U.S. patent application number 17/164095 was filed with the patent office on 2021-12-30 for adhesion promoter compositions for cyclic olefin resin compositions.
This patent application is currently assigned to MATERIA, INC.. The applicant listed for this patent is MATERIA, INC.. Invention is credited to Paul W. BOOTHE, Christopher J. CRUCE, Brian EDGECOMBE, Michael A. GIARDELLO.
Application Number | 20210403654 17/164095 |
Document ID | / |
Family ID | 1000005828004 |
Filed Date | 2021-12-30 |
United States Patent
Application |
20210403654 |
Kind Code |
A1 |
CRUCE; Christopher J. ; et
al. |
December 30, 2021 |
ADHESION PROMOTER COMPOSITIONS FOR CYCLIC OLEFIN RESIN
COMPOSITIONS
Abstract
This invention relates to compositions and methods for improving
the adhesion of resin compositions to substrate materials. More
particularly, the invention relates to compositions and methods for
improving the adhesion of ROMP compositions to substrate materials
using an adhesion promoter composition, where the adhesion promoter
composition comprises a pre-reacted mixture comprising at least one
compound containing at least two isocyanate groups and at least one
compound comprising a heteroatom-containing functional group and a
metathesis active olefin, where the adhesion promoter composition
is storage stable and/or possesses in-resin storage stability when
added to a resin composition, particularly a cyclic olefin resin
composition, such as a ROMP composition. The polymer products
produced via ROMP reactions of the invention may be utilized for a
wide range of materials and composite applications. The invention
has utility in the fields of polymer and materials chemistry and
manufacture.
Inventors: |
CRUCE; Christopher J.;
(Poway, CA) ; EDGECOMBE; Brian; (Anaheim, CA)
; BOOTHE; Paul W.; (Brooklyn, NY) ; GIARDELLO;
Michael A.; (Pasadena, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
MATERIA, INC. |
Pasadena |
CA |
US |
|
|
Assignee: |
MATERIA, INC.
Pasadena
CA
|
Family ID: |
1000005828004 |
Appl. No.: |
17/164095 |
Filed: |
February 1, 2021 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
15120554 |
Aug 22, 2016 |
10907018 |
|
|
PCT/US15/17548 |
Feb 25, 2015 |
|
|
|
17164095 |
|
|
|
|
61945473 |
Feb 27, 2014 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08J 2345/00 20130101;
C08G 2261/418 20130101; C08K 5/101 20130101; C08J 5/24 20130101;
C08G 61/08 20130101; C08J 5/10 20130101; C08K 5/29 20130101; C08G
18/672 20130101; C08L 65/00 20130101; C08G 18/6715 20130101; C08G
2261/3325 20130101; C08G 2261/3324 20130101 |
International
Class: |
C08J 5/10 20060101
C08J005/10; C08L 65/00 20060101 C08L065/00; C08G 18/67 20060101
C08G018/67; C08J 5/24 20060101 C08J005/24; C08G 61/08 20060101
C08G061/08; C08K 5/101 20060101 C08K005/101; C08K 5/29 20060101
C08K005/29 |
Claims
1. A resin composition, comprising: at least one cyclic olefin; at
least one olefin metathesis catalyst; and at least one adhesion
promoter composition, where the at least one adhesion promoter
composition comprises a pre-reacted mixture of at least one
compound containing at least two isocyanate groups and at least one
compound comprising at least one heteroatom-containing functional
group and at least one metathesis active olefin, wherein the at
least one compound comprising at least one heteroatom-containing
functional group and at least one metathesis active olefin have the
following structure: (O.sup.M)-(Q*)n-(X*)--H wherein O.sup.M, Q*,
and X* are as follows: O.sup.M is a metathesis active olefin
fragment selected from cyclic olefins and acyclic olefins, where
the carbon-carbon double bond is not tetra-substituted; Q* is an
optional linker group selected from the group consisting of a
hydrocarbylene, substituted hydrocarbylene, heteroatom-containing
hydrocarbylene, and substituted heteroatom-containing
hydrocarbylene; n=0 or 1; and X* is oxygen, sulfur, or a
heteroatom-containing fragment selected from the group consisting
of N(R.sup.X), P(R.sup.X), OP(R.sup.X), OP(R.sup.X)O,
OP(OR.sup.X)O, P(.dbd.O)(R.sup.X), OP(.dbd.O)(R.sup.X),
OP(.dbd.O)(R.sup.X)O, OP(.dbd.O)(OR.sup.X)O, Si(R.sup.X).sub.2,
Si(R.sup.X).sub.2O, Si(OR.sup.X).sub.2O, and
Si(R.sup.X)(OR.sup.X)O, wherein each R.sup.X is, independent of one
another, a hydrogen, an aryl, and a lower alkyl group, wherein the
mol ratio of the at least one compound comprising at least one
heteroatom-containing functional group and at least one metathesis
active olefin relative to the at least one compound containing at
least two isocyanate groups ranges from 0.01:1 to 0.5:1.
2. The resin composition of claim 1, wherein the at least one
compound containing at least two isocyanate groups is selected from
the group consisting of methylene diphenyl diisocyanate and
hexamethylene diisocyanate and the at least one compound comprising
at least one heteroatom containing functional group and at least
one metathesis active olefin is selected from the group consisting
of 2-hydroxyethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate (HENB),
2-hydroxyethyl acrylate (HEA), oleyl alcohol, and 9-decen-1-ol.
3. The resin composition of claim 2, wherein the pre-reacted
mixture of 2-hydroxyethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate
(HENB) and methylene diphenyl diisocyanate comprises
##STR00068##
4. The resin composition of claim 1, wherein the adhesion promoter
is present in an amount ranging from 0.001-50 phr.
5. The resin composition of claim 1, wherein the at least one
adhesion promoter composition is storage stable.
6. The resin composition of claim 1, wherein the at least one
adhesion promoter composition is in-resin storage stable.
7. The resin composition of claim 1, further comprising: at least
one substrate material.
8. The resin composition of claim 7, wherein the substrate material
is a glass substrate or a carbon substrate.
9. The resin composition of claim 1, wherein the at least one
olefin metathesis catalyst is a Group 8 transition metal complex
having the structure of Formula (I): ##STR00069## wherein M is a
Group 8 transition metal selected from ruthenium and osmium;
L.sup.1, L.sup.2, and L.sup.3 are neutral electron donor ligands; n
is 0 or 1, such that L.sup.3 may or may not be present; m is 0, 1,
or 2; k is 0 or 1; X.sup.1 and X.sup.2 are anionic ligands; and
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, 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.
10. The resin composition of claim 9, wherein the at least one of
12, L.sup.2, and L.sup.3 is an N-heterocyclic carbene ligand.
11. The resin composition of claim 10, wherein the N-heterocyclic
carbene ligand has the structure ##STR00070## wherein, Q is
--CR.sup.11R.sup.12--CR.sup.13R.sup.14-- or
--CR.sup.11.dbd.CR.sup.13--, 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, or wherein 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; and R.sup.3 and
R.sup.4 are 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.
12. The resin composition of claim 1, wherein the at least one
olefin metathesis catalyst is a Group 8 transition metal complex
having the structure of Formula (VII), wherein: ##STR00071## M is
ruthenium; X.sup.1 and X.sup.2 are anionic ligands; L.sup.1 is a
neutral electron donor ligand; Y is a heteroatom selected from N,
O, S, and P; 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, and
borate; n is 0, 1, or 2, such that n is 1 for the divalent
heteroatoms O or S, and n is 2 for the trivalent heteroatoms N or
P; and 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.
13. The resin composition of claim 1, wherein the at least one
olefin metathesis catalyst has the structure of Formula (I):
##STR00072## wherein: M is ruthenium; n is 0; m is 0; k is 1;
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); L.sup.3 is not present; X.sup.1 and X.sup.2 are
chloride; and 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.7 are
taken together to form phenylindenylidene.
14. The resin composition of claim 1, wherein the at least one
olefin metathesis catalyst has the structure of Formula (I):
##STR00073## wherein: M is ruthenium; n is 0; m is 0; k is 1;
L.sup.1 is an N-heterocyclic carbene selected from the group
consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene
and 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; L.sup.2 is a
trisubstituted phosphine independently selected from the group
consisting of tri-n-butylphosphine (Pn-Bus);
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); L.sup.3 is not present;
X.sup.1 and X.sup.2 are chloride; and 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
phenylindenylidene.
15. The resin composition of claim 1, wherein the cyclic olefin is
selected from the group consisting of dicyclopentadiene;
tricyclopentadiene; cyclopentadiene tetramer; cyclopentadiene
pentamer; dicyclohexadiene; norbornene; 5-methyl-2-norbornene;
5-ethyl-2-norbornene; 5-isobutyl-2-norbornene;
5,6-dimethyl-2-norbornene; 5-phenyl norbornene; 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; 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.
16. The resin composition of claim 1, wherein the cyclic olefin is
selected from the group consisting of dicyclopentadiene;
tricyclopentadiene; cyclopentadiene tetramer; cyclopentadiene
pentamer; tetracyclododecene; norbornene; 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.
17. The resin composition of claim 1, wherein the resin composition
further comprises at least one additive.
18. The resin composition of claim 1, wherein the resin composition
further comprises at least one crosslinker.
19. The resin composition of claim 18, wherein the at least one
crosslinker is selected from the group consisting of dialkyl
peroxides, diacyl peroxides, peroxyacids, and mixtures thereof.
20. An article of manufacture comprising at least one resin
composition of claim 1.
21. A method for improving the adhesion of a resin composition to a
substrate material, comprising: combining at least one cyclic
olefin, at least one olefin metathesis catalyst, and the at least
one adhesion promoter composition of claim 1 to form a resin
composition, contacting the resin composition with the substrate
material, and subjecting the resin composition to conditions
effective to promote an olefin metathesis reaction of the cyclic
olefin.
Description
RELATED APPLICATIONS
[0001] This application is a Divisional of U.S. application Ser.
No. 15/120,554, filed Aug. 22, 2016; which is a 371 National Phase
Application of PCT/US2015/017548, filed Feb. 25, 2015; which claims
the benefit of U.S. Provisional Patent Application No. 61/945,473,
filed Feb. 27, 2014, the contents of which is incorporated herein
by reference.
TECHNICAL FIELD
[0002] The present invention relates to methods and compositions
for improving the adhesion of olefin metathesis compositions to
substrate materials. More particularly, the invention relates to
methods and compositions for improving the adhesion of ring opening
metathesis polymerization (ROMP) compositions to substrate
materials and the manufacture of polymer articles (e.g., polymer
composite articles) via ROMP. Polymer products produced via the
metathesis reactions of the invention may be utilized for a wide
range of materials and composite applications. The invention has
utility in the fields of polymer and materials chemistry and
manufacture.
BACKGROUND
[0003] Polymer-matrix composites offer unique combinations of
properties and are useful in a wide range of applications. Such
composites may be fabricated utilizing either thermosetting or
thermoplastic polymer matrix materials with a variety of
particulate or fibrous fillers or reinforcements. It is generally
advantageous to have strong adhesion between the polymer matrix
material and the surfaces of the various particulate or fibrous
substrates and there is considerable art related to substrate
finishes and other treatments to optimize adhesion to polymer
matrices. For example, in the production of long-fiber reinforced
composites, improved adhesion between the polymer matrix and the
fiber reinforcement leads to increased material performance. Good
adhesion is particularly important where failures are likely to
occur by delamination or by other adhesive failure modes.
[0004] As described in, for example, U.S. Pat. Nos. 5,840,238,
6,310,121, and 6,525,125, the disclosures of each of which are
incorporated herein by reference, polymers generated by olefin
metathesis processes are attractive as composite matrix materials.
Of particularly beneficial use are the polymers generated by the
ROMP of cyclic olefins. The low viscosity of cyclic olefin resin
formulations and the ability to control ROMP kinetics (e.g., U.S.
Pat. Nos. 4,708,969 and 5,939,504, the disclosures of both of which
are incorporated herein by reference) facilitate composite
processing and manufacture, and the corrosion resistance and high
toughness of ROMP polymers leads to good composite durability.
Additionally, certain properties of ROMP polymers, e.g., mechanical
strength and stiffness, heat distortion temperature and solvent
resistance, can be further enhanced by crosslinking induced via
thermal treatment (e.g., U.S. Pat. No. 4,902,560, the disclosure of
which is incorporated herein by reference) or chemically by
addition of peroxides (e.g., U.S. Pat. No. 5,728,785, the
disclosure of which is incorporated herein by reference).
[0005] Commercially important ROMP resin formulations are generally
based on readily available and inexpensive cyclic olefins such as
dicyclopentadiene (DCPD), norbornenes, cyclooctadiene (COD), and
various cycloalkenes. However, in contrast to traditional resin
systems (e.g., epoxy, acrylate, urethane, and polyester resins)
based on polar functional group chemistries, these nonpolar ROMP
resins have poor intrinsic adhesion to the relatively polar
surfaces of common carbon, glass, or mineral fillers and
reinforcements. The addition of various silanes to such resin
formulations for improvement of electrical and mechanical
properties of ROMP polymers is described in U.S. Pat. Nos.
5,840,238, 6,001,909, and 7,339,006, the disclosures of each of
which are incorporated herein by reference. Many widely used
commercial silanes do not give optimal properties with ROMP
polymers, however, and the greatest enhancements are only obtained
when the silanes comprise groups with high metathesis activity (the
relative reactivity of various metathesis active groups is
described in J. Am. Chem. Soc., 2003, 125, 11360-11370).
[0006] As described in International Patent Application Number
PCT/US2012/042850, the disclosure of which is incorporated herein
by reference, it was discovered that the addition of an adhesion
promoter comprising a compound containing at least two isocyanate
groups to a cyclic olefin resin formulation (e.g., ROMP resin
formulation) provides beneficial improvements in the adhesion of a
cyclic olefin resin formulation to substrate materials, such as,
for example carbon and glass reinforcement materials.
[0007] According to International Patent Application Number
PCT/US2012/042850, addition of an adhesion promoter comprising a
compound containing at least two isocyanate groups to a cyclic
olefin resin formulation, where the resin formulation comprising
the adhesion promoter was contacted with an olefin metathesis
catalyst and used to manufacture ROMP polymer-matrix composites,
provided improved adhesion of ROMP polymer matrices to composite
substrate materials compared to ROMP polymer matrices without such
adhesion promoters. Adhesion of the ROMP polymer-matrices to
substrate materials was measured by the short beam shear method
according to ASTM D2344. Interlaminar shear strength (ILSS) is a
measure of the adhesion and/or compatibility between the polymer
matrix and the substrate material in a composite.
[0008] In addition, International Patent Application Number
PCT/US2012/042850 also demonstrated that the addition of at least
one compound comprising a heteroatom-containing functional group
and a metathesis active olefin (e.g., 2-hydroxyethyl
bicyclo[2.2.1]hept-2-ene-5-carboxylate (HENB)) to a cyclic olefin
resin formulation (e.g., ROMP resin formulation) comprising at
least one cyclic olefin and an adhesion promoter comprising at
least one compound containing at least two isocyanate groups, where
the resin formulation comprising the adhesion promoter was
contacted with an olefin metathesis catalyst and used to
manufacture ROMP polymer-matrix composites, further improved the
efficacy of the adhesion promoter to effectuate adhesion between
the ROMP polymer-matrix and the composite substrate material.
[0009] While International Patent Application Number
PCT/US2012/042850 demonstrated that compounds containing at least
two isocyanate groups are effective to improve the adhesion of
cyclic olefin resin formulations to substrate materials (e.g.,
carbon and/or glass substrate materials), the in-resin storage
stability of adhesion promoters comprising at least one compound
containing at least two isocyanate groups was not addressed.
Furthermore, the in-resin storage stability of adhesion promoters
comprising at least one compound containing at least two isocyanate
groups, where the cyclic olefin resin formulation (e.g., ROMP resin
formulation) further comprises at least one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin was also not addressed.
[0010] The importance of using additives in resin formulations,
particularly cyclic olefin resin formulations, where the additives
are storage stable and/or possess in-resin storage stability is
known in the art. For example, U.S. Pat. No. 4,943,621 discloses
the importance of using storage stable additives possessing
in-resin storage stability, particularly storage stable
co-catalysts, as components in cyclic olefin resin formulations.
Moreover, preparing cyclic olefin resin formulations which comprise
additives having in-resin storage stability is of particular
importance in the commercial manufacturing of polymer articles
and/or polymer-matrix composites manufactured from such cyclic
olefin resin formulations. For example, for a manufacturer of
cyclic olefin resin formulations to successfully commercialize such
resin formulations it is often necessary to be able transport and
store the resin formulations prior to use, which further
necessitates the need for the use of in-resin storage stable
additives and components. Furthermore, it is often preferable,
particularly from a commercial perspective, that the cyclic olefin
resin formulations be provided to customers, molders, and other
end-users with all of the necessary additives and components
contained in the cyclic olefin resin formulation so that these
individuals can avoid additional processing and therefore use the
resin formulations as received to manufacture articles comprising
ROMP polymers and/or ROMP polymer-matrix composites.
[0011] After further investigation into the in-resin storage
stability of adhesion promoters comprising compounds containing at
least two isocyanate groups, the inventors have discovered that
such adhesion promoters do possess in-resin storage stability,
particularly where the resin is a cyclic olefin resin. This
in-resin storage stability is observed by little or no decrease in
the ILSS over time of polymer-matrix composites prepared using
resin compositions comprising at least one adhesion promoter, where
the at least one adhesion promoter comprises at least one compound
containing at least two isocyanate groups. The in-resin storage
stability of adhesion promoters comprising compounds containing at
least two isocyanate groups, particularly where the resin is a
cyclic olefin resin is demonstrated and discussed infra.
[0012] Surprisingly, however, the inventors have discovered that
when a compound comprising a heteroatom-containing functional group
and a metathesis active olefin (e.g., 2-hydroxyethyl
bicyclo[2.2.1]hept-2-ene-5-carboxylate (HENB)) is independently or
separately added to the cyclic olefin resin formulation containing
an adhesion promoter comprising a compound containing at least two
isocyanate groups, the in-resin storage stability of the adhesion
promoter is adversely affected as observed by a decrease in the
ILSS over time of polymer-matrix composites prepared using such
resin formulations, the results of which are demonstrated and
discussed infra.
[0013] Despite the advances achieved in the art, particularly in
the properties of olefin metathesis polymers (e.g., ROMP polymers
and ROMP polymer-matrix composites) and their associated
applications, a continuing need therefore exists for further
improvement in a number of areas, including the manufacture of
cyclic olefin resin formulations, in particular ROMP resin
formulations, for use in the manufacture of ROMP polymer-matrix
composites, where such composites possess strong adhesion between
the polymer matrix and substrate material (e.g., carbon and/or
glass reinforcement materials) Furthermore, there also exists a
need for further improvement in the manufacture of cyclic olefin
resin formulations, in particular ROMP resin formulations, where
the formulation additives and components, particularly adhesion
promoters, are storage stable and/or possess in-resin storage
stability.
SUMMARY OF INVENTION
[0014] The present invention is directed to addressing one or more
of the aforementioned concerns and relates to the use of an
adhesion promoter composition in a resin composition, such as a
ROMP composition, or as a substrate material pre-treatment to
provide useful improvements in the adhesion of a metathesis
catalyzed composition to the substrate material.
[0015] More particularly, the inventors have discovered that
addition of an adhesion promoter composition according to the
invention to a resin composition, particularly a ROMP composition,
allows for improvements in the adhesion of the polymerized (resin)
composition to the substrate material, without adversely affecting
the mechanical properties of the polymerized resin and/or
polymer-matrix composite. Alternatively, a substrate material may
be pre-treated with an adhesion promoter composition according to
the invention in order to improve the adhesion of the polymerized
(resin) composition to the substrate material, without adversely
affecting the mechanical properties of the polymerized resin and/or
polymer-matrix composite. In addition, the inventors have
discovered that adhesion promoter compositions according to the
invention possess in-resin storage stability when added to a resin
composition, particularly a cyclic olefin resin composition, such
as a ROMP composition.
[0016] Adhesion promoter compositions according to the present
invention, discussed infra, are generally comprised of a
pre-reacted mixture comprising at least one compound containing at
least two isocyanate groups and at least one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin. Adhesion promoter compositions of the invention possess
in-resin storage stability when combined with, contacted with, or
added to a cyclic olefin resin composition (e.g., ROMP resin
composition). Furthermore, adhesion promoter compositions of the
invention may also be storage stable.
[0017] In one embodiment, the invention provides a composition for
improving the adhesion of a resin composition, for example a ROMP
composition, to a substrate material (e.g., carbon and/or glass
reinforcement material), in which an adhesion promoter composition
of the invention is combined with at least one cyclic olefin, and
at least one olefin metathesis catalyst (e.g., a cyclic olefin
metathesis catalyst), thereby forming a composition with improved
mechanical properties.
[0018] In another embodiment, the invention provides a composition
for improving the adhesion of a resin composition, for example a
ROMP composition, to a substrate material (e.g., carbon and/or
glass reinforcement material), in which an adhesion promoter
composition of the invention is combined with at least one cyclic
olefin, at least one olefin metathesis catalyst (e.g., a cyclic
olefin metathesis catalyst), and a substrate material, thereby
forming a composition with improved mechanical properties.
[0019] In another embodiment, the invention provides an adhesion
promoter composition comprising a pre-reacted mixture of at least
one compound containing at least two isocyanate groups, and at
least one compound comprising a heteroatom-containing functional
group and a metathesis active olefin.
[0020] In another embodiment, the invention provides a storage
stable adhesion promoter composition comprising a pre-reacted
mixture of at least one compound containing at least two isocyanate
groups, and at least one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin.
[0021] In another embodiment, the invention provides an adhesion
promoter composition comprising a pre-reacted mixture of at least
one compound containing at least two isocyanate groups, and at
least one compound comprising a heteroatom-containing functional
group and a metathesis active olefin, wherein the adhesion promoter
composition possesses in-resin storage stability when added to a
resin composition, wherein the resin composition comprises at least
one cyclic olefin.
[0022] In another embodiment, the invention provides a storage
stable adhesion promoter composition comprising a pre-reacted
mixture of at least one compound containing at least two isocyanate
groups, and at least one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin, wherein the storage stable adhesion promoter composition
possesses in-resin storage stability when added to a resin
composition, wherein the resin composition comprises at least one
cyclic olefin.
[0023] In another embodiment, the invention provides an adhesion
promoter composition comprising a pre-reacted mixture of at least
one compound comprising at least two isocyanate groups, and at
least one compound comprising a heteroatom-containing functional
group and a metathesis active olefin.
[0024] In another embodiment, the invention provides a storage
stable adhesion promoter composition comprising a pre-reacted
mixture of at least one compound comprising at least two isocyanate
groups, and at least one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin.
[0025] In another embodiment, the invention provides an adhesion
promoter composition comprising a pre-reacted mixture of at least
one compound comprising at least two isocyanate groups, and at
least one compound comprising a heteroatom-containing functional
group and a metathesis active olefin, wherein the adhesion promoter
composition possesses in-resin storage stability when added to a
resin composition, wherein the resin composition comprises at least
one cyclic olefin.
[0026] In another embodiment, the invention provides a storage
stable adhesion promoter composition comprising a pre-reacted
mixture of at least one compound comprising at least two isocyanate
groups, and at least one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin, wherein the storage stable adhesion promoter composition
possesses in-resin storage stability when added to a resin
composition, wherein the resin composition comprises at least one
cyclic olefin.
[0027] In another embodiment, the invention provides a method for
preparing an adhesion promoter composition, comprising combining at
least one compound containing at least two isocyanate groups with
at least one compound comprising a heteroatom-containing functional
group and a metathesis active olefin to form a mixture, and
subjecting the mixture to conditions effective such that a
pre-reaction there between takes place.
[0028] In another embodiment, the invention provides a method for
preparing a storage stable adhesion promoter composition,
comprising combining at least one compound containing at least two
isocyanate groups with at least one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin to form a mixture, and subjecting the mixture to conditions
effective such that a pre-reaction there between takes place.
[0029] In another embodiment, the invention provides a method for
preparing an adhesion promoter composition comprising combining at
least one compound containing at least two isocyanate groups with
at least one compound comprising a heteroatom-containing functional
group and a metathesis active olefin to form a mixture, and
subjecting the mixture to conditions effective that a pre-reaction
there between takes place, wherein the adhesion promoter
composition possesses in-resin storage stability when added to a
resin composition, wherein the resin composition comprises at least
one cyclic olefin.
[0030] In another embodiment, the invention provides a method for
preparing a storage stable adhesion promoter composition comprising
combining at least one compound containing at least two isocyanate
groups with at least one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin to form a mixture, and subjecting the mixture to conditions
effective that a pre-reaction there between takes place, wherein
the storage stable adhesion promoter composition possesses in-resin
storage stability when added to a resin composition, wherein the
resin composition comprises at least one cyclic olefin.
[0031] In another embodiment, the invention provides a method for
preparing an adhesion promoter composition, comprising combining at
least one compound containing at least two isocyanate groups with
at least one compound comprising a heteroatom-containing functional
group and a metathesis active olefin to form a mixture, and
subjecting the mixture to conditions effective such that a reaction
there between takes place.
[0032] In another embodiment, the invention provides a method for
preparing a storage stable adhesion promoter composition,
comprising combining at least one compound containing at least two
isocyanate groups with at least one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin to form a mixture, and subjecting the mixture to conditions
effective such that a reaction there between takes place.
[0033] In another embodiment, the invention provides a method for
preparing an adhesion promoter composition comprising combining at
least one compound containing at least two isocyanate groups with
at least one compound comprising a heteroatom-containing functional
group and a metathesis active olefin to form a mixture, and
subjecting the mixture to conditions effective that a reaction
there between takes place, wherein the adhesion promoter
composition possesses in-resin storage stability when added to a
resin composition, wherein the resin composition comprises at least
one cyclic olefin.
[0034] In another embodiment, the invention provides a method for
preparing a storage stable adhesion promoter composition comprising
combining at least one compound containing at least two isocyanate
groups with at least one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin to form a mixture, and subjecting the mixture to conditions
effective that a reaction there between takes place, wherein the
storage stable adhesion promoter composition possesses in-resin
storage stability when added to a resin composition, wherein the
resin composition comprises at least one cyclic olefin.
[0035] In another embodiment, the invention provides an adhesion
promoter composition comprising a pre-reacted mixture of at least
one compound containing at least two isocyanate groups, and at
least one compound comprising a heteroatom-containing functional
group and a metathesis active olefin, where the adhesion promoter
composition is suitable for use in a cyclic olefin resin
composition, and where the adhesion promoter composition possesses
in-resin storage stability when added to the cyclic olefin resin
composition.
[0036] In another embodiment, the invention provides a storage
stable adhesion promoter composition comprising a pre-reacted
mixture of at least one compound containing at least two isocyanate
groups, and at least one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin, where the storage stable adhesion promoter composition is
suitable for use in a cyclic olefin resin composition, and where
the storage stable adhesion promoter composition possesses in-resin
storage stability when added to the cyclic olefin resin
composition.
[0037] In another embodiment, the invention provides an adhesion
promoter composition comprising a pre-reacted mixture of at least
one compound containing at least two isocyanate groups, and at
least one compound comprising a heteroatom-containing functional
group and a metathesis active olefin, where the adhesion promoter
composition is suitable for use in a cyclic olefin resin
composition.
[0038] In another embodiment, the invention provides a storage
stable adhesion promoter composition comprising a pre-reacted
mixture of at least one compound containing at least two isocyanate
groups, and at least one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin, where the adhesion promoter composition is suitable for use
in a cyclic olefin resin composition.
[0039] In another embodiment, the invention provides a method for
improving the adhesion of a resin composition to a substrate
material comprising combining at least one cyclic olefin, at least
one olefin metathesis catalyst, and at least one adhesion promoter
composition to form the resin composition, contacting the resin
composition with the substrate material, and subjecting the resin
composition to conditions effective to promote an olefin metathesis
reaction of the cyclic olefin, wherein the at least one adhesion
promoter composition comprises a pre-reacted mixture of at least
one compound containing at least two isocyanate groups and at least
one compound comprising a heteroatom-containing functional group
and a metathesis active olefin.
[0040] In another embodiment, the invention provides a method for
improving the adhesion of a resin composition to a substrate
material comprising combining at least one cyclic olefin, at least
one olefin metathesis catalyst, and at least one storage stable
adhesion promoter composition to form the resin composition,
contacting the resin composition with the substrate material, and
subjecting the resin composition to conditions effective to promote
an olefin metathesis reaction of the cyclic olefin, wherein the at
least one storage stable adhesion promoter composition comprises a
pre-reacted mixture of at least one compound containing at least
two isocyanate groups and at least one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin.
[0041] In another embodiment, the invention provides a method for
improving the adhesion of a resin composition to a substrate
material comprising combining at least one cyclic olefin, at least
one olefin metathesis catalyst, and at least one adhesion promoter
composition to form the resin composition, contacting the resin
composition with the substrate material, and subjecting the resin
composition to conditions effective to promote an olefin metathesis
reaction of the cyclic olefin, wherein the at least one adhesion
promoter composition comprises a pre-reacted mixture of at least
one compound containing at least two isocyanate groups and at least
one compound comprising a heteroatom-containing functional group
and a metathesis active olefin, and where the adhesion promoter
composition possesses in-resin storage stability when added to the
resin composition.
[0042] In another embodiment, the invention provides a method for
improving the adhesion of a resin composition to a substrate
material comprising combining at least one cyclic olefin, at least
one olefin metathesis catalyst, and at least one storage stable
adhesion promoter composition to form the resin composition,
contacting the resin composition with the substrate material, and
subjecting the resin composition to conditions effective to promote
an olefin metathesis reaction of the cyclic olefin, wherein the at
least one storage stable adhesion promoter composition comprises a
pre-reacted mixture of at least one compound containing at least
two isocyanate groups and at least one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin, and where the storage stable adhesion promoter composition
possesses in-resin storage stability when added to the resin
composition.
[0043] In another embodiment, the invention provides a method for
improving the adhesion of a resin composition to a substrate
material comprising combining at least one cyclic olefin, at least
one olefin metathesis catalyst, and at least one substrate
material, and at least one adhesion promoter composition to form
the resin composition, and subjecting the resin composition to
conditions effective to promote an olefin metathesis reaction of
the cyclic olefin, wherein the at least one adhesion promoter
composition comprises a pre-reacted mixture of at least one
compound containing at least two isocyanate groups and at least one
compound comprising a heteroatom-containing functional group and a
metathesis active olefin.
[0044] In another embodiment, the invention provides a method for
improving the adhesion of a resin composition to a substrate
material comprising combining at least one cyclic olefin, at least
one olefin metathesis catalyst, and at least one substrate
material, and at least one storage stable adhesion promoter
composition to form the resin composition, and subjecting the resin
composition to conditions effective to promote an olefin metathesis
reaction of the cyclic olefin, wherein the at least one storage
stable adhesion promoter composition comprises a pre-reacted
mixture of at least one compound containing at least two isocyanate
groups and at least one compound comprising a heteroatom-containing
functional group and a metathesis active olefin.
[0045] In another embodiment, the invention provides a method for
improving the adhesion of a resin composition to a substrate
material comprising combining at least one cyclic olefin, at least
one olefin metathesis catalyst, and at least one substrate
material, and at least one adhesion promoter composition to form
the resin composition, and subjecting the resin composition to
conditions effective to promote an olefin metathesis reaction of
the cyclic olefin, wherein the at least one adhesion promoter
composition comprises a pre-reacted mixture of at least one
compound containing at least two isocyanate groups and at least one
compound comprising a heteroatom-containing functional group and a
metathesis active olefin, and where the adhesion promoter
composition possesses in-resin storage stability when added to the
resin composition.
[0046] In another embodiment, the invention provides a method for
improving the adhesion of a resin composition to a substrate
material comprising combining at least one cyclic olefin, at least
one olefin metathesis catalyst, and at least one substrate
material, and at least one storage stable adhesion promoter
composition to form the resin composition, and subjecting the resin
composition to conditions effective to promote an olefin metathesis
reaction of the cyclic olefin, wherein the at least one storage
stable adhesion promoter composition comprises a pre-reacted
mixture of at least one compound containing at least two isocyanate
groups and at least one compound comprising a heteroatom-containing
functional group and a metathesis active olefin, and where the
storage stable adhesion promoter composition possesses in-resin
storage stability when added to the resin composition.
[0047] In another embodiment, the invention provides a resin
composition comprising at least one cyclic olefin, at least one
olefin metathesis catalyst, and at least one adhesion promoter
composition, where the adhesion promoter composition comprises a
pre-reacted mixture of at least one compound comprising at least
two isocyanate groups and at least one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin.
[0048] In another embodiment, the invention provides a resin
composition comprising at least one cyclic olefin, at least one
olefin metathesis catalyst, and at least one storage stable
adhesion promoter composition, where the storage stable adhesion
promoter composition comprises a pre-reacted mixture of at least
one compound comprising at least two isocyanate groups and at least
one compound comprising a heteroatom-containing functional group
and a metathesis active olefin.
[0049] In another embodiment, the invention provides a resin
composition comprising at least one cyclic olefin, at least one
olefin metathesis catalyst, and at least one adhesion promoter
composition, where the adhesion promoter composition comprises a
pre-reacted mixture of at least one compound comprising at least
two isocyanate groups and at least one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin, wherein the adhesion promoter composition is in-resin
storage stable.
[0050] In another embodiment, the invention provides a resin
composition comprising at least one cyclic olefin, at least one
olefin metathesis catalyst, and at least one storage stable
adhesion promoter composition, where the storage stable adhesion
promoter composition comprises a pre-reacted mixture of at least
one compound comprising at least two isocyanate groups and at least
one compound comprising a heteroatom-containing functional group
and a metathesis active olefin, wherein the storage stable adhesion
promoter composition is in-resin storage stable.
[0051] In another embodiment, the invention provides a resin
composition comprising at least one cyclic olefin, at least one
olefin metathesis catalyst, and at least one adhesion promoter
composition, where the adhesion promoter composition comprises a
pre-reacted mixture of at least one compound comprising at least
two isocyanate groups and at least one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin, and where the adhesion promoter composition possesses
in-resin storage stability when added to the resin composition.
[0052] In another embodiment, the invention provides a resin
composition comprising at least one cyclic olefin, at least one
olefin metathesis catalyst, and at least one storage stable
adhesion promoter composition, where the storage stable adhesion
promoter composition comprises a pre-reacted mixture of at least
one compound comprising at least two isocyanate groups and at least
one compound comprising a heteroatom-containing functional group
and a metathesis active olefin, and where the storage stable
adhesion promoter composition possesses in-resin storage stability
when added to the resin composition.
[0053] In another embodiment, the invention provides a resin
composition comprising at least one cyclic olefin, and at least one
adhesion promoter composition, where the adhesion promoter
composition comprises a pre-reacted mixture of at least one
compound comprising at least two isocyanate groups and at least one
compound comprising a heteroatom-containing functional group and a
metathesis active olefin.
[0054] In another embodiment, the invention provides a resin
composition comprising at least one cyclic olefin, and at least one
storage stable adhesion promoter composition, where the storage
stable adhesion promoter composition comprises a pre-reacted
mixture of at least one compound comprising at least two isocyanate
groups and at least one compound comprising a heteroatom-containing
functional group and a metathesis active olefin.
[0055] In another embodiment, the invention provides a resin
composition comprising at least one cyclic olefin, and at least one
adhesion promoter composition, where the adhesion promoter
composition comprises a pre-reacted mixture of at least one
compound comprising at least two isocyanate groups and at least one
compound comprising a heteroatom-containing functional group and a
metathesis active olefin, wherein the adhesion promoter composition
is in-resin storage stable.
[0056] In another embodiment, the invention provides a resin
composition comprising at least one cyclic olefin, and at least one
storage stable adhesion promoter composition, where the storage
stable adhesion promoter composition comprises a pre-reacted
mixture of at least one compound comprising at least two isocyanate
groups and at least one compound comprising a heteroatom-containing
functional group and a metathesis active olefin, wherein the
storage stable adhesion promoter composition is in-resin storage
stable.
[0057] In another embodiment, the invention provides a resin
composition comprising at least one cyclic olefin, and at least one
adhesion promoter composition, where the adhesion promoter
composition comprises a pre-reacted mixture of at least one
compound comprising at least two isocyanate groups and at least one
compound comprising a heteroatom-containing functional group and a
metathesis active olefin, and where the adhesion promoter
composition possesses in-resin storage stability when added to the
resin composition.
[0058] In another embodiment, the invention provides a resin
composition comprising at least one cyclic olefin, and at least one
storage stable adhesion promoter composition, where the storage
stable adhesion promoter composition comprises a pre-reacted
mixture of at least one compound comprising at least two isocyanate
groups and at least one compound comprising a heteroatom-containing
functional group and a metathesis active olefin, and where the
storage stable adhesion promoter composition possesses in-resin
storage stability when added to the resin composition.
[0059] In another embodiment, the invention provides a resin
composition comprising at least one cyclic olefin, at least one
olefin metathesis catalyst, at least one substrate material, and at
least one adhesion promoter composition, where the adhesion
promoter composition comprises a pre-reacted mixture of at least
one compound comprising at least two isocyanate groups and at least
one compound comprising a heteroatom-containing functional group
and a metathesis active olefin.
[0060] In another embodiment, the invention provides a resin
composition comprising at least one cyclic olefin, at least one
olefin metathesis catalyst, at least one substrate material, and at
least one storage stable adhesion promoter composition, where the
storage stable adhesion promoter composition comprises a
pre-reacted mixture of at least one compound comprising at least
two isocyanate groups and at least one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin.
[0061] In another embodiment, the invention provides a resin
composition comprising at least one cyclic olefin, at least one
olefin metathesis catalyst, at least one substrate material, and at
least one adhesion promoter composition, where the adhesion
promoter composition comprises a pre-reacted mixture of at least
one compound comprising at least two isocyanate groups and at least
one compound comprising a heteroatom-containing functional group
and a metathesis active olefin, wherein the adhesion promoter
composition is in-resin storage stable.
[0062] In another embodiment, the invention provides a resin
composition comprising at least one cyclic olefin, at least one
olefin metathesis catalyst, at least one substrate material, and at
least one storage stable adhesion promoter composition, where the
storage stable adhesion promoter composition comprises a
pre-reacted mixture of at least one compound comprising at least
two isocyanate groups and at least one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin, wherein the storage stable adhesion promoter composition is
in-resin storage stable.
[0063] In another embodiment, the invention provides a resin
composition comprising at least one cyclic olefin, at least one
olefin metathesis catalyst, at least one substrate material, and at
least one adhesion promoter composition, where the adhesion
promoter composition comprises a pre-reacted mixture of at least
one compound comprising at least two isocyanate groups and at least
one compound comprising a heteroatom-containing functional group
and a metathesis active olefin, and where the adhesion promoter
composition possesses in-resin storage stability when added to the
resin composition.
[0064] In another embodiment, the invention provides a resin
composition comprising at least one cyclic olefin, at least one
olefin metathesis catalyst, at least one substrate material, and at
least one storage stable adhesion promoter composition, where the
storage stable adhesion promoter composition comprises a
pre-reacted mixture of at least one compound comprising at least
two isocyanate groups and at least one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin, and where the storage stable adhesion promoter composition
possesses in-resin storage stability when added to the resin
composition.
[0065] In another embodiment, the invention provides a resin
composition comprising at least one cyclic olefin, at least one
substrate material, and at least one adhesion promoter composition,
where the adhesion promoter composition comprises a pre-reacted
mixture of at least one compound comprising at least two isocyanate
groups and at least one compound comprising a heteroatom-containing
functional group and a metathesis active olefin.
[0066] In another embodiment, the invention provides a resin
composition comprising at least one cyclic olefin, at least one
substrate material, and at least one storage stable adhesion
promoter composition, where the storage stable adhesion promoter
composition comprises a pre-reacted mixture of at least one
compound comprising at least two isocyanate groups and at least one
compound comprising a heteroatom-containing functional group and a
metathesis active olefin.
[0067] In another embodiment, the invention provides a resin
composition comprising at least one cyclic olefin, at least one
substrate material, and at least one adhesion promoter composition,
where the adhesion promoter composition comprises a pre-reacted
mixture of at least one compound comprising at least two isocyanate
groups and at least one compound comprising a heteroatom-containing
functional group and a metathesis active olefin, wherein the
adhesion promoter is in-resin storage stable.
[0068] In another embodiment, the invention provides a resin
composition comprising at least one cyclic olefin, at least one
substrate material, and at least one storage stable adhesion
promoter composition, where the storage stable adhesion promoter
composition comprises a pre-reacted mixture of at least one
compound comprising at least two isocyanate groups and at least one
compound comprising a heteroatom-containing functional group and a
metathesis active olefin, wherein the storage stable adhesion
promoter is in-resin storage stable.
[0069] In another embodiment, the invention provides a resin
composition comprising at least one cyclic olefin, at least one
substrate material, and at least one adhesion promoter composition,
where the adhesion promoter composition comprises a pre-reacted
mixture of at least one compound comprising at least two isocyanate
groups and at least one compound comprising a heteroatom-containing
functional group and a metathesis active olefin, and where the
adhesion promoter composition possesses in-resin storage stability
when added to the resin composition.
[0070] In another embodiment, the invention provides a resin
composition comprising at least one cyclic olefin, at least one
substrate material, and at least one storage stable adhesion
promoter composition, where the storage stable adhesion promoter
composition comprises a pre-reacted mixture of at least one
compound comprising at least two isocyanate groups and at least one
compound comprising a heteroatom-containing functional group and a
metathesis active olefin, and where the storage stable adhesion
promoter composition possesses in-resin storage stability when
added to the resin composition.
[0071] In another embodiment, the invention provides a cyclic
olefin resin composition comprising at least one cyclic olefin, at
least one olefin metathesis catalyst, and at least one adhesion
promoter composition, where the cyclic olefin resin composition is
contacted with at least one substrate material to provide useful
improvements in the mechanical properties of a polymer-matrix
composite and/or polymerized resin, where the adhesion promoter
composition comprises a pre-reacted mixture of at least
one-compound containing at least two isocyanate groups and at least
one compound comprising a heteroatom-containing functional group
and a metathesis active olefin, where the adhesion promoter
composition possesses in-resin storage stability.
[0072] In another embodiment, the invention provides a cyclic
olefin resin composition comprising at least one cyclic olefin, at
least one olefin metathesis catalyst, and at least one adhesion
promoter composition, where the cyclic olefin resin composition is
contacted with at least one substrate material to provide useful
improvements in the mechanical properties of a polymer-matrix
composite and/or polymerized resin, where the adhesion promoter
composition comprises a pre-reacted mixture of at least
one-compound containing at least two isocyanate groups and at least
one compound comprising a heteroatom-containing functional group
and a metathesis active olefin.
[0073] In another embodiment, the invention provides a cyclic
olefin resin composition comprising at least one cyclic olefin, at
least one olefin metathesis catalyst, and at least one storage
stable adhesion promoter composition, where the cyclic olefin resin
composition is contacted with at least one substrate material to
provide useful improvements in the mechanical properties of a
polymer-matrix composite and/or polymerized resin, where the
storage stable adhesion promoter composition comprises a
pre-reacted mixture of at least one-compound containing at least
two isocyanate groups and at least one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin.
[0074] In another embodiment, the invention provides a cyclic
olefin resin composition comprising at least one cyclic olefin, at
least one olefin metathesis catalyst, and at least one storage
stable adhesion promoter composition, where the cyclic olefin resin
composition is contacted with at least one substrate material to
provide useful improvements in the mechanical properties of a
polymer-matrix composite and/or polymerized resin, where the
storage stable adhesion promoter composition comprises a
pre-reacted mixture of at least one-compound containing at least
two isocyanate groups and at least one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin, where the storage stable adhesion promoter composition
possesses in-resin storage stability.
[0075] In another embodiment, the invention provides a cyclic
olefin resin composition comprising at least one cyclic olefin and
at least one adhesion promoter composition, where the cyclic olefin
resin composition is combined with at least one olefin metathesis
catalyst to form a catalyzed resin composition and the catalyzed
resin composition is contacted with at least one substrate material
to provide useful improvements in the mechanical properties of a
polymer-composite and/or polymerized resin, where the adhesion
promoter composition comprises a pre-reacted mixture of at least
one compound containing at least two isocyanate groups and at least
one compound comprising a heteroatom-containing functional group
and a metathesis active olefin, where the adhesion promoter
composition possesses in-resin storage stability.
[0076] In another embodiment, the invention provides a cyclic
olefin resin composition comprising at least one cyclic olefin and
at least one storage stable adhesion promoter composition, where
the cyclic olefin resin composition is combined with at least one
olefin metathesis catalyst to form a catalyzed resin composition
and the catalyzed resin composition is contacted with at least one
substrate material to provide useful improvements in the mechanical
properties of a polymer-composite and/or polymerized resin, where
the storage stable adhesion promoter composition comprises a
pre-reacted mixture of at least one compound containing at least
two isocyanate groups and at least one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin, where the storage stable adhesion promoter composition
possesses in-resin storage stability.
[0077] In another embodiment, the invention provides an article of
manufacture comprising at least one resin composition comprising at
least one cyclic olefin, at least one olefin metathesis catalyst,
at least one substrate material, and at least one adhesion promoter
composition, where the at least one adhesion promoter composition
comprises a pre-reacted mixture of at least one compound containing
at least two isocyanate groups and at least one compound comprising
at least one heteroatom-containing functional group and at least
one metathesis active olefin.
[0078] In another embodiment, the invention provides an article of
manufacture comprising at least one resin composition comprising at
least one cyclic olefin, at least one olefin metathesis catalyst,
at least one substrate material, and at least one storage stable
adhesion promoter composition, where the at least one storage
stable adhesion promoter composition comprises a pre-reacted
mixture of at least one compound containing at least two isocyanate
groups and at least one compound comprising at least one
heteroatom-containing functional group and at least one metathesis
active olefin.
[0079] In another embodiment, the invention provides an article of
manufacture comprising at least one resin composition comprising at
least one cyclic olefin, at least one olefin metathesis catalyst,
at least one substrate material, and at least one storage stable
adhesion promoter composition, where the at least one storage
stable adhesion promoter composition comprises a pre-reacted
mixture of at least one compound containing at least two isocyanate
groups and at least one compound comprising at least one
heteroatom-containing functional group and at least one metathesis
active olefin, and wherein the at least one storage stable adhesion
promoter composition is in-resin storage stable.
[0080] In another embodiment, the invention provides an article of
manufacture comprising at least one resin composition comprising at
least one cyclic olefin, at least one olefin metathesis catalyst,
at least one substrate material, and at least one storage stable
adhesion promoter composition, where the at least one storage
stable adhesion promoter composition comprises a pre-reacted
mixture of at least one compound containing at least two isocyanate
groups and at least one compound comprising at least one
heteroatom-containing functional group and at least one metathesis
active olefin, and wherein the at least one storage stable adhesion
promoter composition possesses in-resin storage stability.
[0081] In another embodiment, the invention provides a method of
making an article of manufacture comprising contacting at least one
resin composition with at least one olefin metathesis catalyst to
form a catalyzed resin composition, contacting the catalyzed resin
composition with a substrate material, and subjecting the catalyzed
resin composition to conditions effective to promote an olefin
metathesis reaction of the catalyzed resin composition, where the
at least one resin composition comprises at least one cyclic olefin
and at least one adhesion promoter composition, where the at least
one adhesion promoter composition comprises a pre-reacted mixture
of at least one compound containing at least two isocyanate groups
and at least one compound comprising at least one
heteroatom-containing functional group and at least one metathesis
active olefin. In another embodiment, the invention provides a
method of making an article of manufacture comprising contacting at
least one resin composition with at least one olefin metathesis
catalyst to form a catalyzed resin composition, contacting the
catalyzed resin composition with a substrate material, and
subjecting the catalyzed resin composition to conditions effective
to promote an olefin metathesis reaction of the catalyzed resin
composition, where the at least one resin composition comprises at
least one cyclic olefin and at least one storage stable adhesion
promoter composition, where the at least one storage stable
adhesion promoter composition comprises a pre-reacted mixture of at
least one compound containing at least two isocyanate groups and at
least one compound comprising at least one heteroatom-containing
functional group and at least one metathesis active olefin.
[0082] In another embodiment, the invention provides a method of
making an article of manufacture comprising contacting at least one
resin composition with at least one olefin metathesis catalyst to
form a catalyzed resin composition, contacting the catalyzed resin
composition with a substrate material, and subjecting the catalyzed
resin composition to conditions effective to promote an olefin
metathesis reaction of the catalyzed resin composition, where the
at least one resin composition comprises at least one cyclic olefin
and at least one adhesion promoter composition, where the at least
one adhesion promoter composition comprises a pre-reacted mixture
of at least one compound containing at least two isocyanate groups
and at least one compound comprising at least one
heteroatom-containing functional group and at least one metathesis
active olefin, and where the at least one adhesion promoter
composition is in-resin storage stable.
[0083] In another embodiment, the invention provides a method of
making an article of manufacture comprising contacting at least one
resin composition with at least one olefin metathesis catalyst to
form a catalyzed resin composition, contacting the catalyzed resin
composition with a substrate material, and subjecting the catalyzed
resin composition to conditions effective to promote an olefin
metathesis reaction of the catalyzed resin composition, where the
at least one resin composition comprises at least one cyclic olefin
and at least one storage stable adhesion promoter composition,
where the at least one storage stable adhesion promoter composition
comprises a pre-reacted mixture of at least one compound containing
at least two isocyanate groups and at least one compound comprising
at least one heteroatom-containing functional group and at least
one metathesis active olefin, and where the at least one storage
stable adhesion promoter composition is in-resin storage
stable.
[0084] In another embodiment, the invention provides a method of
making an article of manufacture comprising contacting at least one
resin composition with at least one olefin metathesis catalyst to
form a catalyzed resin composition, contacting the catalyzed resin
composition with a substrate material, and subjecting the catalyzed
resin composition to conditions effective to promote an olefin
metathesis reaction of the catalyzed resin composition, where the
at least one resin composition comprises at least one cyclic olefin
and at least one adhesion promoter composition, where the at least
one adhesion promoter composition comprises a pre-reacted mixture
of at least one compound containing at least two isocyanate groups
and at least one compound comprising at least one
heteroatom-containing functional group and at least one metathesis
active olefin, and where the at least one adhesion promoter
composition possesses in-resin storage stability.
[0085] In another embodiment, the invention provides a method of
making an article of manufacture comprising contacting at least one
resin composition with at least one olefin metathesis catalyst to
form a catalyzed resin composition, contacting the catalyzed resin
composition with a substrate material, and subjecting the catalyzed
resin composition to conditions effective to promote an olefin
metathesis reaction of the catalyzed resin composition, where the
at least one resin composition comprises at least one cyclic olefin
and at least one storage stable adhesion promoter composition,
where the at least one storage stable adhesion promoter composition
comprises a pre-reacted mixture of at least one compound containing
at least two isocyanate groups and at least one compound comprising
at least one heteroatom-containing functional group and at least
one metathesis active olefin, and where the at least one storage
stable adhesion promoter composition possesses in-resin storage
stability.
[0086] In another embodiment, the invention provides an adhesion
promoter composition comprising at least one compound containing at
least two isocyanate groups, and at least one compound comprising
at least one heteroatom-containing functional group and at least
one metathesis active olefin.
[0087] In another embodiment, the invention provides a storage
stable adhesion promoter composition comprising at least one
compound containing at least two isocyanate groups, and at least
one compound comprising at least one heteroatom-containing
functional group and at least one metathesis active olefin.
[0088] In another embodiment, the invention provides an adhesion
promoter composition comprising at least one compound containing at
least two isocyanate groups, and at least one compound comprising
at least one heteroatom-containing functional group and at least
one metathesis active olefin, where the adhesion promoter
composition possesses in-resin storage stability when added to a
resin composition, where the resin composition comprises at least
one cyclic olefin.
[0089] In another embodiment, the invention provides a storage
stable adhesion promoter composition comprising at least one
compound containing at least two isocyanate groups, and at least
one compound comprising at least one heteroatom-containing
functional group and at least one metathesis active olefin, where
the storage stable adhesion promoter composition possesses in-resin
storage stability when added to a resin composition, where the
resin composition comprises at least one cyclic olefin.
[0090] The invention is further directed to a resin composition,
for example a ROMP composition, of a cyclic olefin, which may be
functionalized or unfunctionalized and may be substituted or
unsubstituted, an olefin metathesis catalyst (e.g., a cyclic olefin
metathesis catalyst), a substrate material, and an adhesion
promoter composition of the invention. The inventive resin
compositions are easy to handle and use, and when combined with a
substrate material and cured, form resin substrate composite
materials with improved properties. The resin compositions may also
be contacted with a substrate material, rather than, or in addition
to the substrate material added to the resin composition, and then
subjected to conditions effective to promote an olefin metathesis
reaction of the cyclic olefin in the presence of the olefin
metathesis catalyst, the adhesion promoter composition according to
the invention, and the optional added substrate material and/or in
contact with the substrate material.
[0091] The invention is further directed to a resin composition,
for example, a ROMP composition, of a cyclic olefin, which may be
functionalized or unfunctionalized and may be substituted or
unsubstituted, an olefin metathesis catalyst, an adhesion promoter
composition of the invention, and a substrate material, such as,
for example, a glass substrate material or a carbon substrate
material. The adhesion promoter composition of the invention should
be present in an amount effective to increase the adhesion of the
resin composition to a substrate material when the resin
composition is subjected to metathesis catalysis conditions in the
presence of the substrate material.
[0092] The adhesion promoter composition may also comprise a
pre-reacted mixture of more than one compound containing at least
two isocyanate groups and more than one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin. Furthermore, the compound comprising a
heteroatom-containing functional group and a metathesis active
olefin, may possess more than one heteroatom containing functional
group and more than one metathesis active olefin.
[0093] The addition of the adhesion promoter composition according
to the invention provides beneficial improvements in the adhesion
of an olefin metathesis (e.g., ROMP) composition to the substrate
material, such as, for example, a glass substrate material or a
carbon substrate material, as compared to a resin composition that
is the same with the exception that the adhesion promoter
composition according to the invention is not included.
[0094] These and other aspects of the invention will be apparent to
the skilled artisan in light of the following detailed description
and examples.
BRIEF DESCRIPTION OF THE DRAWINGS
[0095] FIG. 1 is a .sup.13C NMR (CDCl.sub.3, 100 MHz) spectrum of
the ethylene bridge region of HENB from an HENB and liquid MDI
(Mondur.RTM. MLQ) pre-reacted mixture at time zero, immediately
after mixing.
[0096] FIG. 2 is a .sup.13C NMR (CDCl.sub.3, 100 MHz) spectrum of
the ethylene bridge region of HENB from an HENB and liquid MDI
(Mondur.RTM. MLQ) pre-reacted mixture five days after mixing.
DETAILED DESCRIPTION OF THE DISCLOSURE
Terminology and Definitions
[0097] Unless otherwise indicated, the invention is not limited to
specific reactants, substituents, catalysts, resin compositions,
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.
[0098] 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 .alpha.-olefin" includes a single .alpha.-olefin
as well as a combination or mixture of two or more .alpha.-olefins,
reference to "a substituent" encompasses a single substituent as
well as two or more substituents, and the like.
[0099] 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.
[0100] 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:
[0101] 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.
[0102] The term "alkylene" as used herein refers to a difunctional
linear, branched, or cyclic alkyl group, where "alkyl" is as
defined above.
[0103] 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.
[0104] The term "alkenylene" as used herein refers to a
difunctional linear, branched, or cyclic alkenyl group, where
"alkenyl" is as defined above.
[0105] 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.
[0106] 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.
[0107] 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.
[0108] 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.
[0109] 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.
[0110] 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.
[0111] 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.
[0112] The terms "halo" and "halogen" are used in the conventional
sense to refer to a chloro, bromo, fluoro, or iodo substituent.
[0113] "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.
[0114] 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.
[0115] 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 (--C.ident.N), 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).
[0116] 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.
[0117] 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 abovementioned hydrocarbyl moieties may be further substituted
with one or more functional groups or additional hydrocarbyl
moieties as noted above.
[0118] "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.
[0119] 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, and macroparticulate density modulators, such
as glass or ceramic beads.
[0120] As used herein, the term "storage stable" means, by way of
example, that an adhesion promoter composition will exhibit little
or no changes in color, little or no changes in viscosity, little
or no gel formation, and/or little or no loss of activity for at
least 150 days, preferably for at least 90 days, and more
preferably for at least 30 days, when stored in a sealed container
under a dry, inert atmosphere (e.g., under argon or nitrogen) at
normal storage, shipping, and use temperatures, which by way of
example may vary from as low as -10.degree. C. to as high as
60.degree. C., preferably from 5.degree. C. to 50.degree. C., and
more preferably from 15.degree. C. to 40.degree. C.
[0121] By way of example, the storage stability of adhesion
promoter compositions may be measured by contacting an adhesion
promoter composition with a resin composition comprising at least
one cyclic olefin, using the resin composition to prepare
polymer-matrix composites, and measuring the ILSS of the
polymer-matrix composites. Adhesion promoter compositions which are
storage stable will exhibit little or no decrease (loss) in
measured ILSS values over some specified time period. Adhesion
promoter compositions which are storage stable for at least 156
days have been prepared as shown herein by the measured ILSS values
of polymer-matrix composites of Examples 32a-33a (Table 12).
[0122] As used herein, the term "dry" means a substantial absence
of water, by way of example the water concentration may vary from 0
ppm to 70 ppm, from 5 ppm to 40 ppm, and from 10 ppm to 35 ppm.
[0123] As used herein, the term "in-resin storage stability" or
"in-resin storage stable" means that an adhesion promoter
composition, when contacted with or added to or combined with a
resin composition comprising at least one cyclic olefin, exhibits
little or no loss of activity for at least 150 days, preferably for
at least 90 days, more preferably for at least 30 days, when the
resin composition is stored in a sealed container under a dry,
inert atmosphere (e.g., under argon or nitrogen) at normal storage,
shipping, and use temperatures, which by way of example may vary
from as low as -10.degree. C. to as high as 60.degree. C.,
preferably from 5.degree. C. to 50.degree. C., and more preferably
from 15.degree. C. to 40.degree. C.
[0124] By way of example, the in-resin storage stability of
adhesion promoter compositions may be measured by preparing
polymer-matrix composites using a resin composition comprising at
least one cyclic olefin and at least one adhesion promoter
composition, and measuring the ILSS of the polymer-matrix
composites. Adhesion promoter compositions having in-resin storage
stability will exhibit little or no decrease (loss) in measured
ILSS values over some specified time period. Adhesion promoter
compositions having in-resin storage stability for at least 326
days have been prepared as shown herein by the as measured ILSS
values of polymer-matrix composites of Examples 7a-7f (Table 3).
Additionally, adhesion promoter compositions having in-resin
storage stability for at least 202 days have been prepared as shown
herein in by the as measured ILSS values of polymer-matrix
composites of Examples 8a-8d (Table 4).
Adhesion Promoter
[0125] 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.
[0126] 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, alkyaryl, 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.
[0127] 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).
[0128] Adhesion promoters that may be used in the present invention
may also 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,
napthyl, biphenyl, diphenylether, benzophenone, and the like.
Preferred aromatic diisocyanates include toluene diisocyanates,
xylene diisocyanate, xylylene diisocyanate, tetramethylxylylene
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.
[0129] 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.
[0130] 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,
tetramethylxylylene diisocyanate (e.g., TMXDI.RTM. diisocyanate
from Cytec Industries Inc.), 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) (H.sub.12MDI); 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) (H.sub.12MDI); 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).
[0131] A compound containing at least two isocyanate groups is
combined with a compound comprising a heteroatom-containing
functional group and a metathesis active olefin and pre-reacted
providing an adhesion promoter composition having in-resin storage
stability and providing an olefin metathesis composite with
improved mechanical properties. Any concentration of a compound
containing at least two isocyanate groups is sufficient for use in
preparing adhesion promoter compositions of the invention, where
the mol % or mol equivalents of a compound containing at least two
isocyanate groups used to form the pre-reacted mixture is greater
than the mol % or mol equivalents of a compound comprising a
heteroatom-containing functional group and a metathesis active
olefin used to form the pre-reacted mixture. Mol ratios of a
compound comprising a heteroatom-containing functional group and a
metathesis active olefin relative to a compound containing at least
two isocyanate groups range from 0.001:1 to 0.90:1. Preferred mol
ratios of a compound comprising a heteroatom-containing functional
group and a metathesis active olefin relative to a compound
containing at least two isocyanate groups range from 0.01:1 to
0.75:1, particularly 0.01:1 to 0.5:1, more particularly 0.02:1 to
0.25:1. One skilled in the art will recognize that the optimal
ratio of a compound comprising a heteroatom-containing functional
group and a metathesis active olefin to a compound containing at
least two isocyanate groups may need to be adjusted as a function
of the amount of adhesion promoter composition added to the cyclic
olefin resin composition.
Compounds Comprising a Heteroatom-Containing Functional Group and a
Metathesis Active Olefin
[0132] The compound comprising a heteroatom-containing functional
group and a metathesis active olefin typically contains between 2
and 20 carbons with hydroxyl, amine, thiol, phosphorus, or silane
functional groups. Compounds comprising a heteroatom-containing
functional group and a metathesis active olefin that may be used in
the present invention disclosed herein are generally compounds
containing at least one heteroatom containing functional group and
at least one metathesis active olefin and are of the following
general structure:
(O.sup.M)-(Q*).sub.n-(X*)--H
wherein O.sup.M, Q*, and X* are as follows:
[0133] O.sup.M is a metathesis active olefin fragment selected from
cyclic olefins and acyclic olefins, where the carbon-carbon double
bond typically is not tetra-substituted (e.g., at least one
substituent is a hydrogen);
[0134] Q* is an optional linker group (e.g., n=0 or 1) such as, for
example, a hydrocarbylene (including, for example, substituted
hydrocarbylene, heteroatom-containing hydrocarbylene, and
substituted heteroatom-containing hydrocarbylene, such as
substituted and/or heteroatom-containing alkylene) or --(CO)--
group; and
[0135] X* is oxygen, sulfur, or a heteroatom-containing fragment
such as N(R.sup.X), P(R.sup.X), OP(R.sup.X), OP(R.sup.X)O,
OP(OR.sup.X)O, P(.dbd.O)(R.sup.X), OP(.dbd.O)(R.sup.X),
OP(.dbd.O)(R.sup.X)O, OP(.dbd.O)(OR.sup.X)O, Si(R.sup.X).sub.2,
Si(R.sup.X).sub.2O, Si(OR.sup.X).sub.2O, or
Si(R.sup.X)(OR.sup.X)O,
[0136] wherein each R.sup.X is, independent of one another, a
hydrogen or a hydrocarbyl group optionally comprising further
functional groups. Each R.sup.X is, independent of one another,
most commonly a hydrogen, aryl, or lower alkyl group.
[0137] Metathesis active olefins include cyclic olefins as
described herein, where 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. Metathesis active olefins also include acyclic
olefins, where such acyclic olefins may be optionally substituted,
optionally heteroatom-containing, mono-unsaturated, di-unsaturated,
or poly-unsaturated C.sub.2 to C.sub.30 hydrocarbons, typically
C.sub.2 to C.sub.20 hydrocarbons, or more typically C.sub.2 to
C.sub.12 hydrocarbons. Acyclic olefins may contain one or more
terminal olefins and/or one or more internal olefins, and/or any
combination of terminal olefins and/or internal olefins.
[0138] In the heteroatom-containing functional group, X* is
commonly oxygen, sulfur, or NR.sup.X and is most commonly oxygen,
i.e., a hydroxy-substituted olefin. Preferred compounds comprising
a heteroatom-containing functional group and a metathesis active
olefin include, but are not limited to, 5-norbornene-2-methanol
(NB-MeOH); 2-hydroxyethyl bicycle[2.2.1]hept-2-ene-carboxylate
(HENB); 2-hydroxyethyl acrylate (HEA); allyl alcohol; oleyl
alcohol; 9-decen-1-ol; vinyl alcohol, allyl alcohol,
cis-13-dodecenol, and trans-9-octadecenol, and other unsaturated
alcohols, norbornyl alcohol, 2-cycloocten-1-ol,
2-cyclooctadiene-1-ol, and p-vinyl phenol, and other alcohols which
have an alicyclic structure; 2-hydroxyethyl methacrylate;
2-hydroxy-3-acryloxypropyl methacrylate, ethoxylated hydroxyethyl
acrylate, ethoxylated hydroxyethyl methacrylate,
polypropyleneglycol monomethacrylate, polypropylene glycol
monoacrylate, phenol acrylate, phenol methacrylate, bisphenol A
type epoxy acrylate, novolac type epoxy acrylate, and brominated
bisphenol A type epoxy acrylate, and other methacrylics or acrylics
which have one or more methacryl or acryl groups and hydroxyl
groups, etc.
[0139] The compound comprising a heteroatom-containing functional
group and a metathesis active olefin is combined with a compound
containing at least two isocyanate groups and pre-reacted providing
an adhesion promoter composition having in-resin storage stability
and providing an olefin metathesis composite with improved
mechanical properties. Any concentration of a compound comprising a
heteroatom-containing functional group and a metathesis active
olefin is sufficient for use in preparing adhesion promoter
compositions of the invention, where the mol % or mol equivalents
of a compound comprising a heteroatom-containing functional group
and a metathesis active olefin used to form the pre-reacted mixture
is less than the mol % or mol equivalents of a compound containing
at least two isocyanate groups used to form the pre-reacted
mixture. Mol ratios of a compound comprising a
heteroatom-containing functional group and a metathesis active
olefin relative to a compound containing at least two isocyanate
groups range from 0.001:1 to 0.90:1. Preferred mol ratios of a
compound comprising a heteroatom-containing functional group and a
metathesis active olefin relative to a compound containing at least
two isocyanate groups range from 0.01:1 to 0.75:1, particularly
0.01:1 to 0.5:1, more particularly 0.02:1 to 0.25:1. One skilled in
the art will recognize that the optimal ratio of a compound
comprising a heteroatom-containing functional group and a
metathesis active olefin to a compound containing at least two
isocyanate groups may need to be adjusted as a function of the
amount of adhesion promoter composition added to the cyclic olefin
resin composition.
Adhesion Promoter Compositions
[0140] Adhesion promoter compositions that may be used in the
present invention disclosed herein are generally compositions
comprising at least one adhesion promoter, discussed supra (i.e.,
at least one compound containing at least two isocyanate groups
(e.g., methylene diphenyl diisocyanate, hexamethylene
diisocyanate)) and at least one compound comprising a
heteroatom-containing functional group and a metathesis active
olefin, discussed supra (e.g., 2-hydroxyethyl
bicyclo[2.2.1]hept-2-ene-5-carboxylate (HENB), 2-hydroxyethyl
acrylate (HEA), oleyl alcohol, 9-decen-1-ol), where the compounds
may be combined in various ratios to form a pre-reacted mixture,
wherein the pre-reacted mixture is then subsequently added to a
cyclic olefin resin composition, and where the adhesion promoter
composition possesses in-resin storage stability. Furthermore,
adhesion promoter compositions of the invention may also be storage
stable.
[0141] Compounds containing at least two isocyanate groups and
compounds comprising a heteroatom-containing functional group and a
metathesis active olefin useful for preparing adhesion promoter
compositions of the invention are disclosed herein.
[0142] Preferred adhesion promoter compositions include pre-reacted
mixtures of liquid MDI (Mondur.RTM. MLQ) and 2-hydroxyethyl
bicycle[2.2.1]hept-2-ene-carboxylate (HENB); pre-reacted mixtures
of liquid MDI (Mondur.RTM. MLQ) and 2-hydroxyethyl acrylate (HEA);
pre-reacted mixtures of liquid MDI (Mondur.RTM. MLQ) and oleyl
alcohol; and pre-reacted mixtures of liquid MDI (Mondur.RTM. MLQ)
and 9-decen-1-ol.
[0143] More preferred adhesion promoter compositions include
prereacted mixtures of liquid MDI (Mondur.RTM. MLQ) and
2-hydroxyethyl bicycle[2.2.1]hept-2-ene-carboxylate (HENB).
[0144] Any concentration of adhesion promoter composition which
improves the mechanical properties of the olefin composite is
sufficient for the invention. In general, suitable amounts of
adhesion promoter composition 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.
Substrate Surfaces
[0145] The present invention is generally suitable for use with any
substrate material in which the addition of an adhesion promoter
composition of the invention provides beneficial improvements in
the adhesion of a resin (e.g., ROMP) composition to the substrate
material as compared to a resin composition that is the same with
the exception that the adhesion promoter composition of the
invention is not included. Furthermore, the present invention is
generally suitable for use with any substrate material in which the
addition of an adhesion promoter composition of the invention
provides beneficial improvements in the adhesion of a
polymer-matrix (e.g., ROMP polymer-matrix) to a substrate material
compared to a polymer-matrix that is the same with the exception
that the adhesion promoter composition of the invention is not
included. The present invention is particularly beneficial for use
with glass and carbon material surfaces suitable for use with epoxy
and methacrylate resins, including those containing finishes or
sizings, in which case the finishes or sizings do not need to be
removed (e.g., by washing or heat cleaning) for the inventive
adhesion promoter compositions to be effective. The present
invention is also suitable for use with wood and aluminum
materials. Suitable substrate materials may also be selected from
fibrous, woven, microparticulate, ceramic, metal, polymer, and
semiconductor materials. A polymer-matrix composite (e.g., ROMP
polymer matrix composite) may be comprised of one substrate
material or a mixture of different substrate materials.
Cyclic Olefin
[0146] Resin 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. 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.
[0147] 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:
[0148] 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.
[0149] 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.
[0150] 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. 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.
[0151] 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, 1-chloropentene, 1-fluorocyclopentene,
4-methylcyclopentene, 4-methoxy-cyclopentene,
4-ethoxy-cyclopentene, cyclopent-3-ene-thiol, cyclopent-3-ene,
4-methyl sulfanyl-cyclopentene, 3-methylcyclohexene,
1-methylcyclooctene, 1,5-dimethylcyclooctene, etc.
[0152] 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.
[0153] 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.
[0154] 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.
[0155] 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.
[0156] 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.
[0157] 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.
[0158] 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).
[0159] 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).
[0160] 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)
[0161] 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.
[0162] 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.
[0163] 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.
[0164] 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.
[0165] 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.
[0166] 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.
[0167] The resin 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.24 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.
[0168] 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.
[0169] 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.
Olefin Metathesis Catalysts
[0170] An 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:
[0171] M is a Group 8 transition metal;
[0172] L.sup.1, L.sup.2, and L.sup.3 are neutral electron donor
ligands;
[0173] n is 0 or 1, such that L.sup.3 may or may not be
present;
[0174] m is 0, 1, or 2;
[0175] k is 0 or 1;
[0176] X.sup.1 and X.sup.2 are anionic ligands; and
[0177] 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,
[0178] 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.
[0179] 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. Additionally, R.sup.1 and R.sup.2 may be taken together to
form a phenylindenylidene.
[0180] Preferred catalysts contain Ru or Os as the Group 8
transition metal, with Ru particularly preferred.
[0181] 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.
[0182] 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.
[0183] 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).
[0184] 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-Cao 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.
[0185] 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.
[0186] 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.
[0187] 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.
[0188] 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;
[0189] 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;
[0190] 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
[0191] 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. Additionally,
R.sup.1 and R.sup.2 may be taken together to form a
phenylindenylidene.
[0192] 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.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. 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.
[0193] 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.
[0194] 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.
[0195] 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##
[0196] Additional examples of N-heterocyclic carbene (NHC) ligands
and acyclic diaminocarbene ligands suitable as L' 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.
[0197] 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.
[0198] 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.
[0199] When M is ruthenium, then, the preferred complexes have the
structure of formula (V)
##STR00016##
[0200] In a more preferred embodiment, Q is a two-atom linkage
having the structure --CR.sup.11R.sup.12CR.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.
[0201] 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).
[0202] 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.
[0203] 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.
[0204] 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 substituent.
[0205] 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.
[0206] 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.
[0207] 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.
[0208] 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.
[0209] 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 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.
[0210] 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.
[0211] 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.).
[0212] 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.24 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.24 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.24 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.
[0213] 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.5-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.
[0214] 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:
[0215] M is a Group 8 transition metal, particularly Ru or Os, or,
more particularly, Ru;
[0216] X.sup.1, X.sup.2, and L.sup.1 are as previously defined
herein for the first and second groups of catalysts;
[0217] Y is a heteroatom selected from N, O, S, and P; preferably Y
is O or N;
[0218] 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, alkyl
sulfonyl, 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;
[0219] n is 0, 1, or 2, such that n is 1 for the divalent
heteroatoms O or S, and n is 2 for the trivalent heteroatoms N or
P; and
[0220] 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.
[0221] 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).
[0222] 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##
[0223] 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##
[0224] 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:
[0225] 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);
[0226] 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);
[0227] 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
[0228] 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:
[0229] 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;
[0230] r and s are independently zero or 1;
[0231] t is an integer in the range of zero to 5;
[0232] k is an integer in the range of zero to 1;
[0233] Y is any non-coordinating anion (e.g., a halide ion,
BF.sub.4.sup.-, etc.);
[0234] 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;
[0235] 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
[0236] 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.
[0237] Additionally, another group of 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;
[0238] 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
[0239] 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.
[0240] 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, and L.sup.2 are as defined
above for Group 8 transition metal complex of formula (XIII);
and
[0241] 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.
[0242] 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, and L.sup.2 are as defined
above for Group 8 transition metal complex of formula (XIII).
[0243] 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;
[0244] X.sup.1 and L.sup.1 are as defined for the first and second
groups of catalysts defined above;
[0245] 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
[0246] 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, alkyl
sulfonyl, 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.
[0247] 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##
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
[0248] 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.
[0249] 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, and R.sup.J11 are as defined above for Group 8
transition metal complex of formula (XVI).
[0250] 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;
[0251] 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;
[0252] Z is selected from the group consisting of oxygen, sulfur,
selenium, NR.sup.K5, PR.sup.K5, AsR.sup.K5, and SbR.sup.K5;
[0253] m is 0, 1, or 2; and
[0254] 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, alkyl
sulfonyl, 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.
[0255] 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, and 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.
[0256] 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.
[0257] 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##
[0258] 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.
[0259] 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
(phenylmethylene) (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
(benzylidene) (triphenylphosphine) ruthenium(II) (C831);
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene] dichloro
(benzylidene)(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(benzylidene) (diethylphenylphosphine) ruthenium(II)
(C735);
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(benzylide-
ne)(tri-n-butylphosphine)ruthenium(II) (C.sub.771);
[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(phenylindenylidene)(triphenylphosphine)ruthenium(II)
(C931); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]
dichloro (phenylindenylidene) (methylphenylphosphine) ruthenium(II)
(C869); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]
dichloro (phenylindenylidene) (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).
[0260] Additional examples of catalysts useful to prepare supported
complexes and in the reactions disclosed herein include the
following:
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(tert-buty-
lvinylidene) (tricyclohexylphosphine)ruthenium(II) (C841);
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylvin-
ylidene) (tricyclohexylphosphine)ruthenium(II), ruthenium (II) and
dichloro (tert-butylvinylidene) bis(tricyclohexylphosphine)
(C815).
[0261] 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:
##STR00041## ##STR00042## ##STR00043##
[0262] 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. Nos. 5,312,940, and
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.
[0263] Preferred 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.
[0264] More preferred olefin metathesis catalysts have the
structure of formula (I)
##STR00044##
wherein:
[0265] M is a Group 8 transition metal;
[0266] L.sup.1, L.sup.2, and L.sup.3 are neutral electron donor
ligands;
[0267] n is 0 or 1;
[0268] m is 0, 1, or 2;
[0269] k is 0 or 1;
[0270] X.sup.1 and X.sup.2 are anionic ligands; and
[0271] 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,
[0272] 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)
##STR00045##
wherein:
[0273] M is a Group 8 transition metal;
[0274] L.sup.1 is a neutral electron donor ligand;
[0275] X.sup.1 and X.sup.2 are anionic ligands;
[0276] Y is a heteroatom selected from 0 or N;
[0277] 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;
[0278] n is 0, 1, or 2; and
[0279] Z is selected from hydrogen, hydrocarbyl, substituted
hydrocarbyl, heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, and functional groups,
[0280] 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.
[0281] Most preferred olefin metathesis catalysts have the
structure of formula (I)
##STR00046##
wherein:
[0282] M is ruthenium;
[0283] n is 0;
[0284] m is 0;
[0285] k is 1;
[0286] 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);
[0287] X.sup.1 and X.sup.2 are chloride; and
[0288] 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)
##STR00047##
wherein:
[0289] M is ruthenium;
[0290] 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;
[0291] X.sup.1 and X.sup.2 are chloride;
[0292] Y is oxygen;
[0293] R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are each
hydrogen;
[0294] n is 1; and
[0295] Z is isopropyl.
[0296] Most preferred olefin metathesis catalysts have the
structure of formula (I)
##STR00048##
wherein:
[0297] M is ruthenium;
[0298] n is 0;
[0299] m is 0;
[0300] k is 1;
[0301] 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);
[0302] X.sup.1 and X.sup.2 are chloride; and
[0303] 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 phenylindenylidene;
and formula (VII)
##STR00049##
wherein:
[0304] M is ruthenium;
[0305] 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;
[0306] X.sup.1 and X.sup.2 are chloride;
[0307] Y is oxygen;
[0308] R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are each
hydrogen;
[0309] n is 1; and
[0310] Z is isopropyl.
[0311] Examples of preferred olefin metathesis catalysts have the
structure of formula (VII)
##STR00050##
wherein:
[0312] M is ruthenium;
[0313] 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;
[0314] X.sup.1 and X.sup.2 are chloride;
[0315] Y is oxygen;
[0316] R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are each
hydrogen;
[0317] n is 1; and
[0318] Z is isopropyl.
[0319] Examples of preferred olefin metathesis catalysts have the
structure of formula (I)
##STR00051##
wherein:
[0320] M is Ruthenium;
[0321] n is 0;
[0322] m is 0;
[0323] k is 1;
[0324] L.sup.1 is an N-heterocyclic carbene selected from the group
consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene
and 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene;
[0325] L.sup.2 is a trisubstituted phosphine 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);
[0326] X.sup.1 and X.sup.2 are chloride; and
[0327] 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 phenylindenylidene.
[0328] Examples of preferred olefin metathesis catalysts have the
structure of formula (I)
##STR00052##
wherein:
[0329] M is Ruthenium;
[0330] n is 0;
[0331] m is 0;
[0332] k is 1;
[0333] L.sup.1 is an N-heterocyclic carbene
1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene;
[0334] L.sup.2 is a trisubstituted phosphine 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);
[0335] X.sup.1 and X.sup.2 are chloride; and
[0336] 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 phenylindenylidene.
[0337] Examples of preferred olefin metathesis catalysts have the
structure of formula (I)
##STR00053##
[0338] wherein:
[0339] M is Ruthenium;
[0340] n is 0;
[0341] m is 0;
[0342] k is 1;
[0343] L.sup.1 is an N-heterocyclic carbene
1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene;
[0344] L.sup.2 is a trisubstituted phosphine 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);
[0345] X.sup.1 and X.sup.2 are chloride; and
[0346] 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 phenylindenylidene.
[0347] Examples of preferred olefin metathesis catalysts have the
structure of formula (I)
##STR00054##
wherein:
[0348] M is Ruthenium;
[0349] n is 0;
[0350] m is 0;
[0351] k is 1;
[0352] L.sup.1 is an N-heterocyclic carbene selected from the group
consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene
and 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene;
[0353] L.sup.2 is a trisubstituted phosphine 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);
[0354] X.sup.1 and X.sup.2 are chloride; and
[0355] R.sup.1 is hydrogen and R.sup.2 is phenyl or
--CH.dbd.C(CH.sub.3).sub.2; or R.sup.1 and R.sup.2 are taken
together to form phenylindenylidene.
[0356] Examples of preferred olefin metathesis catalysts have the
structure of formula (I)
##STR00055##
wherein:
[0357] M is Ruthenium;
[0358] n is 0;
[0359] m is 0;
[0360] k is 1;
[0361] L.sup.1 is an N-heterocyclic carbene
1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene;
[0362] L.sup.2 is a trisubstituted phosphine 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);
[0363] X.sup.1 and X.sup.2 are chloride; and
[0364] R.sup.1 is hydrogen and R.sup.2 is phenyl or
--CH.dbd.C(CH.sub.3).sub.2; or R.sup.1 and R.sup.2 are taken
together to form phenylindenylidene.
[0365] Examples of preferred olefin metathesis catalysts have the
structure of formula (I)
##STR00056##
wherein:
[0366] M is Ruthenium;
[0367] n is 0;
[0368] m is 0;
[0369] k is 1;
[0370] L.sup.1 is an N-heterocyclic carbene
1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene;
[0371] L.sup.2 is a trisubstituted phosphine 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);
[0372] X.sup.1 and X.sup.2 are chloride; and
[0373] R.sup.1 is hydrogen and R.sup.2 is phenyl or
--CH.dbd.C(CH.sub.3).sub.2; or R.sup.1 and R.sup.2 are taken
together to form phenylindenylidene.
[0374] Examples of preferred olefin metathesis catalysts have the
structure of formula (I)
##STR00057##
[0375] wherein:
[0376] M is Ruthenium;
[0377] n is 0;
[0378] m is 0;
[0379] k is 1;
[0380] L.sup.1 is an N-heterocyclic carbene selected from the group
consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene
and 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene;
[0381] L.sup.2 is a trisubstituted phosphine 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);
[0382] X.sup.1 and X.sup.2 are chloride;
[0383] R.sup.1 is hydrogen; and
[0384] R.sup.2 is phenyl or --CH.dbd.C(CH.sub.3).sub.2.
[0385] Examples of preferred olefin metathesis catalysts have the
structure of formula (I)
##STR00058##
wherein:
[0386] M is Ruthenium;
[0387] n is 0;
[0388] m is 0;
[0389] k is 1;
[0390] L.sup.1 is an N-heterocyclic carbene
1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene;
[0391] L.sup.2 is a trisubstituted phosphine 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);
[0392] X.sup.1 and X.sup.2 are chloride;
[0393] R.sup.1 is hydrogen; and
[0394] R.sup.2 is phenyl or --CH.dbd.C(CH.sub.3).sub.2.
[0395] Examples of preferred olefin metathesis catalysts have the
structure of formula (I)
##STR00059##
wherein:
[0396] M is Ruthenium;
[0397] n is 0;
[0398] m is 0;
[0399] k is 1;
[0400] L.sup.1 is an N-heterocyclic carbene
1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene;
[0401] L.sup.2 is a trisubstituted phosphine 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);
[0402] X.sup.1 and X.sup.2 are chloride;
[0403] R.sup.1 is hydrogen; and
[0404] R.sup.2 is phenyl or --CH.dbd.C(CH.sub.3).sub.2.
[0405] Examples of preferred olefin metathesis catalysts have the
structure of formula (I)
##STR00060##
wherein:
[0406] M is Ruthenium;
[0407] n is 0;
[0408] m is 0;
[0409] k is 1;
[0410] L.sup.1 is an N-heterocyclic carbene selected from the group
consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene
and 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene;
[0411] L.sup.2 is a trisubstituted phosphine 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);
[0412] X.sup.1 and X.sup.2 are chloride; and
[0413] R.sup.1 and R.sup.2 are taken together to form
phenylindenylidene.
[0414] Examples of preferred olefin metathesis catalysts have the
structure of formula (I)
##STR00061##
wherein:
[0415] M is Ruthenium;
[0416] n is 0;
[0417] m is 0;
[0418] k is 1;
[0419] L.sup.1 is an N-heterocyclic carbene
1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene;
[0420] L.sup.2 is a trisubstituted phosphine 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);
[0421] X.sup.1 and X.sup.2 are chloride; and
[0422] R.sup.1 and R.sup.2 are taken together to form
phenylindenylidene.
[0423] Examples of preferred olefin metathesis catalysts have the
structure of formula (I)
##STR00062##
wherein:
[0424] M is ruthenium;
[0425] n is 0;
[0426] m is 0;
[0427] k is 1;
[0428] L.sup.1 is an N-heterocyclic carbene
1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene;
[0429] L.sup.2 is a trisubstituted phosphine 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);
[0430] X.sup.1 and X.sup.2 are chloride; and
[0431] R.sup.1 and R.sup.2 are taken together to form
phenylindenylidene.
[0432] Examples of preferred olefin metathesis catalysts have the
structure of formula (I)
##STR00063##
wherein:
[0433] M is ruthenium;
[0434] n is 0;
[0435] m is 1;
[0436] k is 1;
[0437] 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, and
1,3-bis(2,4,6-trimethylphenyl)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);
[0438] X.sup.1 and X.sup.2 are chloride;
[0439] R.sup.1 is hydrogen; and
[0440] R.sup.2 is phenyl or tert-butyl.
[0441] Examples of preferred olefin metathesis catalysts have the
structure of formula (I)
##STR00064##
[0442] wherein:
[0443] M is ruthenium;
[0444] n is 0;
[0445] m is 1;
[0446] k is 1;
[0447] L.sup.1 is an N-heterocyclic carbene selected from the group
consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene
and 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene;
[0448] 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);
[0449] X.sup.1 and X.sup.2 are chloride;
[0450] R.sup.1 is hydrogen; and
[0451] R.sup.2 is phenyl or tert-butyl.
[0452] Examples of preferred olefin metathesis catalysts have the
structure of formula (I)
##STR00065##
wherein:
[0453] M is ruthenium;
[0454] n is 0;
[0455] m is 1;
[0456] k is 1;
[0457] L.sup.1 is an N-heterocyclic carbene
1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene;
[0458] 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);
[0459] X.sup.1 and X.sup.2 are chloride;
[0460] R.sup.1 is hydrogen; and
[0461] R.sup.2 is phenyl or tert-butyl.
[0462] Examples of preferred olefin metathesis catalysts have the
structure of formula (I)
##STR00066##
in which:
[0463] M is ruthenium;
[0464] n is 0;
[0465] m is 1;
[0466] k is 1;
[0467] L.sup.1 is an N-heterocyclic carbene
1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene;
[0468] 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);
[0469] X.sup.1 and X.sup.2 are chloride;
[0470] R.sup.1 is hydrogen; and
[0471] R.sup.2 is phenyl or tert-butyl.
[0472] 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.
[0473] 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.
[0474] 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.
[0475] The metathesis catalysts that are described infra may be
utilized in olefin metathesis reactions according to techniques
known in the art. The catalyst is typically added to the resin
composition as a solid, a solution, or as a suspension. When the
catalyst is added to the resin composition as a suspension, the
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, 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.
[0476] 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.
[0477] 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 200,000:1, 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 and Articles
[0478] Cyclic olefin resin, particularly ROMP, compositions
according to the invention, generally comprise at least one cyclic
olefin, at least one olefin metathesis catalyst, at least one
adhesion promoter composition of the invention, and at least one
substrate material, such as, for example, a glass or carbon
substrate material. In another embodiment, cyclic olefin resin,
particularly ROMP, compositions according to the invention,
generally comprise at least one cyclic olefin, at least one olefin
metathesis catalyst, at least one adhesion promoter composition of
the invention, and at least one heteroatom-functionalized
substrate. The cyclic olefins described hereinabove are suitable
for use and may be functionalized or unfunctionalized, and may be
substituted or unsubstituted. In general, particularly advantageous
results may be obtained for ROMP resin compositions wherein an
adhesion promoter composition of the invention is present in an
amount effective to improve the adhesion of the ROMP composition to
the substrate material when the ROMP composition is subjected to
metathesis catalysis conditions in the presence of the substrate
material. Additionally, cyclic olefin resin compositions according
to the invention may also comprise at least one cyclic olefin, at
least one adhesion promoter composition of the invention, where the
resin composition is combined with at least one olefin metathesis
catalyst, and the resulting resin composition is applied to at
least one substrate, such as, for example, a glass substrate or
carbon substrate. Additionally, cyclic olefin resin compositions
according to the invention may also comprise at least one cyclic
olefin, at least one adhesion promoter composition of the
invention, where the resin composition is combined with at least
one olefin metathesis catalyst, and the resulting resin composition
is applied to at least one substrate, wherein the substrate may be
functionalized substrate, such as, for example, a
heteroatom-functionalized substrate, such as, for example, an
amino-functionalized substrate.
[0479] The amounts of the adhesion promoter composition 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 composition
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 composition
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.
[0480] In a preferred aspect of the invention, increased mechanical
properties may also be obtained for resin compositions comprising
at least one cyclic olefin, at least one olefin metathesis
catalyst, at least one adhesion promoter composition of the
invention, and at least one substrate material, or resin
compositions comprising at least one cyclic olefin, at least one
olefin metathesis catalyst, at least one adhesion promoter
composition of the invention where the resin composition is applied
to at least one substrate material, compared to such resin
compositions without the adhesion promoter composition of the
invention. For example, the inclusion of an adhesion promoter
composition of the invention may provide an improvement in
mechanical properties, such as interlaminar shear strength (ILSS)
compared to the same resin composition that does not contain an
adhesion promoter composition of the invention. In particular
aspects of the present invention, substrate materials may
advantageously comprise an aminosilane-treated substrate.
[0481] 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 for use in the present invention are disclosed in
International Pat. App. No. PCT/US2012/042850, the contents of
which are incorporated herein by reference.
[0482] 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, impact modifiers, 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.
[0483] 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 (Lanxess),
styrene-ethylene/butylene-styrene copolymer Kraton G1651H, Butyl
301 isobutylene-isoprene copolymer (Lanxess), Buna CB 710
polybutadiene (formerly Taktene.RTM. 710; Lanxess),
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.
[0484] 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.
[0485] 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 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 1010;
1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,
e.g., Ethanox 330; 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 3114, 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 492, 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'-biphenylylenediphosphonite,
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.
[0486] 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 trade name), and polyoxazole fibers or
fabrics (such as those produced by the Toyobo Corporation under the
Zylon 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,
M305, 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 50S 12L AF), Mitsubishi (Pyrofil TR 50S 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 Fiberglass) (EKU
1150(0)/50-600); and Owens Corning (L1020/07A06 Xweft 200tex), and
SGL Kumpers (HPT970) based on PPG Hybon.RTM. 2002.
[0487] 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.
[0488] The invention is also directed to articles manufactured from
a resin composition comprising a at least one cyclic olefin, at
least one olefin metathesis catalyst, at least one storage stable
adhesion promoter composition, and at least one substrate material,
where the at least one storage stable adhesion promoter composition
is a pre-reacted mixture of at least one compound containing at
least two isocyanate groups and at least one compound comprising at
least one heteroatom-containing functional group and at least one
metathesis active olefin. Additionally, the invention is directed
to articles manufactured from a resin composition comprising at
least one cyclic olefin and at least one storage stable adhesion
promoter composition, where the where the at least one storage
stable adhesion promoter composition is a pre-reacted mixture of at
least one compound containing at least two isocyanate groups and at
least one compound comprising at least one heteroatom-containing
functional group and at least one metathesis active olefin, where
the resin composition is combined with an olefin metathesis
catalyst, and the resulting resin composition is applied to a
substrate, which may be, for example, a functionalized substrate,
such as, for example, a heteroatom-functionalized substrate, such
as, for example, an amino-functionalized substrate.
[0489] Articles may include, but are not limited to, those formed
by standard manufacturing techniques including casting, centrifugal
casting, pultrusion, molding, rotational molding, open molding,
reaction injection molding (RIM), resin transfer molding (RTM),
pouring, vacuum impregnation, surface coating, filament winding and
other methods known to be useful for production of polymer
articles. Molded parts include but are not limited to reaction
injection molding, resin transfer molding, and vacuum assisted
resin transfer molding. Furthermore, the compositions and articles
of manufacture of the invention are not limited to a single
polymer-surface interface but include also multilayers and
laminates containing multiple polymer-surface interfaces. The
invention is also suitable for manufacture of articles by the
infusion of the resin into a porous material. Such porous materials
include but are not limited to wood, cement, concrete, open-cell
and reticulated foams and sponges, papers, cardboards, felts, ropes
or braids of natural or synthetic fibers, and various sintered
materials. Additionally, other manufacturing techniques include
without limitation 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, 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).
[0490] Furthermore, the present invention also allows for the
making of articles of manufacture of any configuration, weight,
size, thickness, or geometric shape. Examples of articles of
manufacture include without limitation any molded or shaped article
for use as an aerospace component, a marine component, an
automotive component, a sporting goods component, an electrical
component, and industrial component, medical component, dental
component, or military component. In one embodiment an article may
be a turbine component used on aircraft or general power
generation. In one embodiment, turbine components may include
without limitation one or more of an inlet, pylon, pylon fairing,
an acoustic panel, a thrust reverser panel, a fan blade, a fan
containment case, a bypass duct, an aerodynamic cowl, or an airfoil
component. In one embodiment, an article may be a turbine blade
component or may be a turbine blade. In one embodiment, an article
may be a wind rotor blade, tower, spar cap, or nacelle for wind
turbines. In one embodiment, an article may be an airframe
component. Examples of aerospace components may include without
limitation one or more of fuselage skin, wing, fairing, doors,
access panel, aerodynamic control surface, or stiffner. In one
embodiment an article may be an automotive component. Examples of
automotive components may include without limitation one or more of
body panel, fender, spoiler, truck bad, protective plate, hood,
longitudinal rail, pillar, or door. Examples of industrial
components may include without limitation one or more of risers
platforms, impact protection structures for oil and gas; bridges,
pipes, pressure vessels, power poles, coils, containers, tanks,
liners, containment vessels, articles for application in corrosive
environments (e.g., chlor-alkali, caustic, acidic, brine, etc.),
reinforcement structures for concrete architectures and roads, or
radiators. Examples of electrical components may include without
limitation one or more wound articles, such as coils or electric
motors, or insulating devices. In one embodiment, an article may be
an eddy-current shielding component of a magnetic resonance imaging
system or shielding component for any electromagnetic radiation. In
one embodiment, an article may be a military component including
without limitation ballistics resistant armor for personnel or
vehicles, or ballistics resistant structures for protecting
personnel or equipment. In one embodiment, an article may be a
sporting goods component including without limitation an arrow
shaft, a tennis racket frame, a hockey stick, compound bow limbs,
or a golf club shaft.
[0491] 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.
[0492] 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.
[0493] 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.
[0494] 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).
[0495] 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.
[0496] 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 Resynx 1971 (epoxy-modified
polyvinylacetate).
[0497] 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.
[0498] 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.
[0499] 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.
[0500] 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. P103, and
Pluronic.RTM. P105.
[0501] 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.
[0502] 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.
[0503] 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.
[0504] 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.
[0505] 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.
[0506] 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, diethylether, 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.
[0507] 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.
[0508] 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
[0509] 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).
[0510] 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 the adhesion promoter
compositions of the invention and the methods for their use.
EXAMPLES
Materials and Methods
[0511] 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.
[0512] Dicyclopentadiene (Ultrene.RTM. 99) (DCPD) was obtained from
Cymetech Corporation. A modified DCPD base resin containing 20-25%
tricyclopentadiene (and small amounts of higher cyclopentadiene
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 containing 6-8% tricyclopentadiene (and small amounts of
higher cyclopentadiene homologs) was prepared by heat treatment of
Ultrene.RTM. 99 generally as described in U.S. Pat. No.
4,899,005.
[0513] Liquid MDI (50/50 mixture of 4,4'-MDI and 2,4'-MDI) was used
as received from Bayer Material Science (Mondur.RTM. MLQ) and was
used where indicated. Solid MDI (4,4'-methylene diphenyl
diisocyanate) was used as received from Sigma Aldrich (98% purity).
Ethanox.RTM. 4702 antioxidant
(4,4'-methylenebis(2,6-di-tertiary-butylphenol), Albemarle
Corporation) was used where indicated. Crystal Plus 70FG mineral
oil, containing 2 phr CAB-O-SIL.RTM. TS610 fumed silica (Cabot),
was used to prepare the catalyst suspensions. Triphenylphosphine
(TPP) was used as received from Arkema. A hydroperoxide gel
modifier, cumene hydroperoxide (CHP) was used as received from
Sigma Aldrich (88% purity, unless otherwise specified) or Syrgis
Performance Initiators (Norox.RTM. CHP, 85%). CHP was added to
resin formulations as a 1,000 ppm concentration stock solution in
DCPD. Additionally, CHP from Akzo Nobel Polymer Chemicals
(Trigonox.RTM. K-90, 88%) was used as received and added to the
resin formulation (Table 10, Example 31(d) and Table 11, Example
32(d). Oleyl alcohol was used as received from Sigma Aldrich
(technical grade, 85%). 9-decen-1-ol was used as received from
Sigma Aldrich (97% purity).
[0514] 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); 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(benzylide-
ne)(tri-n-butylphosphine)ruthenium(II) (C771);
[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(phenylind-
enylidene)(diethylphenylphosphine)ruthenium(II) (C835).
[0515] Glass fabrics were used as supplied by Vectorply (E-LT
3500-10) based on PPG Hybon.RTM. 2026 ("Vectorply Glass Fabric");
Saertex (U14EU970-01190-T2525-125000) based on PPG Hybon.RTM. 2002
("Saertex Glass Fabric"); Chongqing Polycomp Internation Corp.
(CPIC Fiberglass) (EKU 1150(0)/50-600) ("CPIC Glass Fabric"); Owens
Corning (L1020/07A06 Xweft 200tex) ("Owens Corning Glass Fabric");
SGL Kumpers (HPT970) based on PPG Hybon.RTM. 2002 ("SGL Glass
Fabric").
[0516] Carbon fabrics were used as supplied by Vectorply (C-L 1800)
("Vectorply Carbon Fabric"); Zoltek (Panex 35 UD
Fabic-PX35UD0500-1220) ("Zoltek Carbon Fabric").
[0517] Additives to the resin are reported as ppm, which is defined
as the weight in grams of additive per million grams of resin, or
as phr, which is defined as the weight in grams of the additive per
hundred grams of resin.
[0518] Composite laminates were fabricated for testing by a VARTM
process. A sealed and release-treated aluminum plate, possessing
inlet and outlet ports affixed to the bottom surface, was utilized
as the bottom mold surface. Plies of glass or carbon fabric cut to
dimensions of 3''.times.6'' were arranged on top of the aluminum
mold to achieve a 1/8'' laminate thickness. A peel ply (Bron
Aerotech; PTFE-coated) was placed over the fabric plies, and nylon
resin distribution media (Airtech Greenflow 75) was positioned on
top of the peel ply at opposite ends of the composite laminate
corresponding to the position of the inlet port and outlet port,
respectively. A sheet of vacuum bagging film (Umeco Process
Materials Stretch-Vac 2000) was placed over the completed layup and
affixed to the mold surface using sealant tape (Airtech AT200-Y
tape). Vacuum was applied to the outlet port to evacuate air from
the layup to a vacuum level of between 28 inches-Hg to 29
inches-Hg. Resin prepared as per the examples presented below
herein was degassed under vacuum with stirring for at least 20
minutes. Catalyst suspension was injected into the resin under
vacuum and the catalyzed resin was stirred under vacuum for at
least one minute. The resin and catalyst suspension were at ambient
temperature (20-25.degree. C.) immediately prior to mixing. After
at least one minute, stirring of the catalyzed resin was stopped,
the vacuum source was clamped off, and the catalyzed resin was
backfilled with argon. The catalyzed resin was then infused through
the fabric plies, driven by the pressure gradient between the
ambient pressure and the evacuated fabric layup.
[0519] The glass composite laminates of the examples in Tables 1,
5, 6, 7, and 8 presented below herein were prepared using the VARTM
process with four plies of glass fabric reinforcement. After the
infusion was complete, the glass composite laminate was heated from
ambient temperature (20-25.degree. C.) to 35.degree. C. for two
hours. After two hours at 35.degree. C. the glass composite
laminate was heated to 100.degree. C. at a heating rate of
1.degree. C./min and held at 100.degree. C. for 1 hour and then
allowed to cool to ambient temperature (20-25.degree. C.) and
subsequently demolded.
[0520] The carbon composite laminates of the examples in Tables 1,
5, 6, 7, and 8 presented below herein were prepared using the VARTM
process with six plies of carbon fabric reinforcement. After the
infusion was complete, the carbon composite laminate was heated
from ambient temperature (20-25.degree. C.) to 35.degree. C. for
two hours. After two hours at 35.degree. C. the carbon composite
laminate was heated to 100.degree. C. at a heating rate of
1.degree. C./min and held at 100.degree. C. for 1 hour and then
allowed to cool to ambient temperature (20-25.degree. C.) and
subsequently demolded.
[0521] The glass composite laminates of the examples in Tables 2,
3, 4, and 9 presented below herein were prepared using the VARTM
process with four plies of glass fabric reinforcement, except that
each ply was cut dimensions of 6''.times.10'' and a release film
(Airtech Wrightlon.RTM. 5200B) was used instead of the Bron
Aerotech peel ply. After the infusion was complete, the glass
composite laminate was heated from ambient temperature
(20-25.degree. C.) to 75.degree. C. at 2.degree. C./min, and then
heated from 75.degree. C. to 120.degree. C. at 2.degree. C./min and
held at 120.degree. C. for 2 hours, and then allowed to cool to
ambient temperature (20-25.degree. C.) and subsequently
demolded.
[0522] The glass composite laminates of the examples in Tables 10
and 12 presented below herein were prepared using the VARTM process
with four plies of glass fabric reinforcement. After the infusion
was complete, the glass composite laminate was heated from ambient
temperature (20-25.degree. C.) to 35.degree. C. for 2 hours. After
2 hours at 35.degree. C. the glass composite laminate was heated to
120.degree. C. at a heating rate of 2.degree. C./min and held at
120.degree. C. for 2 hours and then allowed to cool to ambient
temperature (20-25.degree. C.) and subsequently demolded.
[0523] The carbon composite laminates of the examples in Table 11
and 12 presented below herein were prepared using the VARTM process
with six plies of carbon fabric reinforcement. After the infusion
was complete, the carbon composite laminate was heated from ambient
temperature (20-25.degree. C.) to 35.degree. C. for 2 hours. After
2 hours at 35.degree. C. the carbon composite laminate was heated
to 120.degree. C. at a heating rate of 2.degree. C./min and held at
120.degree. C. for 2 hours and then allowed to cool to ambient
temperature (20-25.degree. C.) and subsequently demolded.
[0524] The mechanical properties were measured using standard
techniques. Interlaminar shear strength (ILSS) at 10% strain was
measured by the short-beam shear method according to ASTM D2344 on
1''.times.1/4''.times.1/8'' samples. The ILSS values were reported
in units of pounds per square inch (psi). Interlaminar shear
strength (ILSS) is a measure of the adhesion and/or compatibility
between polymer matrix and fiber reinforcement in a composite.
Reported ILSS values are the average of 3 samples. All ILSS samples
were stored and tested at ambient room conditions. The following
criteria, based on interlaminar shear strength values, was used to
characterize the adhesion and/or compatibility between the polymer
matrix and the glass or carbon fiber reinforcement materials.
Composites having poor adhesion and/or compatibility between the
polymer matrix and fiber reinforcement were characterized as having
ILSS values less than about 3,000 psi suggesting a lack of covalent
adhesion between the polymer matrix and fiber reinforcement.
Composites having moderate adhesion and/or compatibility between
the polymer matrix and fiber reinforcement were characterized as
having ILSS values from about 3,000 psi to about 6,000 psi
suggesting minimal to no covalent adhesion between the polymer
matrix and fiber reinforcement. Composites having superior adhesion
and/or compatibility between the polymer matrix and fiber
reinforcement were characterized as having ILSS values greater than
about 6,000 psi suggesting a higher degree of covalent adhesion
between the polymer matrix and fiber reinforcement.
[0525] Synthesis of HENB (2-hydroxyethyl
bicyclo[2.2.1]hept-2-ene-5-carboxylate) HEA (2-hydroxyethyl
acrylate) (640 g, 1.0 mol eq.) was added to a 3 L round bottom
flask containing toluene (1 kg). DCPD (dicyclopentadiene) (1.5 kg)
was added to a separate 3 L round bottom flask, and the 3 L flask
containing DCPD was affixed with a Vigreaux column and distillation
head connected to the condenser. The 3 L flask containing HEA and
toluene was connected to the condenser. The DCPD was heated to
>160.degree. C. under an inter atmosphere to "crack" the DCPD
and form CPD (cyclopentadiene). The CPD (740 g, 2.0 mol eq.) was
added dropwise to the HEA/toluene mixture at 10-40.degree. C. under
an inert atmosphere. Conversion of HEA to HENB (2-hydroxyethyl
bicyclo[2.2.1]hept-2-ene-5-carboxylate) was monitored by GC (gas
chromatography). Toluene and reformed DCPD (364 g) were removed
from the reaction mixture by vacuum distillation to give the
desired HENB product as a colorless liquid (1,004 g, quantitative
yield, approx. 98% purity).
[0526] Adhesion Promoter Composition (A). Liquid MDI (Modur.RTM.
MLQ) (465 g) was added to a 2 L round bottom flask containing
toluene (800 g, dried over molecular sieves). Synthesized HENB
(2-hydroxyethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate) (35 g) was
added to the 2 L round bottom flask containing the toluene and
liquid MDI. The 2 L round bottom flask was stirred overnight at
40.degree. C. under an inert atmosphere. The toluene was removed in
vacuo and the remaining reaction mixture was analyzed by .sup.13C
NMR as described below herein. The remaining reaction mixture was
used as prepared.
[0527] Adhesion Promoter Composition (B). Synthesized HENB
(2-hydroxyethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate) (0.001 mol
eq., 0.0728 g) was added to liquid MDI (Mondur.RTM. MLQ) (1.0 mol
eq., 99.93 g) at ambient temperature (22-25.degree. C.) in a 125 mL
round bottom flask and stirred under an inert atmosphere for a
minimum of 24 hours. The progress of the reaction was monitored by
.sup.13C NMR as described below herein. The reaction mixture was
used as prepared.
[0528] Adhesion Promoter Composition (C). Synthesized HENB
(2-hydroxyethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate) (0.01 mol
eq., 0.7229 g) was added to liquid MDI (Mondur.RTM. MLQ) (1.0 mol
eq., 99.28 g) at ambient temperature (22-25.degree. C.) in a 125 mL
round bottom flask and stirred under an inert atmosphere for a
minimum of 24 hours. The progress of the reaction was monitored by
.sup.13C NMR as described below herein. The reaction mixture was
used as prepared.
[0529] Adhesion Promoter Composition (D). Synthesized HENB
(2-hydroxyethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate) (0.10 mol
eq., 338 g) was added to liquid MDI (Mondur.RTM. MLQ) (1.0 mol eq.,
4646 g) at ambient temperature (22-25.degree. C.) and stirred under
an inert atmosphere for a minimum of 24 hours. The progress of the
reaction was monitored by .sup.13C NMR as described below herein.
The reaction mixture was used as prepared.
[0530] Adhesion Promoter Composition (E). Synthesized HENB
(2-hydroxyethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate) (0.25 mol
eq., 15.4 g) was added to liquid MDI (Mondur.RTM. MLQ) (1.0 mol
eq., 84.6 g) at ambient temperature (22-25.degree. C.) in a 100 mL
round bottom flask and stirred under an inert atmosphere for a
minimum of 24 hours. The progress of the reaction was monitored by
.sup.13C NMR as described below herein. The reaction mixture was
used as prepared.
[0531] Adhesion Promoter Composition (F). Synthesized HENB
(2-hydroxyethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate) (0.40 mol
eq., 22.6 g) was added to liquid MDI (Mondur.RTM. MLQ) (1.0 mol
eq., 77.4 g) at ambient temperature (22-25.degree. C.) in a 100 mL
round bottom flask and stirred under an inert atmosphere for a
minimum of 24 hours. The progress of the reaction was monitored by
.sup.13C NMR as described below herein. The reaction mixture was
used as prepared.
[0532] Adhesion Promoter Composition (G). Synthesized HENB
(2-hydroxyethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate) (0.50 mol
eq., 26.7 g) was added to liquid MDI (Mondur.RTM. MLQ) (1.0 mol
eq., 73.3 g) at ambient temperature (22-25.degree. C.) in a 100 mL
round bottom flask and stirred under an inert atmosphere for a
minimum of 24 hours. The progress of the reaction was monitored by
.sup.13C NMR as described below herein. The reaction mixture was
used as prepared.
[0533] Adhesion Promoter Composition (H). Synthesized HENB
(2-hydroxyethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate) (0.75 mol
eq., 35.3 g) was added to liquid MDI (Mondur.RTM. MLQ) (1.0 mol
eq., 69.7) at ambient temperature (22-25.degree. C.) in a 100 mL
round bottom flask and stirred under an inert atmosphere for a
minimum of 24 hours. The progress of the reaction was monitored by
.sup.13C NMR as described below herein. The reaction mixture was
used as prepared.
[0534] Adhesion Promoter Composition (I). Synthesized HENB
(2-hydroxyethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate) (1.0 mol
eq., 42.1 g) was added to liquid MDI (Mondur.RTM. MLQ) (1.0 mol
eq., 57.9 g) at ambient temperature (22-25.degree. C.) in a 100 mL
round bottom flask and stirred under an inert atmosphere for a
minimum of 24 hours. The progress of the reaction was monitored by
.sup.13C NMR as described below herein. The reaction mixture was
used as prepared.
[0535] Adhesion Promoter Composition (J). 2-Hydroxyethyl acrylate
(HEA) (0.1 mol eq., 4.3 g) was added to liquid MDI (Mondur.RTM.
MLQ) (1.0 mol eq., 93.0 g) at ambient temperature (22-25.degree.
C.) in a 100 mL round bottom flask and stirred under an inert
atmosphere for a minimum of 24 hours. The progress of the reaction
was monitored by .sup.13C NMR in a similar manner as described
below herein. The reaction mixture was used as prepared.
[0536] Adhesion Promoter Composition (K). 9-Decen-1-ol (0.1 mol
eq., 6 g) was added to liquid MDI (Mondur.RTM. MLQ) (1.0 mol eq.,
93 g) at ambient temperature (22-25.degree. C.) in a 100 mL round
bottom flask and stirred under an inert atmosphere for a minimum of
24 hours. The progress of the reaction was monitored by .sup.13C
NMR in a similar manner as described below herein. The reaction
mixture was used as prepared.
[0537] Adhesion Promoter Composition (L). Oleyl alcohol (0.1 mol
eq., 10 g) was added to liquid MDI (Mondur.RTM. MLQ) (1.0 mol eq.,
93 g) at ambient temperature (22-25.degree. C.) in a 125 mL round
bottom flask and stirred under an inert atmosphere for a minimum of
24 hours. The progress of the reaction was monitored by .sup.13C
NMR in a similar manner as described below herein. The reaction
mixture was used as prepared.
[0538] Synthesis of MDI-HENB Mono Adduct,
C.sub.25H.sub.24N.sub.2O.sub.5.
##STR00067## [0539] Chemical Formula:
C.sub.25H.sub.24N.sub.2O.sub.5 [0540] Exact Mass: 432.17 [0541]
Molecular Weight: 432.47
[0542] In a glovebox under argon atmosphere, 20.0 g (79.9 mmol, 1.0
equiv) 4,4'-methylene diphenyl diisocyanate (solid MDI) was charged
to a 1-L 3-neck round bottom flask equipped with a large stirbar.
500 mL anhydrous toluene (Sigma Aldrich) was added. The flask was
capped with rubber septa and a gas-adapter and removed from the
glovebox. The gas adapter was connected to a Schlenk line. Under a
strong flow of argon, a reflux condenser and digital thermometer
were connected to the two remaining 24/40 ports. 29.87 g (163.8
mmol, 2.05 equiv) synthesized HENB was added dropwise via syringe
in .about.1 mL portions over 45 minutes. The resulting suspension
was heating to an internal temperature of 70.degree. C. for 24 h
then cooled to room temperature. After several minutes at
70.degree. C. the mixture becomes completely homogeneous followed
by slow precipitation of a transparent solid. Upon cooling to room
temperature, more solid precipitates leaving a cloudy suspension.
The mixture was filtered through a course glass frit and the
resulting solids washed with 100 mL toluene. Volatiles were
subsequently removed by rotary evaporation at 50.degree. C.,
leaving a thick, viscous oil with the strong odor of HENB. This oil
was dissolved in dichloromethane and purified by column
chromatography (10% EtOAc in DCM). Volatiles were removed from the
fraction of interest, first by rotovap then by drying on a Schlenk
line overnight, yielding 29.0 g (83.9%) of a hard, hygroscopic
solid, which was stored under argon. .sup.1H and .sup.13C NMR
reveals a clean mixture (78:22) of the desired products (endo- and
exo-configuration of norbornene ring, respectively).
[0543] .sup.1H NMR (CDCl.sub.3, 400 MHz): .delta.=7.30 (m,
overlapping, phenyls), 7.10 (broad, distorted d, phenyls), 6.99
(broad s, phenyls), 6.16 (m, endo-C.dbd.CH), 6.11 (m,
exo-C.dbd.CH), 6.09 (m, exo-CH.dbd.C), 5.92 (m, endo-CH.dbd.C)
4.2-4.4 (overlapping m, O--CH.sub.2CH.sub.2--O), 3.87 (s,
Ph-CH.sub.2-Ph), 3.20 (s, norbornene), 3.04 (s, norbornene), 2.97
(m, norbornene), 2.89 (broad s, norbornene), 2.25 (broad m,
norbornene); 2.01 (m, norbornene), 1.89 (distorted m, norbornene),
1.24-1.55 (overlapping peaks, norbornene).
[0544] .sup.13C NMR (CDCl.sub.3, 100 MHz): .delta.=176.23
(exo-NB--CO--O), 174.75 (endo-NB--C(O)--O), 155.37 (NHC(O)--O),
138.21, 137.97, 135.94, 135.75, 132.37, 129.49, 119.09 (NCO), 63.07
(O--CH.sub.2CH.sub.2--O), 62.56 (exo-O--CH.sub.2CH.sub.2--O), 62.30
(endo-O--CH.sub.2CH.sub.2--O), 49.71, 46.88, 46.40, 45.83, 43.31,
43.15, 42.61, 41.75, 40.62, 30.45, 29.37.
[0545] .sup.13C NMR (CDCl.sub.3, 100 MHz) Analysis of Adhesion
Promoter Compositions (HENB and MDI Pre-Reacted Mixtures). The
primary diagnostic region of HENB and liquid MDI (Mondur.RTM. MLQ)
pre-reacted mixtures is the --C(.dbd.O)O--CH.sub.2--CH.sub.2--OH
region (ethylene bridge region) of HENB. FIG. 1 is a .sup.13C NMR
spectrum of the ethylene bridge region of an HENB and liquid MDI
(Mondur.RTM. MLQ) pre-reacted mixture at time zero, immediately
after mixing. In CDCl.sub.3 HENB gives carbon peaks in two groups,
Group A and Group B (FIG. 1) corresponding to the carbons of the
ethylene bridge region. The two carbon peaks in Group A have
chemical shifts around 66.1011 ppm and 65.9157 ppm corresponding to
the --CH.sub.2-- carbon connected to the to the oxygen of the ester
group (--CH.sub.2--O--C(.dbd.O)--) of HENB, exo and endo isomers,
respectively (FIG. 1). The two carbon peaks in Group B have
chemical shifts around 61.1841 ppm and 61.2156 ppm corresponding to
the --CH.sub.2-- carbon connected to the to the oxygen of the
hydroxyl group (--CH.sub.2--OH) of HENB, exo and endo isomers,
respectively (FIG. 1). As the reaction between HENB and liquid MDI
(Mondur.RTM. MLQ) proceeds, these peaks disappear and are replaced
by carbon peaks in two groups, Group C and Group D (FIG. 2),
thereby demonstrating that HENB is no longer present in the mixture
in its native form. FIG. 2 is a .sup.13C NMR spectrum of the
ethylene bridge region of an HENB and liquid MDI (Mondur.RTM. MLQ)
pre-reacted mixture after mixing for 5 days under inert atmosphere
at ambient temperature (20-25.degree. C.). In FIG. 2, the broad
carbon peak in Group C having a chemical shift around 63.0490 ppm
is consistent with the --CH.sub.2-- carbon connected to the oxygen
of the carbamate group (--NH--C(.dbd.O)--O--CH.sub.2--) of the
MDI-HENB mono adduct as shown above herein, where the broadness of
the peak indicates overlapping of the exo and endo isomers. In FIG.
2, the carbon peak in Group D having a chemical shift around
62.5340 ppm is consistent with the --CH.sub.2-- carbon connected to
the oxygen of the ester group (--CH.sub.2--O--C(.dbd.O)--) of the
MDI-HENB mono adduct as shown above herein, exo isomer. In FIG. 2,
the carbon peak in Group D having a chemical shift around 62.2901
ppm is consistent with the --CH.sub.2-- carbon connected to the
oxygen of the ester group (--CH.sub.2--O--C(.dbd.O)--) of the
MDI-HENB mono adduct as shown above herein, endo isomer.
Examples 1(a-c)-5(a-c)
ILSS of Glass and Carbon Composites Prepared by VARTM
[0546] The modified DCPD (containing 20-25% tricyclopentadiene) was
formulated with 0.6 phr TPP, 2 phr Ethanox.RTM. 4702 antioxidant,
and 0 phr, 2 phr, or 4 phr liquid MDI (Mondur.RTM. MLQ). The resin
was catalyzed by the addition of C827 (monomer to catalyst ratio
45,000:1) in a suspension of mineral oil. VARTM samples were
prepared using commercial glass fabrics and commercial carbon
fabrics as described above herein. The composite laminates were
cured as described above herein. The ILSS of the resulting
composites are shown in (Table 1).
TABLE-US-00001 TABLE 1 ILSS Example Adhesion 1 2 3 4 5 Promoter
Vectorply Zoltek Vectorply Saertex CPIC (Mondur .RTM. Carbon Carbon
Glass Glass Glass MLQ) Fabric Fabric Fabric Fabric Fabric a None
3120 1715 1756 1253 1692 b 2 phr 9154 3734 8628 6048 8628 c 4 phr
9786 3607 8865 6073 8637
Examples (6a,6b)
ILSS of Glass Composites Prepared by VARTM
[0547] On Day 1, modified DCPD (containing 20-25%
tricyclopentadiene) was formulated with 20 ppm CHP, 2 phr
Ethanox.RTM. 4702 antioxidant, and 2 phr liquid MDI (Mondur.RTM.
MLQ) to give Resin Formulation (A1). Also on Day 1, modified DCPD
(containing 20-25% tricyclopentadiene) was formulated with 20 ppm
CHP, 2 phr Ethanox.RTM. 4702 antioxidant, 2 phr MDI (Mondur.RTM.
MLQ), and 2 phr HENB to give Resin Formulation (B1). The liquid MDI
(Mondur.RTM. MLQ) and HENB were independently added to Resin
Formulation (B1) as separate additives. Resin Formulation (A1) and
Resin Formulation (B1) were sparged with argon and stored in
separate air-tight containers at ambient temperature (20-25.degree.
C.).
[0548] On Day 1, Day 7, Day 28, Day 58, and Day 105 a portion of
Formulation (A1) was catalyzed by the addition of C827 (monomer to
catalyst ratio 30,000:1) in a suspension of mineral oil and a VARTM
sample was prepared as described above herein using commercial
glass fabric SGL Kumpers (HPT970E0) based on PPG Hybon.RTM. 2002
("SGL Glass Fabric"). The composite laminates were cured as
described above herein. The ILSS of the resulting composites are
shown below in Table 2.
[0549] On Day 1, Day 7, and Day 28 a portion of Formulation (B1)
was catalyzed by the addition of C827 (monomer to catalyst ratio
30,000:1) in a suspension of mineral oil and a VARTM sample was
prepared as described above herein using commercial glass fabric
SGL Kumpers (HPT970E0) based on PPG Hybon.RTM. 2002 ("SGL Glass
Fabric"). The composite laminates were cured as described above
herein. The ILSS of the resulting composites are shown below in
Table 2.
TABLE-US-00002 TABLE 2 ILSS Resin Example Formulation Day 1 Day 7
Day 28 Day 58 Day 105 6a A1 7564 7561 7596 7224 7417 6b B1 8070
6783 4916 Not Not measured measured
Examples 7(a)-7(f)
ILSS of Glass Composites Prepared by VARTM
[0550] On Day 1, modified DCPD (containing 20-25%
tricyclopentadiene) was formulated with 0.4 phr TPP, 2 phr
Ethanox.RTM. 4702 antioxidant, and 2 phr adhesion promoter
composition (A) to give Resin Formulation (C.sub.1). Resin
Formulation (C.sub.1) was sparged with argon and stored in an
air-tight container at ambient temperature (20-25.degree. C.). The
adhesion promoter composition (A) was prepared as described above
herein.
[0551] On Day 1, Day 69, Day 104, Day 151, and Day 201, and Day 326
a portion of Formulation (C1) was catalyzed by the addition of C827
(monomer to catalyst ratio 30,000:1) in a suspension of mineral oil
and a VARTM sample was prepared as described above herein using
commercial glass fabric SGL Kumpers (HPT970E0) based on PPG
Hybon.RTM. 2002 ("SGL Glass Fabric"). The composite laminates were
cured as described above herein. The ILSS of the resulting
composites are shown below in Table 3.
TABLE-US-00003 TABLE 3 ILSS Example Day ILSS 7a 1 7945 7b 69 8016
7c 104 8063 7d 151 7984 7e 201 7895 7f 326 8162
Examples 8(a)-8(d)
ILSS of Glass Composites Prepared by VARTM
[0552] On Day 1, modified DCPD (containing 20-25%
tricyclopentadiene) was formulated with 0.4 phr TPP, 2 phr
Ethanox.RTM. 4702 antioxidant, and 2 phr adhesion promoter
composition (A) to give Resin Formulation (D1). Resin Formulation
(D1) was sparged with argon and stored in an air-tight container at
ambient temperature (40.degree. C.). The adhesion promoter
composition (A) was prepared as described above herein.
[0553] On Day 1, Day 72, Day 151, and Day 202, a portion of
Formulation (D1) was catalyzed by the addition of C827 (monomer to
catalyst ratio 30,000:1) in a suspension of mineral oil and a VARTM
sample was prepared as described above herein using commercial
glass fabric SGL Kumpers (HPT970E0) based on PPG Hybon.RTM. 2002
("SGL Glass Fabric"). The composite laminates were cured as
described above herein. The ILSS of the resulting composites are
shown below in Table 4.
TABLE-US-00004 TABLE 4 ILSS Example Day ILSS 8a 1 7945 8b 72 7512
8c 151 7811 8d 202 7687
Examples 9(a-h)-13(a-h)
ILSS of Glass and Carbon Composites Prepared by VARTM
[0554] The modified DCPD (containing 20-25% tricyclopentadiene) was
formulated with 0.6 phr TPP, 2 phr Ethanox.RTM. 4702 antioxidant,
and 4 phr of the appropriate adhesion promoter composition. The
resin was catalyzed by the addition of C827 (monomer to catalyst
ratio 45,000:1) in a suspension of mineral oil. VARTM samples were
prepared using commercial glass fabrics and commercial carbon
fabrics as described above herein. The composite laminates were
cured as described above herein. The adhesion promoter compositions
were prepared as described above herein. The ILSS of the resulting
composites are shown in below in Table 5.
TABLE-US-00005 TABLE 5 ILSS Example 9 10 11 12 13 Adhesion
Vectorply Zoltek Vectorply Saertex CPIC Promoter Carbon Carbon
Glass Glass Glass Composition Fabric Fabric Fabric Fabric Fabric a
(B) 9269 4462 9330 6797 8639 b (C) 9232 6865 9370 8184 8877 c (D)
9769 9390 9294 8605 9027 d (E) 10622 9252 9275 8832 9425 e (F) 9976
9423 9694 8924 9248 f (G) 8921 9276 9094 8715 8957 g (H) 7759 8838
8806 8112 8487 h (I) 6865 6787 7413 7803 7742
Examples 14(a)-18(a)
ILSS of Glass and Carbon Composites Prepared by VARTM
[0555] The modified DCPD (containing 20-25% tricyclopentadiene) was
formulated with 0.6 phr TPP, 2 phr Ethanox.RTM. 4702 antioxidant,
and 4 phr of adhesion promoter composition (J). The resin was
catalyzed by the addition of C827 (monomer to catalyst ratio
45,000:1) in a suspension of mineral oil. VARTM samples were
prepared using commercial glass fabrics and commercial carbon
fabrics as described above herein. The composite laminates were
cured as described above herein. The adhesion promoter composition
(J) was prepared as described above herein. The ILSS of the
resulting composites are shown below in Table 6.
TABLE-US-00006 TABLE 6 ILSS Example 14 15 16 17 18 Adhesion
Vectorply Zoltek Vectorply Saertex CPIC Promoter Carbon Carbon
Glass Glass Glass Composition Fabric Fabric Fabric Fabric Fabric a
(J) 9845 9126 9188 8769 9532
Examples 19(a)-23(a)
ILSS of Glass and Carbon Composites Prepared by VARTM
[0556] The modified DCPD (containing 20-25% tricyclopentadiene) was
formulated with 0.6 phr TPP, 2 phr Ethanox.RTM. 4702 antioxidant,
and 0.6 phr of the MDI-HENB mono adduct. The resin was catalyzed by
the addition of C827 (monomer to catalyst ratio 45,000:1) in a
suspension of mineral oil. VARTM samples were prepared using
commercial glass fabrics and commercial carbon fabrics as described
above herein. The composite laminates were cured as described above
herein. The MDI-HENB mono adduct was prepared as described above
herein. The ILSS of the resulting composites are shown below in
Table 7.
TABLE-US-00007 TABLE 7 ILSS Example 19 20 21 22 23 Vectorply Zoltek
Vectorply Saertex CPIC Carbon Carbon Glass Glass Glass Fabric
Fabric Fabric Fabric Fabric a 2563 2051 2580 1881 1762
Examples 24(a)-28(a)
ILSS of Glass and Carbon Composites Prepared by VARTM
[0557] The modified DCPD (containing 20-25% tricyclopentadiene) was
formulated with 0.6 phr TPP, 2 phr Ethanox.RTM. 4702 antioxidant,
3.4 phr liquid MDI (Mondur.RTM. MLQ), and 0.6 phr of the MDI-HENB
mono adduct. The liquid MDI (Mondur.RTM. MLQ and the mono MDI-HENB
mono adduct were independently added to the modified DCPD as
separate additives. The resin was catalyzed by the addition of C827
(monomer to catalyst ratio 45,000:1) in a suspension of mineral
oil. VARTM samples were prepared using commercial glass fabrics and
commercial carbon fabrics as described above herein. The composite
laminates were cured as described above herein. The MDI-HENB mono
adduct was prepared as described above herein. The ILSS of the
resulting composites are shown below in Table 8.
TABLE-US-00008 TABLE 8 ILSS Example 24 25 26 27 28 Vectorply Zoltek
Vectorply Saertex CPIC Carbon Carbon Glass Glass Glass Fabric
Fabric Fabric Fabric Fabric a 9150 5173 9450 7431 8402
Examples 29(a-d)
ILSS of Glass Composites Prepared by VARTM
[0558] The modified DCPD (containing 20-25% tricyclopentadiene) was
formulated with 20 ppm CHP, 2 phr Ethanox.RTM. 4702 antioxidant, 2
phr liquid MDI (Mondur.RTM. MLQ), and 2 phr of 9-decen-1-ol to form
Resin Formulation (E1). The liquid MDI (Mondur.RTM. MLQ) and
9-decen-1-ol were independently added to Resin Formulation (E1) as
separate additives. The modified DCPD (containing 20-25%
tricyclopentadiene) was formulated with 20 ppm CHP, 2 phr
Ethanox.RTM. 4702 antioxidant, 2 phr liquid MDI (Mondur.RTM. MLQ),
and 2 phr of oleyl alcohol to form Resin Formulation (F1). The
liquid MDI (Mondur.RTM. MLQ) and oleyl alcohol were independently
added to Resin Formulation (F1) as separate additives. The modified
DCPD (containing 20-25% tricyclopentadiene) was formulated with 20
ppm CHP, 2 phr Ethanox.RTM. 4702 antioxidant, 2 phr of adhesion
promoter composition (K) to form Resin Formulation (G1). The
modified DCPD (containing 20-25% tricyclopentadiene) was formulated
with 20 ppm CHP, 2 phr Ethanox.RTM. 4702 antioxidant, 2 phr of
adhesion promoter composition (L) to form Resin Formulation (H1).
The resin formulations (E1-H1) were catalyzed by the addition of
C.sub.827 (monomer to catalyst ratio 30,000:1) in a suspension of
mineral oil. VARTM samples was prepared as described above herein
using commercial glass fabric SGL Kumpers (HPT970E0) based on PPG
Hybon.RTM. 2002 ("SGL Glass Fabric"). The composite laminates were
cured as described above herein. The ILSS of the resulting
composites are shown below in Table 9.
TABLE-US-00009 TABLE 9 ILSS Resin Example Formulation ILSS 29a E1
6109 29b F1 7865 29c G1 8680 29d H1 8203
Examples 30(a-f)
ILSS of Glass Composites Prepared by VARTM
[0559] DCPD (containing 6-8% tricyclopentadiene) was formulated
with 2 phr Ethanox.RTM. 4702 antioxidant, 4 phr adhesion promoter
composition (D), and with the inhibitor described in Table 10. The
resin was catalyzed by the addition of the catalyst listed in Table
10 (monomer to catalyst ratio between 5,000:1 and 60,000:1 as
listed in Table 10) in a suspension of mineral oil. VARTM samples
were prepared using commercial glass fabric Vectorply (E-LT
3500-10) based on PPG Hybon.RTM. 2026 ("Vectorply Glass Fabric").
The composite laminates were cured as described above herein. The
adhesion promoter composition was prepared as described above
herein. The ILSS of the resulting composites are shown below in
Table 10.
TABLE-US-00010 TABLE 10 ILSS Monomer to ILSS Example Catalyst
Catalyst Ratio Inhibitor (psi) 30a C771 45,000:1 None 8028 30b C801
5,000:1 TPP (0.1 phr) 8830 30c C627 60,000:1 TPP (1.0 phr) 8533 30d
C827 30,000:1 CHP 8166 (20 ppm) 30e C835 29,040:1 None 8106 30f
C747 60,000:1 TPP (0.4 phr) 8029
Examples 31(a-f)
ILSS of Carbon Composites Prepared by VARTM
[0560] DCPD (containing 6-8% tricyclopentadiene) was formulated
with 2 phr Ethanox.RTM. 4702 antioxidant, 4 phr adhesion promoter
composition (D), and with the inhibitor described in Table 11. The
resin was catalyzed by the addition of the catalyst listed in Table
11 (monomer to catalyst ratio between 5,000:1 and 60,000:1 as
listed in Table 11) in a suspension of mineral oil. VARTM samples
were prepared using commercial carbon fabric Vectorply (C-L 1800)
("Vectorply Carbon Fabric"). The composite laminates were cured as
described above herein. The adhesion promoter composition was
prepared as described above herein. The ILSS of the resulting
composites are shown in below in Table 11.
TABLE-US-00011 TABLE 11 ILSS Monomer to ILSS Example Catalyst
Catalyst Ratio Inhibitor (psi) 31a C771 45,000:1 None 9119 31b C801
5,000:1 TPP (0.1 phr) 9172 31c C627 60,000:1 TPP (1.0 phr) 8765 31d
C827 30,000:1 CHP 9295 (20 ppm) 31e C835 29,040:1 None 8943 31f
C747 60,000:1 TPP (0.4 phr) 8831
Example 32(a)-33(a)
ILSS of Glass Composites Prepared by VARTM
[0561] DCPD (containing 6-8% tricyclopentadiene) was formulated
with 2 phr Ethanox.RTM. 4702 antioxidant, 0.6 phr TPP, and 4 phr
adhesion promoter composition (D). The adhesion promoter
composition (D) was prepared as described above herein. The
adhesion promoter composition (D) had been prepared 156 days before
being formulated into (added to) the resin composition as described
above. The adhesion promoter composition (D) was stored in a sealed
container under a dry, inert atmosphere (e.g., under argon or
nitrogen) at normal storage temperatures as defined herein (e.g.,
5.degree. C.-50.degree. C.) before being formulated into (added to)
the resin composition as described above. The resin was catalyzed
by the addition of C827 (monomer to catalyst ratio 45,000:1) in a
suspension of mineral oil. VARTM samples were prepared using
commercial glass fabric and commercial carbon fabric as described
above herein. The composite laminates were cured as described above
herein. The ILSS of the resulting composites are shown in below in
Table 12.
TABLE-US-00012 TABLE 12 ILSS Example 32 33 Vectorply Vectorply
Carbon Glass Fabric Fabric a 9752 8417
[0562] 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.
* * * * *