
mol %), TeCPD (0.05 mol %).
[0458] Cyclic Olefin Composition (D): DNB/TCPD mixture (94 grams),
TCPD (25 grams), and DCPD-HT (55 grams) were combined. Cyclic
olefin composition (D) comprised DNB (42.47 mol %), DCPD (35.08 mol
%), TCPD (21.84 mol %), and TeCPD (0.62 mol %).
[0459] Cyclic Olefin Composition (E): DNB/TCPD mixture (165.3
grams), TCPD (59.7 grams), and DCPD-HT (66.1 grams) were combined.
Cyclic olefin composition (E) comprised DNB (47.4 mol %), DCPD
(25.38 mol %), TCPD (26.6 mol %), and TeCPD (0.61 mol %).
[0460] Cyclic Olefin Composition (F): DNB/TCPD mixture (90 grams),
TCPD (41 grams), and DCPD-HT (45 grams) were combined. Cyclic
olefin composition (F) comprised DNB (41.87 mol %), DCPD (28.03 mol
%), TCPD (29.42 mol %), and TeCPD (0.68 mol %).
[0461] Cyclic Olefin Composition (G): HNB (82 grams), TCPD (28
grams), and DCPD-HT (66 grams) were combined. Cyclic olefin
composition (G) comprised HNB (43.58 mol %), DCPD (35.09 mol %),
TCPD (20.72 mol %), and TeCPD (0.62 mol %).
[0462] Cyclic Olefin Composition (H): HNB (90 grams), TCPD (24
grams), and DCPD-HT (62 grams) were combined. Cyclic olefin
composition (H) comprised HNB (47.96 mol %), DCPD (33.04 mol %),
TCPD (18.43 mol %), and TeCPD (0.56 mol %).
[0463] Cyclic Olefin Composition (I): Tolyl-NB/TCPD mixture (345
grams), TCPD (30 grams), and DCPD (135 grams) were combined. Cyclic
olefin composition (I) comprised Tolyl-NB (42.88 mol %), DCPD
(34.21 mol %), TCPD (21.23 mol %), and TeCPD (0.03 mol %).
[0464] Cyclic Olefin Composition (J): DNB/TCPD mixture (156 grams),
HNB (106 grams), TCPD (106 grams), and DCPD (131 grams) were
combined. Cyclic olefin composition (J) comprised DNB (21.3 mol %),
HNB (21.3 mol %), DCPD (36.0 mol %), TCPD (21.1 mol %), and TeCPD
(0.03 mol %).
[0465] Cyclic Olefin Composition (K): ONB/TCPD mixture (11050
grams) was combined with DCPD-HT (6950 grams). Cyclic olefin
composition (K) comprised ONB (40.2 mol %), DCPD (37.43 mol %),
TCPD (21.6 mol %), TeCPD (0.67 mol %).
[0466] Cyclic Olefin Composition (L): ONB/TCPD mixture (7259 grams)
was combined with DCPD-HT (3907 grams). Cyclic olefin composition
(L) comprised ONB (42.66 mol %), DCPD (35.46 mol %), TCPD (21.39
mol %), TeCPD (0.49 mol %).
[0467] Cyclic Olefin Composition (M): ONB/TCPD mixture (115.4 kg)
was combined with DCPD-HT (60.2 kg). Cyclic olefin composition (M)
comprised ONB (42.02 mol %), DCPD (35.05 mol %), TCPD (22.36 mol
%), TeCPD (0.57 mol %).
[0468] Resin Composition (A): Irgonox.RTM. 1076, BASF (1 phr) and
CHP (Trigonox.RTM. K-90, Akzo Nobel) (5 ppm) were added to cyclic
olefin composition (A) at room temperature.
[0469] Resin Composition (B): Irgonox.RTM. 1076, BASF (1 phr) and
CHP (Trigonox.RTM. K-90, Akzo Nobel) (5 ppm) were added to cyclic
olefin composition (B) at room temperature.
[0470] Resin Composition (C): Irgonox.RTM. 1076, BASF (1 phr) was
added to cyclic olefin composition (B) at room temperature.
[0471] Resin Composition (D): Irgonox.RTM. 1076 (1 phr) and CHP (5
ppm) were added to cyclic olefin composition (C) at room
temperature.
[0472] Resin Composition (E): Irgonox.RTM. 1076 (1 phr) and CHP (5
ppm) were added to cyclic olefin composition (D) at room
temperature.
[0473] Resin Composition (F): Irgonox.RTM. 1076 (1 phr) and CHP (5
ppm) were added to cyclic olefin composition (E) at room
temperature.
[0474] Resin Composition (G): Irgonox.RTM. 1076 (1 phr) and CHP (5
ppm) were added to cyclic olefin composition (F) at room
temperature.
[0475] Resin Composition (H): Irgonox.RTM. 1076 (1 phr) and CHP (5
ppm) were added to cyclic olefin composition (G) at room
temperature.
[0476] Resin Composition (I): Irgonox.RTM. 1076 (1 phr) and CHP (5
ppm) were added to cyclic olefin composition (H) at room
temperature.
[0477] Resin Composition (J): Irgonox.RTM. 1076 (1 phr) and CHP (5
ppm) were added to cyclic olefin composition (I) at room
temperature.
[0478] Resin Composition (K): Irgonox.RTM. 1076 (1 phr) and CHP (5
ppm) were added to cyclic olefin composition (J) at room
temperature.
[0479] Resin Composition (L1): Irgonox.RTM. 1076 (1 phr) was added
to cyclic olefin composition (K) at room temperature.
[0480] Resin Composition (L2): Irgonox.RTM. 1076 (1 phr) and TPP
(0.4 phr) were added to cyclic olefin composition (K) at room
temperature.
[0481] Resin Composition (L3): Irgonox.RTM. 1076 (1 phr) and TPP
(1.0 phr) were added to cyclic olefin composition (K) at room
temperature.
[0482] Resin Composition (M1): Irgonox.RTM. 1076 (1 phr) and TPP
(0.1 phr) were added to cyclic olefin composition (L) at room
temperature.
[0483] Resin Composition (M2): Irgonox.RTM. 1076 (1 phr) and CHP
(20 ppm) were added to cyclic olefin composition (L) at room
temperature.
[0484] Resin Composition (N1): Irgonox.RTM. 1076 (1 phr) was added
to cyclic olefin composition (M) at room temperature.
[0485] Resin Composition (N2): Irgonox.RTM. 1076 (1 phr) and TPP
(0.2 phr) were added to cyclic olefin composition (M) at room
temperature.
[0486] Resin Composition (N3): Irgonox.RTM. 1076 (1 phr) and CHP
(150 ppm) were added to cyclic olefin composition (M) at room
temperature.
[0487] Resin Composition (N4): Irgonox.RTM. 1076 (1 phr) and TPP
(0.3 phr) were added to cyclic olefin composition (M) at room
temperature.
[0488] Resin Composition (N5): Irgonox.RTM. 1076 (1 phr) and TPP
(0.1 phr) were added to cyclic olefin composition (M) at room
temperature.
[0489] Resin Composition (O): K-20 glass microspheres (23.8 PHR)
and Cab-O-Sil (0.5 PHR) were added to Resin Composition (A) at room
temperature.
[0490] Catalyst Composition (A) was prepared by suspending C827
(monomer to catalyst ratio 45,000:1) and C848 (monomer to catalyst
ratio 500,000:1) in mineral oil (Crystal Plus 500 FG) containing 2
phr CAB-O-SIL.RTM. TS610 (Cabot Corporation). Catalyst composition
(A) was prepared so as to have a monomer to catalyst ratio of
45,000:1 for C827 and 500,000:1 for C848 at 2 grams of catalyst
suspension per 100 grams of DCPD monomer.
[0491] Catalyst Composition (B): C747 was suspended in mineral oil
(Crystal Plus 500 FG) containing 2 phr CAB-O-SIL.RTM. TS610.
Catalyst composition (B) was prepared so as to have a monomer to
catalyst ratio of 60,000:1 at 2 grams of catalyst suspension per
100 grams of DCPD monomer.
[0492] Catalyst Composition (C): C771 was suspended in mineral oil
(Crystal Plus 500 FG) containing 2 phr CAB-O-SIL.RTM. TS610.
Catalyst composition (C) was prepared so as to have a monomer to
catalyst ratio of 45,000:1 at 2 grams of catalyst suspension per
100 grams of DCPD monomer.
[0493] Catalyst Composition (D): C801 was suspended in mineral oil
(Crystal Plus 500 FG) containing 2 phr CAB-O-SIL.RTM. TS610.
Catalyst composition (D) was prepared so as to have a monomer to
catalyst ratio of 5,000:1 at 2 grams of catalyst suspension per 100
grams of DCPD monomer.
[0494] Catalyst Composition (E): C627 was suspended in mineral oil
(Crystal Plus 500 FG) containing 2 phr CAB-O-SIL.RTM. TS610.
Catalyst composition (E) was prepared so as to have a monomer to
catalyst ratio of 60,000:1 at 2 grams of catalyst suspension per
100 grams of DCPD monomer.
[0495] Catalyst Composition (F): C827 was suspended in mineral oil
(Crystal Plus 500 FG) containing 2 phr CAB-O-SIL.RTM. TS610.
Catalyst composition (F) was prepared so as to have a monomer to
catalyst ratio of 30,000:1 at 2 grams of catalyst suspension per
100 grams of DCPD monomer.
[0496] Catalyst Composition (G): C835 was suspended in mineral oil
(Crystal Plus 500 FG) containing 2 phr CAB-O-SIL.RTM. TS610.
Catalyst composition (G) was prepared so as to have a monomer to
catalyst ratio of 30,000:1 at 2 grams of catalyst suspension per
100 grams of DCPD monomer.
[0497] Catalyst Composition (H): C827 was suspended in mineral oil
(Crystal Plus 500 FG) containing 2 phr CAB-O-SIL.RTM. TS610.
Catalyst composition (H) was prepared so as to have a monomer to
catalyst ratio of 45,000:1 at 2 grams of catalyst suspension per
100 grams of DCPD monomer.
[0498] Catalyst Composition (I): C848 was suspended in mineral oil
(Crystal Plus 500 FG) containing 2 phr CAB-O-SIL.RTM. TS610.
Catalyst composition (I) was prepared so as to have a monomer to
catalyst ratio of 60,000:1 at 2 grams of catalyst suspension per
100 grams of DCPD monomer.
[0499] Catalyst Composition (J): C949 was suspended in mineral oil
(Crystal Plus 500 FG) containing 2 phr CAB-O-SIL.RTM. TS610.
Catalyst composition (J) was prepared so as to have a monomer to
catalyst ratio of 45,000:1 at 2 grams of catalyst suspension per
100 grams of DCPD monomer.
[0500] Catalyst Composition (K): C835 and C848 were suspended in
mineral oil (Crystal Plus 500 FG) containing 2 phr CAB-O-SIL.RTM.
TS610. Catalyst composition (K) was prepared so as to have a
monomer to catalyst ratio of 45,000:1 for C835 and 200,000:1 for
C848 at 2 grams of catalyst suspension per 100 grams of DCPD
monomer.
[0501] Catalyst Composition (L): C949 and C827 were suspended in
mineral oil (Crystal Plus 500 FG) containing 2 phr CAB-O-SIL.RTM.
TS610. Catalyst composition (L) was prepared so as to have a
monomer to catalyst ratio of 90,000:1 for C949 and 90,000:1 for
C827 at 2 grams of catalyst suspension per 100 grams of DCPD
monomer.
Example 1
ROMP Polymer Coated Pipe
[0502] Resin Composition (A) (800 grams) was placed into a 3-neck
round bottom flask and degassed under vacuum for 20 minutes with
stirring. The flask was sealed under vacuum and the resin
composition (A) was heated to 35.degree. C. in an oven. A three
inch long piece of 5.5 inch O.D. low carbon steel pipe was cut and
polished on each face. The outer surface layer of the pipe was
removed by blasting with hard steel grit (GH 25) until the depth
profile was at least 2.0 mils as determined by replica tape (ASTM
4417). The grit-blasted pipe surface was cleaned by spraying with
acetone and scrubbing with a towel followed by air drying. The pipe
was heated to 50.degree. C. in an oven. Simultaneously, a
cylindrical mold with a solid steel bottom was heated to 35.degree.
C. in an oven. The pipe and mold were removed from the oven(s) and
the pipe was placed inside the mold with an o-ring positioned
underneath the pipe face to seal the interior of the pipe from the
pipe exterior. The pipe was centered in the mold. Resin composition
(A) was catalyzed by the addition of catalyst composition (A) (16
grams) and the catalyzed resin was poured into the mold. The
temperature of the catalyzed resin was monitored during the
polymerization process. The catalyzed resin achieved a peak
exotherm temperature of 180.degree. C. at approximately 4 minutes
after catalyzation. The ROMP polymer coated pipe was cooled to room
temperature and then machined on a lathe to reduce the thickness of
the pipe and the ROMP polymer to a uniform thickness of 0.75
inches.
TABLE-US-00001 TABLE 1 Measured properties of the ROMP polymer from
Example 1. ROMP Polymer Property Method Units (Example 1) Glass
transition temperature (T.sub.g) ASTM E1356 .degree. C. 51 Thermal
conductivity ASTM C518 W/m K 0.175 Hardness ASTM D2240 Shore D 74
Tensile strength (20 in/min) ASTM D638 MPa 35 Tensile modulus ASTM
D638 MPa 1302 Elongation @ yield ASTM D638 % 7 Elongation @ break
ASTM D638 % 179 Compressive modulus (0.5''/min) ASTM D695 MPa 1017
Compressive strength (5% strain) ASTM D695 MPa 29 Compressive
strength (10% strain) ASTM D695 MPa 23 Density g/cm.sup.3 0.981
Impact strength ASTM D256 J/m 95 Flash point (uncatalyzed resin)
ASTM D93 .degree. C. 61 CTE (below Tg) ASTM E831 1/.degree. C. 159
10.sup.-6 CTE (above Tg) ASTM E831 1/.degree. C. 198 10.sup.-6 Heat
of cure ASTM E1356 kJ/kg 239
Example 2
ROMP Polymer Coated Pipe and ROMP Polymer Coated Field Joint
[0503] A 1.5'' outside diameter (O.D.), 24'' long grade SAE 4130
steel pipe was blasted with G25 steel grit until the blast profile
was 2.0 mils and all visible dark corrosion/mill scale was removed.
Dust was removed from the pipe surface using compressed air. A
cylindrical, 24'' aluminum mold was heated to 35.degree. C. in an
oven. The blasted pipe was heated to 60.degree. C. in an oven. The
heated pipe was removed from the oven and quickly assembled in the
aluminum mold. Resin Composition (B) (6,590 grams) was degassed for
1 hour under vacuum and heated to 35.degree. C. The degassed Resin
Composition (B) (6,590 grams) was catalyzed by the addition of
catalyst composition (A) (132 grams) and the catalyzed resin was
poured in the hot aluminum mold containing the hot steel pipe. The
catalyzed resin was allowed to exotherm to form a cured polymer.
The ROMP polymer coated pipe was cooled to room temperature.
[0504] A section of cured polymer was machined (i.e., cut away)
from the center of the polymer coated pipe to expose an 8'' section
of pipe thereby forming two independent opposing sections of
polymer coated pipe. Next, additional amounts of polymer was
further removed from the two independent opposing sections of
polymer coated pipe to form a 45.degree. chamfer of the polymer
from the pipe surface to the outer diameter of each independent
opposing section of polymer. This machining process formed what we
referred to as the "field joint assembly". The field joint assembly
possessing what we referred to as the "field joint gap" (see FIG.
1). The field joint gap being the 8'' section of exposed pipe
located between the two independent opposing sections of polymer
coated pipe. The field joint gap was designed to simulate an actual
field joint as defined herein. Overall, the field joint assembly
possessed a dumbbell like shape.
[0505] The 8'' section of exposed pipe was re-blasted with G25
steel grit to remove residual polymer and flash rust. To each of
the two independent opposing sections of polymer, the chamfer
region of the polymer and 4'' of the O.D. extending away from the
edge of the chamfer was sanded with 80 grit sandpaper in a
cross-hatch pattern. O-rings were fitted 4'' from the edge of the
chamfer and the field joint assembly was heated to 60.degree. C. in
an oven.
[0506] Sudan blue pigment (0.0003 phr) was added to Resin
Composition (C) (3,900 grams). The pigmented Resin Composition (C)
was degassed for 1 hour under vacuum and heated to 35.degree. C.
The field joint assembly was removed from the 60.degree. C. oven,
placed in a horizontal orientation, and fitted with a flexible
metal molding to form a sealed cylindrical cavity around the entire
field joint assembly with an open trench at the top of the mold for
adding catalyzed resin. The degassed Resin Composition (C) (3,900
grams) was catalyzed by the addition of catalyst composition (A)
(78.0 grams) and the catalyzed resin was poured in the open trench
at the top of the mold. The catalyzed resin was allowed to exotherm
to form a cured polymer, and the cured polymer was cooled to room
temperature. The mold was removed to provide a ROMP polymer coated
field joint as described herein, where the field joint (e.g.,
simulated field joint) was encased by (or coated with) a thermal
insulation material of the invention (e.g. a ROMP polymer or ROMP
composition). Furthermore, the thermal insulation material used to
coat the field joint (e.g. simulated field joint) not only coated
the field joint, but also partially coated (partially encased) the
two independent opposing sections of polymer used to originally
coat the pipe (see FIG. 2).
Examples 3-8
[0507] Resin Compositions (D)-(I) were separately degassed under
vacuum for 20 minutes at ambient temperature (20-25.degree. C.).
Degassed Resin Compositions (D)-(I) were each separately catalyzed
at ambient temperature by the addition of Catalyst Composition (A)
(2 phr) to form ROMP Compositions (D)-(I). ROMP Compositions
(D)-(I) were separately degassed for 1 minute under vacuum at
ambient temperature. Each degassed ROMP Composition (D)-(I) was
poured into a separate set of two aluminum molds preheated to
35.degree. C. in a laboratory oven, the first mold being
rectangular and having dimensions (10''.times.10''.times.1/8'') and
the second mold being cylindrical and having dimensions
(0.81''.times.15''). After the molds were filled, the ROMP
compositions (D)-(I) were held at 35.degree. C. for 15 minutes and
then heated from 35.degree. C. to 140.degree. C. at a heating rate
of 3.5.degree. C./min, and then held at 140.degree. C. for 2 hours,
and then allowed to cool to ambient temperature and demolded. The
mechanical and thermal properties of the demolded ROMP polymer
articles corresponding to ROMP Compositions (D)-(I) were measured
according to the methods designated in Tables 2 and 3.
TABLE-US-00002 TABLE 2 Measured properties of the ROMP polymers
from ROMP Compositions (D)-(F) Example 3 4 5 ROMP ROMP ROMP
Composition Composition Composition Property Method Units (D) (E)
(F) Glass transition ASTM .degree. C. 51 45 50 temperature (Tg)
E1356 Tensile strength ASTM MPa 38 26 29 (2''/min) D638 Tensile
modulus ASTM MPa 1148 1237 1261 D638 Elongation @ yield ASTM % 6 6
6 D638 Elongation @ break ASTM % 284 66 218 D638 Compressive
modulus ASTM MPa 1017 1032 1083 (0.5''/min) D695 Compressive
strength ASTM MPa 29 28 30 (5% strain) D695 Compressive strength
ASTM MPa 23 24 24 (10% strain) D695 Thermal conductivity ASTM W/m *
K 0.176.sup.a Not Measured Not Measured C518 .sup.aThermal
conductivity was measured using a heat flow instrument (FOX-50,
LaserComp).
TABLE-US-00003 TABLE 3 Measured properties of the ROMP polymers
from ROMP Compositions (G)-(I) Example 6 7 8 ROMP ROMP ROMP
Composition Composition Composition Property Method Units (G) (H)
(I) Glass transition ASTM .degree. C. 67 80 62 temperature (Tg)
E1356 Tensile strength ASTM MPa 35 35 31 (2''/min) D638 Tensile
modulus ASTM MPa 1447 1492 1355 D638 Elongation @ yield ASTM % 7 7
6 D638 Elongation @ break ASTM % 204 121 144 D638 Compressive
modulus ASTM MPa 1238 1333 1258 (0.5''/min) D695 Compressive
strength ASTM MPa 37 44 38 (5% strain) D695 Compressive strength
ASTM MPa 32 37 32 (10% strain) D695 Thermal conductivity ASTM W/m*K
Not Not Not C518 Measured Measured Measured
Examples 9-10
[0508] Resin Compositions (J), (K) were separately degassed under
vacuum for 20 minutes at ambient temperature (20-25.degree. C.) and
then heated to 35.degree. C. under vacuum. Degassed Resin
Compositions (J), (K) were each separately catalyzed at 35.degree.
C. under vacuum by the addition of Catalyst Composition (A) (2 phr)
to form ROMP Compositions (J), (K). Each ROMP Composition (J), (K)
was poured into a separate set of three aluminum molds preheated to
35.degree. C. in a laboratory oven, the first mold being
rectangular and having dimensions (10''.times.10''.times.1/8'') and
the second mold being cylindrical and having dimensions
(0.81''.times.15'') and the third mold being rectangular and having
dimensions (4''.times.6''.times.0.032''). After the molds were
filled, the ROMP compositions (J), (K) were held at 35.degree. C.
for 30 minutes and then heated from 35.degree. C. to 140.degree. C.
at a heating rate of 3.5.degree. C./min, and then held at
140.degree. C. for 2 hours, and then allowed to cool to ambient
temperature and demolded. The mechanical and thermal properties of
the demolded ROMP polymer articles corresponding to ROMP
Compositions (J), (K) were measured according to the methods
designated in Table 4.
TABLE-US-00004 TABLE 4 Measured properties of the ROMP polymers
from ROMP Compositions (J), (K) Example 9 10 ROMP ROMP Composition
Composition Property Method Units (J) (K) Glass transition ASTM
.degree. C. 119 45 temperature (Tg) E1356 Tensile strength ASTM MPa
65 31 (2''/min) D638 Tensile modulus ASTM MPa 2279 1349 D638
Elongation @ yield ASTM % 7.7 6.7 D638 Elongation @ break ASTM % 21
66 D638 Compressive modulus ASTM MPa 1928 1112 (0.5''/min) D695
Compressive strength ASTM MPa 77 32 (5% strain) D695 Compressive
strength ASTM MPa 66 25 (10% strain) D695 Thermal conductivity ASTM
W/m*K Not Not C518 Measured Measured
Examples 11-16
[0509] Resin Compositions (L1) (two separate portions), (L2), (L3),
(M1), (M2) were separately degassed under vacuum for 20 minutes at
ambient temperature (20-25.degree. C.) and then heated to
35.degree. C. under vacuum. Degassed Resin Compositions (L1) (two
separate portions), (L2), (L3), (M1), (M2) were each separately
catalyzed at 35.degree. C. under vacuum by the addition of a
catalyst composition (2 phr) as indicated in Tables 5 and 6 to form
ROMP Compositions (L1A), (L1B), (L2), (L3), (M1), (M2). Each ROMP
Composition (L1A), (L1B), (L2), (L3), (M1), (M2) was poured into a
separate set of three aluminum molds preheated to 35.degree. C. in
a laboratory oven, the first mold being rectangular and having
dimensions (10''.times.10''.times.1/8'') and the second mold being
cylindrical and having dimensions (0.81''.times.15'') and the third
mold being rectangular and having dimensions
(4''.times.6''.times.0.032''). After the molds were filled, the
ROMP compositions (L1A), (L1B), (L2), (L3), (M1), (M2) were held at
35.degree. C. for 30 minutes and then heated from 35.degree. C. to
140.degree. C. at a heating rate of 3.5.degree. C./min, and then
held at 140.degree. C. for 2 hours, and then allowed to cool to
ambient temperature and demolded. The mechanical and thermal
properties of the demolded ROMP polymer articles corresponding to
ROMP Compositions (L1A), (L1B), (L2), (L3), (M1), (M2) were
measured according to the methods designated in Tables 5 and 6.
TABLE-US-00005 TABLE 5 Measured properties of the ROMP polymers
from ROMP Compositions (L1A), (L1B), (L2) Example 11 12 13 ROMP
ROMP ROMP Composition Composition Composition Property Method Units
(L1A).sup.a (L1B).sup.b (L2).sup.c Glass transition ASTM .degree.
C. 59 61 51 temperature (Tg) E1356 Tensile strength ASTM MPa 34 35
33 (2''/min) D638 Tensile modulus ASTM MPa 1424 1431 1359 D638
Elongation @ yield ASTM % 7.3 7.3 6.6 D638 Elongation @ break ASTM
% 121 73 226 D638 Compressive modulus ASTM MPa 1175 1195 1174
(0.5''/min) D695 Compressive strength ASTM MPa 36 36 34 (5% strain)
D695 Compressive strength ASTM MPa 30 29 27 (10% strain) D695
Thermal conductivity ASTM W/m*K Not Not Not C518 Measured Measured
Measured .sup.a= Catalyst Composition (C); .sup.b= Catalyst
Composition (G); .sup.c= Catalyst Composition (B)
TABLE-US-00006 TABLE 6 Measured properties of the ROMP polymers
from ROMP Compositions (L3), (M1), (M2) Example 14 15 16 ROMP ROMP
ROMP Composition Composition Composition Property Method Units
(L3).sup.a (M1).sup.b (M2).sup.c Glass transition ASTM .degree. C.
52 49 51 temperature (Tg) E1356 Tensile strength ASTM MPa 33 37 31
(2''/min) D638 Tensile modulus ASTM MPa 1346 1533 1345 D638
Elongation @ yield ASTM % 6.7 7.1 6.7 D638 Elongation @ break ASTM
% 198 71 133 D638 Compressive modulus ASTM MPa 1162 1233 1096
(0.5''/min) D695 Compressive strength ASTM MPa 33 38 31 (5% strain)
D695 Compressive strength ASTM MPa 27 30 25 (10% strain) D695
Thermal conductivity ASTM W/m*K Not Not Not C518 Measured Measured
Measured .sup.a= Catalyst Composition (E); .sup.b= Catalyst
Composition (D); .sup.c= Catalyst Composition (F)
Examples 17-20
[0510] Resin Compositions (N1) (two separate portions), (N4), (N5)
were separately degassed under vacuum for 20 minutes at ambient
temperature (20-25.degree. C.). Degassed Resin Compositions (N1)
(two separate portions), (N4), (N5) were each separately catalyzed
at ambient temperature under vacuum by the addition of a catalyst
composition (2 phr) as indicated in Table 7 to form ROMP
Compositions (N1A), (N1B), (N4), (N5). Each ROMP Composition (N1A),
(N1B), (N4), (N5) was poured into a separate set of two aluminum
molds preheated to 35.degree. C. in a laboratory oven, the first
mold being rectangular and having dimensions
(1.5''.times.1.5''.times.11'') and the second mold being
cylindrical and having dimensions (0.79''.times.14''). After the
molds were filled, the ROMP compositions (N1A), (N1B), (N4), (N5)
were held at 35.degree. C. for 30 minutes and then heated from
35.degree. C. to 140.degree. C. at a heating rate of 3.5.degree.
C./min, and then held at 140.degree. C. for 2 hours, and then
allowed to cool to ambient temperature and demolded. The mechanical
and thermal properties of the demolded ROMP polymer articles
corresponding to ROMP Compositions (N1A), (N1B), (N4), (N5) were
measured according to the methods designated in Table 7.
TABLE-US-00007 TABLE 7 Measured properties of the ROMP polymers
from ROMP Compositions (N1A), (N1B), (N4), (N5) Example 17 18 19 20
ROMP ROMP ROMP ROMP Composition Composition Composition Composition
Property Method Units (N1A).sup.a (N1B).sup.b (N4).sup.c (N5).sup.d
Glass transition ASTM .degree. C. 54 55 51 54 temperature (Tg)
E1356 Tensile strength ASTM MPa 31 31 30 30 (2"/min) D638 Tensile
modulus ASTM MPa 1419 1373 1347 1358 D638 Elongation @ yield ASTM %
6.8 6.6 6.6 6.5 D638 Elongation @ break ASTM % 133 119 154 151 D638
Compressive modulus ASTM MPa 977 984 966 972 (0.5"/min) D695
Compressive strength ASTM MPa 31 31 29 30 (5% strain) D695
Compressive strength ASTM MPa 25 25 24 24 (10% strain) D695 Thermal
conductivity ASTM W/m*K Not Measured Not Measured Not Measured Not
Measured C518 a = Catalyst Composition (J); b = Catalyst
Composition (L); c = Catalyst Composition (I); d = Catalyst
Composition (K)
Examples 21-22
[0511] Resin Compositions (N2), (N3) were separately degassed under
vacuum for 20 minutes at ambient temperature (20-25.degree. C.).
Degassed Resin Compositions (N2), (N3) were each separately
catalyzed at ambient temperature under vacuum by the addition of a
catalyst composition (2 phr) as indicated in Table 8 to form ROMP
Compositions (N2), (N3). Each ROMP Composition (N2), (N3) was
poured into a separate set of two aluminum molds preheated to
35.degree. C. in a laboratory oven, the first mold being
rectangular and having dimensions (1.5''.times.1.5''.times.11'')
and the second mold being cylindrical and having dimensions
(0.79''.times.14''). After the molds were filled, the ROMP
compositions (N2), (N3) were heated from 35.degree. C. to
140.degree. C. at a heating rate of 3.5.degree. C./min, and then
held at 140.degree. C. for 2 hours, and then allowed to cool to
ambient temperature and demolded. The mechanical and thermal
properties of the demolded ROMP polymer articles corresponding to
ROMP Compositions (N2), (N3) were measured according to the methods
designated in Table 8.
TABLE-US-00008 TABLE 8 Measured properties of the ROMP polymers
from ROMP Compositions (N2), (N3) Example 21 22 ROMP ROMP
Composition Composition Property Method Units (N2).sup.a (N3).sup.b
Glass transition ASTM .degree. C. 51 51 temperature (Tg) E1356
Tensile strength ASTM MPa 31 30 (2''/min) D638 Tensile modulus ASTM
MPa 1396 1353 D638 Elongation @ yield ASTM % 6.7 6.6 D638
Elongation @ break ASTM % 128 167 D638 Compressive modulus ASTM MPa
970 956 (0.5''/min) D695 Compressive strength ASTM MPa 30 29 (5%
strain) D695 Compressive strength ASTM MPa 25 23 (10% strain) D695
Thermal conductivity ASTM W/m*K Not Not C518 Measured Measured
.sup.a= Catalyst Composition (H); .sup.b= Catalyst Composition
(E)
Examples 23-25
[0512] Resin Compositions (N1), (N2), (N3) were separately degassed
under vacuum for 20 minutes at ambient temperature (20-25.degree.
C.). Degassed Resin Compositions (N1), (N2), (N3) were each
separately catalyzed at ambient temperature under vacuum by the
addition of a catalyst composition (2 phr) as indicated in Table 9
to form ROMP Compositions (N1C), (N2), (N3). Each ROMP Composition
(N1C), (N2), (N3) was poured into a separate set of two aluminum
molds preheated to 35.degree. C. in a laboratory oven, the first
mold being rectangular and having dimensions
(1.5''.times.1.5''.times.11'') and the second mold being
cylindrical and having dimensions (0.79''.times.14''). After the
molds were filled, the temperature of the oven was held at
35.degree. C. and the ROMP compositions (N1C), (N2), (N3) were
allowed to polymerize (exotherm) and then allowed to cool to
ambient temperature and demolded. The mechanical and thermal
properties of the demolded ROMP polymer articles corresponding to
ROMP Compositions (N1C), (N2), (N3) were measured according to the
methods designated in Table 9.
TABLE-US-00009 TABLE 9 Measured properties of the ROMP polymers
from ROMP Compositions (N1C), (N2), (N3) Example 23 24 25 ROMP ROMP
ROMP Composition Composition Composition Property Method Units
(N1C).sup.a (N2).sup.b (N3).sup.c Glass transition ASTM .degree. C.
54 54 50 temperature (Tg) E1356 Tensile strength ASTM MPa 31 31 29
(2''/min) D638 Tensile modulus ASTM MPa 1342 1366 1299 D638
Elongation @ yield ASTM % 6.8 6.6 6.6 D638 Elongation @ break ASTM
% 142 148 172 D638 Compressive modulus ASTM MPa 998 979 964
(0.5''/min) D695 Compressive strength ASTM MPa 32 31 30 (5% strain)
D695 Compressive strength ASTM MPa 25 25 23 (10% strain) D695
Thermal conductivity ASTM W/m*K Not Not Not C518 Measured Measured
Measured .sup.a= Catalyst Composition (A); .sup.b= Catalyst
Composition (H); .sup.c= Catalyst Composition (E)
Example 26
[0513] Resin Composition (O) was degassed under vacuum for 20
minutes at ambient temperature (20-25.degree. C.). Degassed Resin
Composition (O) was catalyzed at ambient temperature under vacuum
by the addition of catalyst composition (A) (2 phr) to form ROMP
Composition (O). ROMP Composition (O) was poured into a set of two
aluminum molds preheated to 35.degree. C. in a laboratory oven, the
first mold being rectangular and having dimensions
(1.5''.times.1.5''.times.11'') and the second mold being
cylindrical and having dimensions (0.79''.times.14''). After the
molds were filled, the temperature of the oven was held at
35.degree. C. and ROMP Composition (O) was allowed to polymerize
(exotherm) and then allowed to cool to ambient temperature and
demolded. The mechanical and thermal properties of the demolded
ROMP polymer composite articles (e.g., syntactic foam)
corresponding to ROMP Composition (O) were measured according to
the methods designated in Table 10.
TABLE-US-00010 TABLE 10 Measured properties of the ROMP polymer
composites (e.g. syntactic foam) from ROMP Composition (O). Example
26 ROMP Composition Property Method Units (O) Glass transition ASTM
.degree. C. Not temperature (Tg) E1356 Measured Tensile strength
ASTM MPa 10.3 (2''/min) D638 Tensile modulus ASTM MPa 1658 D638
Elongation @ yield ASTM % 0.21 D638 Elongation @ break ASTM % 1.5
D638 Compressive modulus ASTM MPa 1099 (0.5''/min) D695 Compressive
strength ASTM MPa 19 (5% strain) D695 Compressive strength ASTM MPa
NA (10% strain) D695 Thermal conductivity ASTM W/m*K Not C518
Measured
Example 27
[0514] A common test in pipeline insulation testing is a simulated
service test (SST) designed to determine the thermal insulating
capacity and structural integrity of the polymeric material coating
the pipe after exposure to anticipated service conditions (high
temperature/high pressure) after a predetermined time period. Two
steel pipe samples (A and B) coated with thermal insulation of the
invention were prepared for this activity. Insulated Pipe Sample
(A) was prepared in a manner that allowed it to be exposed to high
temperature high pressure (HTHP) conditions (i.e., aged) of the
simulated service test and Insulated Pipe Sample (B) was prepared
as a control sample (i.e., un-aged) that was not exposed to the
HTHP conditions of the simulated service test.
[0515] Pipe Sample (A): A 6.625'' OD, 5.125'' ID, 8 ft length steel
pipe, equipped with a pressure rated flange fitting at one end and
closed off by a steel cap at the other end (Pipe Sample A), was
stripped of a prior fusion bonded epoxy (FBE) coating and rust by
blasting with garnet (silicates) before texturing to NACE "white"
specification with G25 steel grit to a blast profile of 4.5 mils.
The blast profile was checked with replica tape before coating Pipe
Sample (A) with thermal insulation material of the invention.
Particulates were removed from Pipe Sample (A) after blasting by
blowing on the pipe with >50 psi compressed air. Pipe Sample (A)
and a mold were pre-heated to 60.degree. C. and 40.degree. C.,
respectively, in insulated and temperature regulated heating boxes.
Insulated pipe sample (A): 91.80 kg of resin composition (D) was
added to a 30 gallon stainless steel pressure vessel with a bottom
drain for dispensing the resin composition. Resin composition (D)
was heated to 40.degree. C. in the stainless steel pressure vessel
and degassed for 2 hours under vacuum. Before dispensing resin
composition (D), the stainless steel pressure vessel was backfilled
with nitrogen gas. Resin composition (D) was dispensed and mixed
with Catalyst composition (A) using GS Manufacturing metering
equipment attached to a static mixer. Resin composition (D) was
mixed with catalyst composition (A) at a ratio of 50:1 (resin to
catalyst) as the resin stream entered the mix head of the mixed
metering equipment. The catalyzed resin composition (ROMP
composition) flowed into the heated mold surrounding pipe sample
(A) under air atmosphere. The thickness of cured ROMP polymer
(thermal insulation material) applied to the pipe sample (A) was
2''. It was undesirable for part quality to monitor the
temperatures of the pipe surface, mold surface, and ROMP
composition inside the mold cavity using thermocouples. However, it
was anticipated that peak temperature and time to exotherm values
were similar to those observed and recorded for Pipe Sample (B)
below.
[0516] Pipe Sample (B): Another steel pipe (Pipe Sample B) having
the same dimensions as Pipe Sample (A) was prepared in the same
manner as Pipe Sample (A). The blast profile was checked with
replica tape before coating Pipe Sample (B) with thermal insulation
material of the invention. Particulates were removed from Pipe
Sample (B) after blasting by blowing on the pipe with >50 psi
compressed air. Pipe Sample (B) and a mold were pre-heated to
60.degree. C. and 40.degree. C., respectively, in insulated and
temperature regulated heating boxes. Insulated pipe sample (B):
104.0 kg of resin composition (D) was added to a 30 gallon
stainless steel pressure vessel with a bottom drain for dispensing
the resin composition. Resin composition (D) was heated to
40.degree. C. in the stainless steel pressure vessel and degassed
for 2 hours under vacuum. Before dispensing resin composition (D),
the stainless steel pressure vessel was backfilled with nitrogen
gas. Resin composition (D) was dispensed and mixed with Catalyst
composition (A) using GS Manufacturing metering equipment attached
to a static mixer. Resin composition (D) was mixed with catalyst
composition (A) at a ratio of 50:1 (resin to catalyst) as the resin
stream entered the mix head of the mixed metering equipment. The
catalyzed resin composition (ROMP composition) flowed into the
heated mold surrounding the pipe sample (B) under air atmosphere.
The thickness of cured ROMP polymer (thermal insulation material)
applied to the pipe sample (B) was 2''. During the application of
the ROMP composition to Pipe Sample (B), temperature readings were
collected every 3 seconds by K-type thermocouples positioned in the
part at 28'' from the outlet port. One thermocouple (3) was
positioned at the ROMP composition/pipe interface, one thermocouple
(1) was positioned in the middle of the ROMP composition (1'' from
the mold and the pipe) and one thermocouple (2) was positioned at
the ROMP composition/mold interface. The peak temperatures measured
at the three thermocouple positions during curing of the ROMP
composition: thermocouple (1), thermocouple (2), and thermocouple
(3) were 183.degree. C., 182.degree. C., and 158.degree. C.,
respectively. The ROMP composition cure profile of Pipe Sample (B)
at the three different thermocouple positions was recorded as shown
in FIG. 3. In addition, the temperature of the pipe, the
temperature of the mold, and the temperature of the ROMP
composition immediately prior to applying the ROMP composition to
Pipe Sample (B) were also recorded and were found to be 47.degree.
C., 33.degree. C., and 34.degree. C., respectively. The time
required to fill the mold was 12 minutes. The ROMP composition had
a cure time (time to exotherm following catalyzation) of 31
minutes.
[0517] Simulated Service Test (HTHP conditions): Insulated pipe
sample (A) was attached to a heat source via the flange fitting and
submersed in a large chamber filled with simulated sea water. The
chamber was pressurized hydrostatically with a hydrostatic pump to
4500 psia. Simulated sea water in the chamber was cooled to
39.degree. F. (4.degree. C.). The pipe was heated such that the
hottest measured pipe/polymer interface temperature was equal to
400.degree. F. (204.degree. C.). These conditions were maintained
for 28 days at which point the heat source was removed and the
sample allowed to cool to 39.degree. F. (4.degree. C.). The cool
down profile was recorded using thermocouples at 8 separate
locations. The hottest thermocouple cooled from 400.degree. F. to
100.degree. F. in about 10 hours. The insulated pipe sample (A) was
removed from the chamber at 39.degree. F. (4.degree. C.). Adhesion
of the insulation material (ROMP polymer) to Insulated Pipe Sample
(A) after the simulated service test was excellent by visual
inspection.
[0518] Samples of the ROMP polymer (thermal insulation) were
obtained from insulated Pipe Sample A (aged) and insulated Pipe
Sample B (unaged) at three different locations designated as
follows: Inner (I)=ROMP polymer/pipe interface; Outer (O): Exterior
surface of ROMP polymer; and Center (C): ROMP polymer with inner
surface and exterior surface removed. The following properties of
the ROMP polymer samples were tested: tensile (elongation at yield,
elongation at break, maximum tensile strength), compression
(maximum compression strength), hardness (Shore D) and density.
Test results for aged samples (Insulated Pipe Sample A) and unaged
samples (Insulated Pipe Sample B) are presented below in Tables
11-14.
TABLE-US-00011 TABLE 11 Hardness determination with Shore D
Indenter (ASTM D2240) for ROMP polymer (thermal insulation) samples
obtained from insulated Pipe Sample (A) and insulated Pipe Sample
(B). Condition Outer (O) Center (C) Inner (I) Unaged (Insulated
Pipe Sample B) 72 73 72 Aged (Insulated Pipe Sample A) 72 72 71
TABLE-US-00012 TABLE 12 Density measurements (g/cm.sup.3) for ROMP
polymer (thermal insulation) samples obtained from insulated Pipe
Sample (A) and insulated Pipe Sample (B). Condition Outer (O) Inner
(I) Unaged (Insulated Pipe Sample B) 0.99 0.99 Aged (Insulated Pipe
Sample A) 0.99 0.99
TABLE-US-00013 TABLE 13 Tensile property data for ROMP polymer
(thermal insulation) samples obtained from insulated Pipe Sample
(A) and insulated Pipe Sample (B). ASTM D638 Type I samples.
2''/min strain rate. % elongation % elongation Max tensile
Condition Location at yield at break strength (psi) Unaged Outer
(O) 4.83 119 4911 Insulated Center (C) 4.79 102 4907 Pipe Sample B
Inner (I) 4.54 117 4830 Aged Outer (O) 4.75 138 5051 Insulated
Center (C) 4.25 111 4771 Pipe Sample A Inner (I) 4.89 141 4852
TABLE-US-00014 TABLE 14 Compression properties. ASTM D695.
0.5''/min strain rate. for ROMP polymer (thermal insulation)
samples obtained from insulated Pipe Sample (A) and insulated Pipe
Sample (B). % compression Max compression Condition Location at
yield strength (psi) Unaged Outer (O) 4.50 5780 Insulated Inner (I)
4.45 5678 Pipe Sample B Aged Outer (O) 4.38 5481 Insulated Inner
(I) 4.47 5435 Pipe Sample A
Example 28
[0519] Hot/wet aging. An extreme service condition of thermal
insulation on a subsea pipeline is taken to be direct contact of
hot insulation material with salt water at full hydrostatic
pressure. Thus, tensile and compression samples of a ROMP polymer
(thermal insulation) of the invention were subjected to hydrostatic
hot/wet aging.
[0520] Resin composition (A) was degassed under vacuum for 20
minutes at ambient temperature (20-25.degree. C.). Degassed resin
composition (A) was catalyzed at ambient temperature under vacuum
by the addition of catalyst composition (A) (2 phr) to form a ROMP
composition. The ROMP composition was poured into an aluminum mold
having dimension s (24''.times.24''.times.1/8'') preheated to
35.degree. C. in a laboratory oven. After the mold was filled, the
ROMP composition was held at 35.degree. C. for 15 minutes and then
heated from 35.degree. C. to 140.degree. C. at a heating rate of
3.5.degree. C./min, and then held at 140.degree. C. for 2 hours,
and then allowed to cool to ambient temperature, where the
resulting ROMP polymer panel was demolded.
[0521] ASTM D638 Type I tensile test samples and cylindrical 0.79''
diameter.times.1.58'' long ASTM D695 compression test samples
obtained from the molded ROMP polymer panel were aged in simulated
seawater for 6 months at 400.degree. F./204.degree. C. in a test
chamber. Weight change, hardness, T.sub.g, tensile and compression
properties of the ROMP polymer test samples were monitored by
occasionally opening the test chamber to remove ROMP polymer test
samples then resealing the test chamber. Dissolved oxygen content
in the simulated sea water was monitored by sampling the simulated
sea water in the test chamber prior to and after completion of each
aging duration (prior to an after a test sample was removed) and
was observed to be between 2-6 ppm, which was consistent with
anticipated subsea conditions. Test results for the hot/wet aging
of the ROMP polymer of Example 30 are presented below in Tables
15-18.
TABLE-US-00015 TABLE 15 Compression data for hydrostatic aging
(ASTM D695, 0.5''/min strain rate) of the ROMP polymer from Example
30. Compressive Compressive Aging strength at strength at
Compressive Compressive duration 5% strain 10% strain modulus Peak
Stress (days) (MPa) (MPa) (MPa) (MPa) 0 32.6 25.3 1112 34.5 15 33.8
27.2 1087 34.3 30 34.2 27.9 1094 34.7 60 38.4 31.8 1178 38.7 120
38.0 34.0 1139 38.0 180 38.8 37.1 1154 39.1
TABLE-US-00016 TABLE 16 Tensile data for hydrostatic aging (ASTM
D638 Type I samples, 2''/min strain rate) of the ROMP polymer from
Example 30 Aging Elongation Elongation Tensile Tensile duration at
break at yield strength modulus (days) (%) (%) (MPa) (MPa) 0 258.3
6.3 36.7 1313 30 36.9 6.6 32.1 1185 60 9.8 6.7 34.2 1420 120 12.9
7.2 34.7 1298 180 16.9 7.7 35.9 1394
TABLE-US-00017 TABLE 17 T.sub.g data for hydrostatic aging (by DSC,
ASTM E1356) of the ROMP polymer from Example 30. Aging duration
Glass transition (days) temperature (T.sub.g, .degree. C.) 0 50.04
15 52.37 30 54.96 60 56.72 120 66.18 180 77.35
TABLE-US-00018 TABLE 18 Weight change and hardness (ASTM D2240)
data for hydrostatic aging of the ROMP polymer from Example 30.
Aging duration Hardness Change (Shore D) (days) Wt. Change (%)
EXP-1464 15 0.50 1.0 30 0.41 0.5 60 0.29 0.5 120 0.20 1.5 180 0.12
2.5
Example 29
[0522] Impact Strength Testing: A key characteristic of subsea
pipeline insulation (thermal insulation) is its resistance to
removal (delamination) from the pipe or catastrophic failure due to
a high intensity impact that can be experienced during installation
of the pipeline or during transportation and handling of insulated
pipe segments prior to or during pipeline assembly and/or
installation.
[0523] An approximately 3-foot long section of insulated Pipe
Sample (B) (unaged) as described above herein, was secured to a
fixture and impacted with a free swinging mass at an energy of 22
kJ. The impacted sample survived with minimal surface damage; most
notably, an approximately 1/2''.times.6'' area was indented on the
outside diameter of the pipe insulation approximately 1/4'' deep.
There was no tearing or catastrophic failure of the insulation
material and the insulated pipe sample (B) was considered to be
suitable for installation following the impact test.
[0524] It is to be understood that while the invention has been
described in conjunction with specific embodiments thereof, that
the description above as well as the examples that follow are
intended to illustrate and not limit the scope of the invention.
Other aspects, advantages, and modifications within the scope of
the invention will be apparent to those skilled in the art to which
the invention pertains.
* * * * *