U.S. patent application number 16/571350 was filed with the patent office on 2020-04-16 for adhesion promoters and gel-modifiers for olefin metathesis 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, Farshad J. Motamedi, Tessa Schulze, Anthony R. Stephen, Mark S. Trimmer, Li-Sheng Wang.
Application Number | 20200115277 16/571350 |
Document ID | / |
Family ID | 47357796 |
Filed Date | 2020-04-16 |
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United States Patent
Application |
20200115277 |
Kind Code |
A1 |
Wang; Li-Sheng ; et
al. |
April 16, 2020 |
ADHESION PROMOTERS AND GEL-MODIFIERS FOR OLEFIN METATHESIS
COMPOSITIONS
Abstract
This invention relates to compositions and methods for improving
the adhesion of resin compositions to substrate materials,
pre-treating substrate materials to improve the adhesion of resin
compositions to the substrate materials, and/or controlling gel
formation of resin compositions. More particularly, the invention
relates to compositions and methods for improving the adhesion of
ring opening metathesis polymerization (ROMP) compositions to
substrate materials using adhesion promoters containing isocyanate
groups in a resin composition. The invention also relates to
methods for improving the adhesion of resin compositions to
substrate materials by pre-treating substrate materials with
adhesion promoters containing isocyanate groups. The invention
further relates to a method of providing a gel-modified ROMP
composition, in which a hydroperoxide is added to a ROMP
polymerizable resin composition in order to control gel formation
of the polymerizing resin. An improved ROMP composition is further
disclosed, comprising a cyclic olefin, a ROMP metathesis catalyst,
an adhesion promoter, and an added hydroperoxide gel modifier. 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 catalysis,
organic synthesis, and polymer and materials chemistry and
manufacture.
Inventors: |
Wang; Li-Sheng; (Azusa,
CA) ; Stephen; Anthony R.; (South Pasadena, CA)
; Boothe; Paul W.; (Brooklyn, NY) ; Schulze;
Tessa; (Altadena, CA) ; Giardello; Michael A.;
(Pasadena, CA) ; Trimmer; Mark S.; (Monrovia,
CA) ; Cruce; Christopher J.; (Poway, CA) ;
Motamedi; Farshad J.; (Claremont, CA) ; Edgecombe;
Brian; (Anaheim, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
MATERIA, INC. |
Pasadena |
CA |
US |
|
|
Assignee: |
MATERIA, INC.
Pasadena
CA
|
Family ID: |
47357796 |
Appl. No.: |
16/571350 |
Filed: |
September 16, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14125837 |
Jul 17, 2014 |
10457597 |
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PCT/US2012/042850 |
Jun 17, 2012 |
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16571350 |
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61498528 |
Jun 17, 2011 |
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61654744 |
Jun 1, 2012 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C03C 25/30 20130101;
C08K 2201/014 20130101; C08K 5/29 20130101; C08G 2261/418 20130101;
C08F 32/02 20130101; C08G 61/08 20130101; C08G 2261/3325 20130101;
C08K 5/14 20130101; C08K 5/0025 20130101; C08K 5/14 20130101; C08L
65/00 20130101; C08K 5/29 20130101; C08L 65/00 20130101; C08K
5/0025 20130101; C08L 65/00 20130101 |
International
Class: |
C03C 25/30 20060101
C03C025/30; C08K 5/29 20060101 C08K005/29; C08K 5/14 20060101
C08K005/14; C08K 5/00 20060101 C08K005/00; C08F 32/02 20060101
C08F032/02 |
Claims
1-83. (canceled)
84. A composition, comprising: at least one cyclic olefin; at least
one olefin metathesis catalyst; at least one adhesion promoter
containing at least one compound containing at least two isocyanate
groups and a compound containing a heteroatom-containing functional
group and a metathesis-active olefin; and wherein the at least one
compound containing at least two isocyanate groups is selected from
the group consisting of 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;
hexamethylenediisocyanate; isophorone diisocyanate, 4,4'methylene
bis(cyclohexyl isocyanate); polymeric MDI; MDI prepolymer; and
liquid carbodiimide modified 4,4'-MDI; and wherein the compound
containing a heteroatom-containing functional group and a
metathesis-active olefin is selected from the group consisting of
5-norbornene-2-methanol (NB-MeOH); 2-hydroxyethyl
bicyclo[2.2.1]hept-2-ene-5-carboxylate (HENB); and allyl
alcohol.
85. The composition of claim 84, wherein the at least one cyclic
olefin is selected from the group consisting of strained cyclic
olefins, unstrained cyclic olefins, dienes, unsaturated polymers,
and mixtures thereof, wherein the cyclic olefin may contain a
functional group, or be substituted with a group, selected from
halogen, hydroxyl, hydrocarbyl, alkoxy, alkenyloxy, alkynyloxy,
aryloxy, aralkyloxy, alkaryloxy, acyl, acyloxy, alkoxycarbonyl,
alkylcarbonato, arylcarbonato, carboxy, carboxylato, carbamoyl,
alkyl-substituted carbamoyl, haloalkyl-substituted carbamoyl,
aryl-substituted carbamoyl, thiocarbamoyl alkyl-substituted
thiocarbamoyl, aryl-substituted thiocarbamoyl, carbamido, cyano,
cyanato, thiocyanato, formyl, thioformyl, amino, alkyl-substituted
amino, aryl-substituted amino, alkylamido, arylamido, imino,
alkylimino, arylimino, nitro, nitroso, sulfo, sulfonato,
alkylsulfanyl, arylsulfanyl, alkylsulfinyl, arylsulfinyl,
alkylsulfonyl, alkylaminosulfonyl, arylsulfonyl, boryl, borono,
boronato, phosphono, phosphonato, phosphinato, phospho, phosphino,
and mixtures thereof.
86. The composition of claim 84, wherein the at least one cyclic
olefin is selected from the group consisting of cyclobutene,
cycloheptene, cyclooctene, cyclononene, cyclodecene,
cyclooctadiene, cyclononadiene, cyclododecatriene,
tetracyclododecadiene, substituted norbornenes, substituted
dicyclopentadienes, 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-ethoxycarbony-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, or 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.
87. The composition of claim 84, wherein the at least one olefin
metathesis catalyst is a Group 8 transition metal complex having
the structure of formula (I) ##STR00048## wherein: M is a Group 8
transition metal; L.sup.1, L.sup.2, and L.sup.3 are independently
selected from 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 independently anionic ligands; and
R.sup.1 and R.sup.2 are independently selected from the group
consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl,
heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, and functional groups; wherein
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 the group
consisting of hydrocarbylene, substituted hydrocarbylene,
heteroatom-containing hydrocarbylene, and 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, wherein any
two or more of X1, 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.
88. The composition of claim 87, wherein at least one of L.sup.1,
L.sup.2, and L.sup.3 is an N-heterocyclic carbene ligand.
89. The composition of claim 84, wherein the at least one olefin
metathesis catalyst has the structure ##STR00049## wherein: M is a
Group 8 transition metal; n is 0 or 1; m is 0, 1, or 2; k is 0 or
1; X.sup.1 and X.sup.2 are independently selected from anionic
ligands; L.sup.2 and L.sup.3 are independently selected from
neutral electron donor ligands, or may be taken together to form a
single bidentate electron-donating heterocyclic ligand; R.sup.1 and
R.sup.2 are independently selected from the group consisting of
hydrogen, hydrocarbyl, substituted hydrocarbyl,
heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, and functional groups; X and Y
are independently selected from the group consisting of C, N, O, S,
and P; p is zero when X is O or S, and p is 1 when X is N or P; q
is zero when Y is O or S, and q is 1 when Y is N or P; Q.sup.1,
Q.sup.2, Q.sup.3, and Q.sup.4 are independently selected from the
group consisting of hydrocarbylene, substituted hydrocarbylene,
heteroatom-containing hydrocarbylene, substituted
heteroatom-containing hydrocarbylene, and --(CO)--, and further
wherein two or more substituents on adjacent atoms within Q may be
linked to form an additional cyclic group; w, x, y, and z are
independently zero or 1; and R.sup.3, R.sup.3A, R.sup.4, and
R.sup.4A are independently selected from the group consisting of
hydrogen, hydrocarbyl, substituted hydrocarbyl,
heteroatom-containing hydrocarbyl, and substituted
heteroatom-containing hydrocarbyl, wherein any two or more of
X.sup.1, X.sup.2, L.sup.2, L.sup.3, R.sup.1, R.sup.2, Q.sup.1,
Q.sup.2, Q.sup.3, Q.sup.4, R.sup.3, R.sup.3A, R.sup.4, and R.sup.4A
can be taken together to form a cyclic group, and further wherein
any one or more of X1, 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.
90. The composition of claim 89, wherein R.sup.1 and R.sup.2 are
taken together to form an indenylidene moiety.
91. The composition of claim 89, wherein M is ruthenium, w, x, y,
and z are zero, X and Y are N, and R.sup.3A and R.sup.4A are linked
to form -Q-, such that the complex has the structure ##STR00050##
wherein: Q is --CR.sup.11R.sup.12--CR.sup.13R.sup.14-- or
--CR.sup.11.dbd.CR.sup.13--, wherein R.sup.1, R.sup.12, R.sup.3,
and R.sup.14 are independently selected from the group consisting
of 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; R.sup.3 and R.sup.4 are aromatic;
R.sup.1 and R.sup.2 are independently selected from the group
consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl,
heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, and functional groups; or
R.sup.1 and R.sup.2 are taken together to form an indenylidene
moiety; and X.sup.1 and X.sup.2 are halogen.
92. The composition of claim 91, wherein: Q is
--CR.sup.11R.sup.12--CR.sup.13R.sup.14-- wherein R.sup.11,
R.sup.12, R.sup.3, and R.sup.14 are independently selected from the
group consisting of 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; and
R.sup.3 and R.sup.4 are unsubstituted phenyl or phenyl substituted
with one or more substituents selected from the group consisting of
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, and halogen.
93. The composition of claim 84, wherein the at least one olefin
metathesis catalyst has the structure ##STR00051## wherein: M is a
Group 8 transition metal; X.sup.1 and X.sup.2 are independently
anionic ligands; L.sup.1 is selected from neutral electron donor
ligands; Y is a heteroatom selected from the group consisting of 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,
isocyanate, hydroxyl, ester, ether, amine, imine, amide,
trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane,
siloxane, phosphine, phosphate, borate, and -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; and
any combination of R.sup.5, R.sup.6, R.sup.7, and R.sup.8 can be
linked to form one or more cyclic groups; n is 1 or 2, such that n
is 1 for the divalent heteroatoms 0 or S, and n is 2 for the
trivalent heteroatoms N or P; and Z is a group selected from the
group consisting of hydrogen, alkyl, aryl, functionalized alkyl,
functionalized aryl where the functional group may independently be
one or more or the following: alkoxy, aryloxy, halogen, carboxylic
acid, ketone, aldehyde, nitrate, 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.
94. The composition of claim 84, further comprising at least one
substrate material.
95. The composition of claim 94, wherein the substrate material is
selected from the group consisting of reinforcing materials, glass
fibers, glass fabrics, carbon fibers, carbon fabrics, aramid
fibers, aramid fabrics, polyolefin fibers, polyolefin fabrics,
polymer fibers, polymer fabrics, and mixtures thereof.
96. The composition of claim 84, wherein the concentration of the
adhesion promotor is 0.5 to 4.0 phr, based on the weight of
adhesion promoter per hundred grams of base resin.
97. A method for improving the adhesion of a resin composition to a
substrate material, comprising: contacting the resin composition of
claim 84 with the substrate material, and subjecting the resin
composition to conditions effective to promote an olefin metathesis
reaction of the at least one cyclic olefin.
98. The method of claim 97, wherein the at least one cyclic olefin
is selected from the group consisting of strained cyclic olefins,
unstrained cyclic olefins, dienes, unsaturated polymers, and
mixtures thereof, wherein the cyclic olefin may contain a
functional group, or be substituted with a group, selected from
halogen, hydroxyl, hydrocarbyl, alkoxy, alkenyloxy, alkynyloxy,
aryloxy, aralkyloxy, alkaryloxy, acyl, acyloxy, alkoxycarbonyl,
alkylcarbonato, arylcarbonato, carboxy, carboxylato, carbamoyl,
alkyl-substituted carbamoyl, haloalkyl-substituted carbamoyl,
aryl-substituted carbamoyl, thiocarbamoyl alkyl-substituted
thiocarbamoyl, aryl-substituted thiocarbamoyl, carbamido, cyano,
cyanato, thiocyanato, formyl, thioformyl, amino, alkyl-substituted
amino, aryl-substituted amino, alkylamido, arylamido, imino,
alkylimino, arylimino, nitro, nitroso, sulfo, sulfonato,
alkylsulfanyl, arylsulfanyl, alkylsulfinyl, arylsulfinyl,
alkylsulfonyl, alkylaminosulfonyl, arylsulfonyl, boryl, borono,
boronato, phosphono, phosphonato, phosphinato, phospho, phosphino,
and mixtures thereof.
99. The method of claim 97, wherein the at least one olefin
metathesis catalyst is a Group 8 transition metal complex having
the structure of formula (I) ##STR00052## wherein: M is a Group 8
transition metal; L.sup.1, L.sup.2, and L.sup.3 are independently
selected from 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 independently anionic ligands; and
R.sup.1 and R.sup.2 are independently selected from the group
consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl,
heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, and functional groups; wherein
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 the group
consisting of hydrocarbylene, substituted hydrocarbylene,
heteroatom-containing hydrocarbylene, and 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, wherein any
two or more of X1, 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 X1, 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.
100. The method of claim 97, wherein the substrate material is
selected from the group consisting of reinforcing materials, glass
fibers, glass fabrics, carbon fibers, carbon fabrics, aramid
fibers, aramid fabrics, polyolefin fibers, polyolefin fabrics,
polymer fibers, polymer fabrics, and mixtures thereof.
101. An article of manufacture comprising at least one resin
composition of claim 84.
102. The article of manufacture of claim 101, wherein the at least
one cyclic olefin is selected from the group consisting of strained
cyclic olefins, unstrained cyclic olefins, dienes, unsaturated
polymers, and mixtures thereof, wherein the cyclic olefin may
contain a functional group, or be substituted with a group,
selected from the group consisting of halogen, hydroxyl,
hydrocarbyl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, aralkyloxy,
alkaryloxy, acyl, acyloxy, alkoxycarbonyl, alkylcarbonato,
arylcarbonato, carboxy, carboxylato, carbamoyl, alkyl-substituted
carbamoyl, haloalkyl-substituted carbamoyl, aryl-substituted
carbamoyl, thiocarbamoyl alkyl-substituted thiocarbamoyl,
aryl-substituted thiocarbamoyl, carbamido, cyano, cyanato,
thiocyanato, formyl, thioformyl, amino, alkyl-substituted amino,
aryl-substituted amino, alkylamido, arylamido, imino, alkylimino,
arylimino, nitro, nitroso, sulfo, sulfonato, alkylsulfanyl,
arylsulfanyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl,
alkylaminosulfonyl, arylsulfonyl, boryl, borono, boronato,
phosphono, phosphonato, phosphinato, phospho, phosphino, and
mixtures thereof.
103. The article of manufacture of claim 101, wherein the at least
one olefin metathesis catalyst is a Group 8 transition metal
complex having the structure of formula (I) ##STR00053## wherein: M
is a Group 8 transition metal; L, L.sup.2, and L.sup.3 are
independently selected from 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 independently anionic ligands;
and R.sup.1 and R.sup.2 are independently selected from the group
consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl,
heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, and functional groups; wherein
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 the group
consisting of hydrocarbylene, substituted hydrocarbylene,
heteroatom-containing hydrocarbylene, and 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, 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 X1, 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.
Description
RELATED APPLICATIONS
[0001] This application is a Continuation of U.S. application Ser.
No. 14/125,837, filed Jul. 17, 2014; which is a national stage
application of PCT/US2012/042850, filed Jun. 17, 2012; which claims
the benefit of U.S. Provisional Patent Application No. 61/498,528,
filed Jun. 17, 2011, and U.S. Provisional Patent Application No.
61/654,744, filed Jun. 1, 2012, and the contents of which are
incorporated herein by reference in its entirety.
TECHNICAL FIELD
[0002] The present invention relates to methods and compositions
for improving the adhesion of olefin metathesis compositions to
substrate materials, and for catalyzing and controlling olefin
metathesis reactions. More particularly, the invention relates to
methods and compositions for improving the adhesion of ring opening
metathesis polymerization (ROMP) compositions to substrate
materials, and for catalyzing and controlling ROMP reactions and
the manufacture of polymer 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 catalysis, organic
synthesis, and 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] Polymers generated by ROMP are particularly well-suited for
casting of molded parts and infusion of resin-glass and resin-wood
composites, as non-limiting examples. According to one method
process, the cyclic olefin monomer is blended with appropriate
additives and fillers, and then mixed with an olefin metathesis
catalyst. The initial resin mixture is typically a low-viscosity
liquid, allowing for a wide range of resin infusion and casting
techniques. As the polymerization proceeds, the resin first "gels"
(increases in viscosity such that it no longer flows freely) and
then "cures" as the resin reaches peak monomer conversion. The
kinetics of the rate of gel and cure of olefin metathesis
polymerizations depend on monomer, catalyst, and temperature.
[0007] When manufacturing articles using olefin metathesis
polymerization, any pouring or infusion of catalyzed resin must be
complete before the resin viscosity increases to the point that the
resin no longer flows to fill the mold under the manufacturing
conditions. Pouring or infusion of highly viscous (pre-gelled) or
gelled resin may lead to inclusion of trapped air, or produce other
defects or conditions that decrease the mechanical properties or
visual appearance of the manufactured part. It would, therefore, be
desirable to control the gel formation process, in particular to
delay the onset of viscosity increase and the onset of the resin
gel and cure states, through the use of a gel modification agent.
Once the pour or infusion is complete, it would be further
advantageous for the onset of polymerization to begin within a
reasonable time after the mold is filled, and to proceed at a
desirable rate of cure.
[0008] The time during which the liquid monomer/catalyst mixture
can be worked after the monomer and catalyst is mixed is called the
"pot life" of the polymerization reaction mixture. The ability to
control the "pot life" becomes even more important for the molding
of large parts and to achieve defect-free infusion of porous
materials. It would be particularly useful to be able to control
the gel formation process, especially the onset of the gel state,
of catalyzed ROMP reactions when such large parts are to be
produced, or when defects arising from viscosity build-up are to be
reduced or eliminated.
[0009] Certain limited types of gel modification agents for olefin
metathesis polymerizations have been disclosed. For example, U.S.
Pat. No. 5,939,504 discloses the use of phosphines, pyridines, and
other Lewis bases as gel modifiers. While useful, the effect of
such gel modifiers in ROMP reactions can be difficult to control,
particularly where relatively small changes in the onset of
polymerization are desired. For example, while the addition of
small amounts of tributylphosphine, a commercially attractive
additive because of its low cost, may produce no noticeable change
in pot life, adding a slightly greater amount may overshoot the
desired effect by creating a significantly longer delay in the
onset of polymerization than desired. From a practical perspective,
the inability to finely control the gel formation process makes
these gel modifiers less useful in the manufacture of articles of
large or varying dimensions. Certain gel modifiers, such as
phosphines, also oxidize quite quickly in resin thereby decreasing
the ability of the modifier to extend the pot life. Resin
compositions relying on phosphine compounds for gel modification,
therefore, cannot be stored for any appreciable length of time
without reformulation with fresh gel modification additive.
[0010] Although acting as activators in some systems (e.g., U.S.
Pat. Nos. 4,380,617 and 4,049,616), active oxygen containing
compounds, including hydroperoxides, are generally considered to
have a negative impact on metathesis catalyst performance. Olefins
intended for use in metathesis reactions are often chemically
treated (e.g., U.S. Pat. No. 5,378,783) or pre-treated with an
adsorbent such as alumina or zeolites (e.g., U.S. Pat. Nos.
7,700,698; 4,943,397; and 4,584,425) to reduce the concentration of
oxygen-containing impurities such as hydroperoxides. For example,
U.S. Pat. No. 4,584,425 shows that hydroperoxide compounds have a
significant negative impact on the ROMP of DCPD with a two part
tungsten metathesis catalyst and U.S. Pat. No. 7,576,227 teaches
that it is advantageous to remove hydroperoxides and other catalyst
poisons to improve cross metathesis turnover number when using
ruthenium alkylidene catalysts.
[0011] Hydroperoxide additives have been suggested as
post-polymerization radical crosslinking initiators for ROMP
polymers (e.g., U.S. Pat. Nos. 7,025,851 and 7,476,716). However,
U.S. Pat. No. 5,728,785 specifically shows that ROMP of
dicyclopentadiene fails in the presence of 1 wt. % (relative to
dicyclopentadiene) of tert-butyl hydroperoxide, a level typically
useful to effect post-polymerization cross-linking. Others teach
that additives used in ROMP formulations should not contain
hydroperoxide functionalities, so as to avoid adverse interactions
with metathesis catalysts (e.g., U.S. Pat. Nos. 6,323,296 and
6,890,650, the disclosures of which are incorporated herein by
reference).
[0012] Despite the advances achieved in the art, particularly in
the properties of olefin metathesis polymers and their associated
applications, a continuing need therefore exists for further
improvement in a number of areas, including the adhesion of olefin
metathesis compositions, in particular, ROMP compositions, to
substrate materials, especially the wide variety of existing
substrate materials that have been used with traditional resin
systems, and the use of certain gel-modifiers to control the gel
formation process of polymerizing ROMP compositions.
SUMMARY OF THE INVENTION
[0013] The invention is directed to addressing one or more of the
aforementioned concerns and relates to the use of an adhesion
promoter 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, and to the use of a hydroperoxide gel modifier
in a ROMP composition to provide useful improvements in the ability
to control a ROMP reaction. More particularly, the inventors have
discovered that addition of an adhesion promoter 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. Alternatively,
a substrate material may be pre-treated with an adhesion promoter
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. In addition, the inventors have discovered that addition of
a hydroperoxide to the reaction mixture of a ROMP composition
allows for superior control over the resin gel and cure formation
process, without adversely affecting the mechanical properties of
the polymerized ROMP material. Furthermore, the gel modification
effect of hydroperoxides is remarkably stable in resin compared to
other gel modification agents known in the art.
[0014] In one embodiment, the invention provides a method for
improving the adhesion of an olefin metathesis reaction, for
example, a ROMP reaction, of a cyclic olefin catalyzed by an olefin
metathesis catalyst (e.g., a cyclic olefin metathesis catalyst) to
a substrate material, in which an adhesion promoter is combined
with a cyclic olefin, an olefin metathesis catalyst (e.g., a cyclic
olefin metathesis catalyst), and a substrate material thereby
forming a resin composition with improved mechanical properties. In
another embodiment, the invention provides a method for improving
the adhesion of an olefin metathesis reaction, for example, a ROMP
reaction, of a cyclic olefin catalyzed by an olefin metathesis
catalyst (e.g., a cyclic olefin metathesis catalyst) to a substrate
material, such as, for example, a glass substrate material, in
which an adhesion promoter is combined with a cyclic olefin, an
olefin metathesis catalyst (e.g., a cyclic olefin metathesis
catalyst), and a substrate material, such as, for example, a glass
substrate material, thereby forming a resin substrate composite
material with improved properties. The invention is further
directed to a ROMP composition of a cyclic olefin, which may be
functionalized or unfunctionalized and may be substituted or
unsubstituted, a cyclic olefin metathesis catalyst, a hydroperoxide
gel modifier, and an adhesion promoter. The inventive ROMP
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 adhesion promoter according
to the invention, discussed infra, is generally comprised of a
compound containing at least two isocyanate groups. An optionally
metathesis active compound containing at least one heteroatom may
be present in the ROMP composition. The resin composition is 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, and substrate material.
The resin composition 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, and the optional added substrate material and/or
in contact with the substrate material.
[0015] 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,
and a substrate material, such as, for example, a glass substrate
material. In general, the adhesion promoter comprises a compound
with at least two isocyanate groups. The adhesion promoter 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. The adhesion promoter may also
be a mixture of compounds, wherein each compound contains at least
two isocyanates. In another embodiment, the adhesion promoter
contains at least two isocyanates and contains an olefin metathesis
active group. In another embodiment, the adhesion promoter contains
at least two isocyanates and does not contain an olefin metathesis
active group. In a further embodiment, the adhesion promoter may
also contain an optional compound comprising a
heteroatom-containing functional group and a metathesis active
olefin.
[0016] The addition of the adhesion promoter of 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, as compared to a resin
composition that is the same with the exception that the adhesion
promoter of the invention is not included.
[0017] In another embodiment, the invention provides a method for
modifying the onset of a ROMP reaction of a cyclic olefin catalyzed
by a cyclic olefin metathesis catalyst, in which a hydroperoxide
gel modifier is combined with a cyclic olefin and a cyclic olefin
metathesis catalyst, thereby forming a ROMP composition. The ROMP
composition is then subjected to conditions effective to promote a
ROMP reaction of the cyclic olefin in the presence of the cyclic
olefin metathesis catalyst and the added hydroperoxide gel
modifier.
[0018] The invention is further directed to a ROMP composition of a
cyclic olefin, which may be functionalized or unfunctionalized and
may be substituted or unsubstituted, a cyclic olefin metathesis
catalyst, and a hydroperoxide gel modifier. The invention is also
directed to a composition comprising a cyclic olefin, which may be
functionalized or unfunctionalized and may be substituted or
unsubstituted, a cyclic olefin metathesis catalyst, a hydroperoxide
gel modifier, and an adhesion promoter of the invention.
[0019] In general, the hydroperoxide gel modifier is added in an
amount effective to increase the gel time of a ROMP reaction of the
cyclic olefin catalyzed by the cyclic olefin metathesis catalyst in
the presence of the added hydroperoxide compared to a ROMP reaction
of the same cyclic olefin catalyzed by the same cyclic olefin
metathesis catalyst in the absence of the added hydroperoxide.
[0020] While the invention is of particular benefit for
ring-opening metathesis polymerization (ROMP) reactions, it may
also find use in combination with other metathesis reactions, such
as a ring-opening cross metathesis reaction, a cross metathesis
reaction, a self-metathesis reaction, an ethenolysis reaction, an
alkenolysis reaction, or an acyclic diene metathesis polymerization
reaction, as well as combinations of such metathesis reactions.
[0021] 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
[0022] FIG. 1 depicts the effect of cumyl hydroperoxide (CHP) on
exotherm time as described in the Examples.
[0023] FIG. 2 depicts the viscosity profile for ROMP of
CHP-modified DCPD resin as described in the Examples.
DETAILED DESCRIPTION OF THE DISCLOSURE
Terminology and Definitions
[0024] Unless otherwise indicated, the invention is not limited to
specific reactants, substituents, catalysts, 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.
[0025] 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.
[0026] 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.
[0027] 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:
[0028] 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.
[0029] The term "alkylene" as used herein refers to a difunctional
linear, branched, or cyclic alkyl group, where "alkyl" is as
defined above.
[0030] 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.
[0031] The term "alkenylene" as used herein refers to a
difunctional linear, branched, or cyclic alkenyl group, where
"alkenyl" is as defined above.
[0032] 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.
[0033] 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.
[0034] 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.
[0035] 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.
[0036] 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, for example,
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.
[0037] The term "acyl" refers to substituents having the formula
--(CO)-alkyl, --(CO)-aryl, or --(CO)-aralkyl, and the term
"acyloxy" refers to substituents having the formula --O(CO)-alkyl,
--O(CO)-aryl, or --O(CO)-aralkyl, wherein "alkyl," "aryl," and
"aralkyl" are as defined above. Additionally, the term "acyl" also
refers to substituents having the formula --(CO)-alkaryl,
--(CO)-alkenyl, or --(CO)-alkynyl and the term "acyloxy" also
refers to substituents having the formula --O(CO)-alkaryl,
--O(CO)-alkenyl, or --O(CO)-alkynyl wherein "alkaryl", "alkenyl,"
and "alkynyl" are as defined above.
[0038] 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.
[0039] The terms "halo" and "halogen" are used in the conventional
sense to refer to a chloro, bromo, fluoro, or iodo substituent.
[0040] "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, 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 hydrocarbylene moieties, respectively.
[0041] 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 alkoxyaryl,
alkylsulfanyl-substituted alkyl, N-alkylated amino alkyl, and the
like. Examples of heteroaryl substituents include pyrrolyl,
pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl,
imidazolyl, 1,2,4-triazolyl, tetrazolyl, etc., and examples of
heteroatom-containing alicyclic groups are pyrrolidino, morpholino,
piperazino, piperidino, etc.
[0042] 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--(C.sub.5-C.sub.24 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--(C.sub.5-C.sub.24 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), 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=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=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=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 is 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).
Additional functional groups referred to herein as "Fn", include
without limitation, isocyanate (--N.dbd.C.dbd.O), and
thioisocyanate (--N.dbd.C.dbd.S).
[0043] 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.
[0044] In addition, the aforementioned functional groups may, if a
particular group permits, be further substituted with one or more
additional functional groups or with one or more hydrocarbyl
moieties such as those specifically mentioned above. Analogously,
the above-mentioned hydrocarbyl moieties may be further substituted
with one or more functional groups or additional hydrocarbyl
moieties as noted above.
[0045] "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.
[0046] 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 into 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.
[0047] In reference to the ROMP reaction of a cyclic olefin
catalyzed by the cyclic olefin metathesis catalyst, the term "onset
of a ROMP reaction" generally refers to the initial rapid increase
in the viscosity of the resin composition that occurs during
polymerization just prior to gelation. The progress of an olefin
metathesis polymerization can be monitored by measuring the
increase in viscosity as the reaction proceeds from the monomer to
the gelled state.
[0048] The progress of an exothermic olefin metathesis
polymerization may also be conveniently monitored by measuring the
temperature increase as the metathesis reaction proceeds from the
monomer to the cured state. In the context of the present
invention, and as described in the examples herein, the term "time
to exotherm" (or "exotherm time") is defined as the last measured
time point after which the temperature of a metathesis catalyzed
resin composition increases by more than 1.degree. C./second. As
shown in FIG. 1, the initial increase in the exotherm profile is
distinct allowing for a precise measurement of the exotherm onset,
the exotherm time, and the exotherm peak temperature. The exotherm
peak temperature is the maximum temperature the resin reaches
during the polymerization and is related to the completeness of the
polymerization reaction. Lowered peak temperatures can be an
indication of incomplete polymerization. In general, measurement of
the exotherm profile is convenient and provides an understanding of
the cure behavior and when the cured state is achieved.
[0049] The terms "pot life" and "gel time" are generally used
interchangeably. Various techniques and equipment useful for
determining gel time are known in the art and may be utilized in
the present invention. For example, the gel behavior, including the
gel time and pot life, may be determined using a viscometer, as
described in the examples, or by other suitable techniques. In many
cases, it is convenient and sufficient to estimate the gel time by
qualitative observation of properties such as pourability or
elasticity. Such techniques must necessarily allow for an increase
in the gel time to be determined, such that, in the context of the
present invention, the difference in gel time can be determined
between ROMP compositions containing added hydroperoxide and ROMP
compositions that do not contain added hydroperoxide. The skilled
artisan will appreciate that measurement of the actual gel time may
depend on the equipment and techniques utilized, as well the type
of composition being evaluated. However, in the context of the
present invention, a determination of the relative increase in gel
time achieved through the addition of hydroperoxide to a ROMP
composition should not be affected by the particular technique or
equipment utilized to determine the gel time.
[0050] The skilled artisan will also appreciate that the "working
time" (or "workable pot life") may vary for different ROMP
compositions and, for a particular ROMP composition, may also
depend on the application or equipment utilized. Typically, the
working time is greater than the time to onset of the
polymerization (e.g., when the viscosity begins to rise rapidly),
but less than the exotherm time.
Adhesion Promoter
[0051] One aspect of this invention is directed to adhesion
promoters generally comprising a compound containing at least two
isocyanate groups (such as, for example, methylene diphenyl
diisocyanate and hexamethylene diisocyanate). In one embodiment,
the adhesion promoter is a diisocyanate, triisocyanate, or
polyisocyanate (i.e., containing four or more isocyanate groups).
In a further embodiment, the adhesion promoter is 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.
[0052] In general, the adhesion promoter 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.
[0053] In one embodiment the adhesion promoter is 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, cycloctyl, 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).
[0054] In another embodiment, the adhesion promoter is 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, xylene, naphthyl, biphenyl,
diphenylether, benzophenone, and the like. Preferred aromatic
diisocyanates include toluene diisocyanates, tetramethylxylene
diisocyanate (TMXDI), and methylene diphenyl diisocyanate (MDI),
which may comprise any mixture of its three isomers, 2,2'-MDI,
2,4'-MDI, and 4,4'-MDI.
[0055] In another embodiment, the adhesion promoter is 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.
[0056] In yet another embodiment, the adhesion promoter is a trimer
of alkyl diisocyanates and aryl diisocyanates. In its simplest
form, any combination of polyisocyanate compounds may be trimerized
to form an isocyanurate ring containing isocyanate functional
groups. Trimers of alkyl diisocyanate and aryl diisocyanates may
also be referred to as isocyanurates of alkyl diisocyanate or aryl
diisocyanate. Preferred alkyl diisocyanate and aryl diisocyanate
trimers include, but are not limited to, hexamethylene diisocyanate
trimer (HDIt), isophorone diisocyanate trimer, toluene diisocyanate
trimer, tetramethylxylene diisocyanate trimer, methylene diphenyl
diisocyanate trimers, and the like. More preferred adhesion
promoters are toluene diisocyanates, tetramethylxylene diisocyanate
(TMXDI), and methylene diphenyl diisocyanate (MDI) including any
mixture of its three isomers 2,2'-MDI, 2,4'-MDI and 4,4'-MDI;
liquid MDI; solid MDI; hexamethylenediisocyanatetrimer (HDIt);
hexamethylenediisocyanate (HDI); isophorone diisocyanate (IPDI),
4,4'methylene bis(cyclohexyl isocyanate) (H12MDI); polymeric MDI
(PM200); MDI prepolymer (Lupranate.RTM. 5080); liquid carbodiimide
modified 4,4'-MDI (Lupranate.RTM. MM103); liquid MDI
(Lupranate.RTM. MI); liquid MDI (Mondur.RTM. ML). 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); hexamethylenediisocyanate
(HDI); isophorone diisocyanate (IPDI), 4,4'methylene bis(cyclohexyl
isocyanate) (H12MDI); polymeric MDI (PM200); MDI prepolymer
(Lupranate.RTM. 5080); liquid carbodiimide modified 4,4'-MDI
(Lupranate.RTM. MM103); liquid MDI (Lupranate.RTM. MI); liquid MDI
(Mondur.RTM. ML).
[0057] In further embodiments, the adhesion promoter may include an
optional compound with a heteroatom-containing functional group and
a metathesis active olefin. The compound containing a
heteroatom-containing functional group and a metathesis-active
olefin reacts with an isocyanate group and may provide the olefin
metathesis composite with improved mechanical properties. The
compound containing a heteroatom-containing functional group and a
metathesis-active olefin typically contains between 2 and 20
carbons with oxygen, nitrogen, sulfur, phosphorus, or silicon
functional groups. Preferred compounds containing a
heteroatom-containing functional group and a metathesis-active
olefin typically contain between 5 and 10 carbons with hydroxyl,
amine, thiol, phosphorus-containing functional groups, or silane
functional groups. Phosphorous-containing functional groups
include, for example, alkyl and aryl-substituted phosphonato,
phosphoryl, phosphanyl, and phosphino compounds. More preferred
compounds containing a heteroatom-containing functional group and a
metathesis-active olefin derived from norbornenes, oxanorbornenes,
cyclooctenes, and cyclooctadienes, which typically contain between
7 and 10 carbons with hydroxyl, amine, thiol, phosphorus-containing
functional groups, or silane functional groups. Further preferred
compounds containing a heteroatom-containing functional group and a
metathesis-active olefin include, but are not limited to,
5-norbornene-2-methanol (NB-MeOH); 2-hydroxyethyl
bicyclo[2.2.1]hept-2-ene-5-carboxylate (HENB); and allyl
alcohol.
[0058] Any concentration of adhesion promoter which improves the
mechanical properties of the olefin composite is sufficient for the
invention. In general, suitable amounts of adhesion promoter range
from 0.001-50 phr, particularly, from 0.05-10 phr, more
particularly, 0.1-10 phr, or, even more particularly, 0.5-4.0
phr.
[0059] In one embodiment, the adhesion promoter is contacted with a
cyclic olefin, an olefin metathesis catalyst, and a substrate
material, such as, for example, a glass substrate material, thereby
forming a resin composition, for example, a ROMP composition. The
resin composition is then subjected to conditions effective to
promote an olefin metathesis reaction. In a further embodiment, the
adhesion promoter may be applied to or contacted with the substrate
surface, such as, for example, a glass substrate, to functionalize
the surface prior to application of the resin composition. In a
further embodiment, the adhesion promoter is combined with a resin
composition comprising a cyclic olefin, the resin composition is
combined with an olefin metathesis catalyst, and the resulting
resin composition is applied to the substrate material, such as,
for example, a glass substrate.
[0060] In an additional embodiment, the adhesion promoter is
contacted with a cyclic olefin, an olefin metathesis catalyst, a
hydroperoxide gel modifier, and a substrate material thereby
forming a resin composition, for example, a ROMP composition. The
resin composition is then subjected to conditions effective to
promote an olefin metathesis reaction. In a further embodiment, the
adhesion promoter may be applied to or contacted with the substrate
surface to functionalize the surface prior to application of the
resin composition. In a further embodiment, the adhesion promoter
is combined with a resin composition comprising a cyclic olefin and
a hydroperoxide gel modifier, the resin composition is combined
with an olefin metathesis catalyst, and the resulting resin
composition is applied to the substrate material.
Substrate Surfaces
[0061] The invention is generally suitable for use with any
substrate material in which the addition of the adhesion promoter
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 is not included. The invention is directed to the use of
any substrate material in which the surfaces of such materials are
capable of reacting with the adhesion promoters of the invention
having at least two isocyanate groups. The 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 promoters to be
effective. The 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.
Method for Modifying Gel Formation
[0062] In another aspect, the invention provides a method for
modifying the onset of a ROMP reaction of a cyclic olefin catalyzed
by a cyclic olefin metathesis catalyst, in which a hydroperoxide
gel modifier is combined with a cyclic olefin and a cyclic olefin
metathesis catalyst, thereby forming a ROMP composition. The ROMP
composition is then subjected to conditions effective to promote a
ROMP reaction of the cyclic olefin in the presence of the cyclic
olefin metathesis catalyst and the added hydroperoxide gel
modifier.
[0063] The addition of an olefin metathesis catalyst to an olefinic
composition can, under appropriate conditions, initiate a
polymerization reaction, thereby forming a catalyzed resin. The
period of time during which the catalyzed resin has sufficiently
low viscosity such that the resin will flow for the manufacturing
process is known as the pot life. As the polymerization reaction
progresses, the viscosity of the resin increases such that the
resin is no longer able to flow freely. This is known as the gel
state. After the resin has achieved a gel state, the polymerization
reaction continues until no further monomer is consumed under the
reaction conditions. This is known as the cured state. In some
embodiments, the polymerization may be exothermic, driving the
polymerization to the cured state. The progress of an olefin
metathesis polymerization is commonly monitored by measuring the
increase in viscosity from the monomer to the gelled state, or by
monitoring the temperature increase of an exothermic polymerization
from the monomer to the cured state.
[0064] The onset of the gel state can be varied by many factors,
including the chemical nature of the monomer, type of olefin
metathesis catalyst, catalyst concentration, reaction temperature
and the effect of various additives. It is often useful to be able
to delay the onset of the gel state and to increase the gel time in
a controlled fashion to tailor the polymerization process to the
desired application or reaction conditions. Use of gel-modification
additives allows the pot life of the catalyzed resin to be extended
such that the resin remains fluid during the pour, cast, injection,
or infusion into the mold. Gel-modification additives must offer
controlled changes in the viscosity profile and time to exotherm
such that the resin polymerizes efficiently once the mold is
filled, to minimize mold cycle time. Ideally controlling the amount
of gel modification agent allows control of the gel time over
several hours. Furthermore, it is important the gel-modifying agent
does not adversely affect the mechanical properties of the cured
resin.
[0065] Applicants have discovered that the use of
hydroperoxide-containing compounds allows the onset of the resin
gel and cure states in olefin metathesis polymerizations to be
delayed in a controlled manner. Although in general the
hydroperoxide may be any organic hydroperoxide that is effective to
delay the onset of the gel state, the hydroperoxide is typically an
alkyl, for example, C.sub.2-C.sub.24 alkyl, aryl, for example,
C.sub.5-C.sub.24 aryl, aralkyl, or alkaryl, for example,
C.sub.6-C.sub.24 alkaryl, hydroperoxide, especially secondary or
tertiary aliphatic or aromatic hydroperoxides. More specific
hydroperoxides suitable for use include tert-butyl hydroperoxide,
tert-amyl hydroperoxide, cumene hydroperoxide, diisopropyl benzene
hydroperoxide, (2,5-dihydroperoxy)-2,5-dimethylhexane, cyclohexyl
hydroperoxide, triphenylmethyl hydroperoxide, pinane hydroperoxide
(e.g., Glidox.RTM. 500; LyondellBasell), and paramenthane
hydroperoxide (e.g., Glidox.RTM. 300; LyondellBasell). More
preferably, the hydroperoxides suitable for use include tert-butyl
hydroperoxide and cumene hydroperoxide. Gel-modification additives
may be added to the reaction mixture in the absence of solvent, or
as organic or aqueous solutions. A single hydroperoxide compound
may be used as the gel-modification additive, or a combination of
two or more different hydroperoxide compounds may be used.
[0066] The hydroperoxide compounds can generally be added to the
reaction mixture at any point prior to the onset of the gel state.
Conveniently, an appropriate amount of hydroperoxide gel modifier
may be added to the resin during the formulation step at which time
any other additives can be included prior to coming into contact
with catalyst. Unlike other gel-modification additives known in the
art, hydroperoxides may be added to a stock solution of resin and
have a usable shelf life of many weeks or months while
substantially maintaining the gel-modification activity.
Alternatively, the hydroperoxide compound can be added directly to
the catalyst and/or a catalyst carrier and delivered to the resin
during the catalyzation step. In another embodiment, the
hydroperoxide may be added to the catalyzed resin mixture after
addition of the catalyst.
[0067] The invention includes all concentrations of hydroperoxide
which delay the onset of the gel-state of a particular metathesis
polymerization. Advantageously, the use of hydroperoxides gel
modifiers has been found to substantially maintain the properties
of the cured polymer including peak exotherm temperature and
mechanical properties. While not necessarily limited, the
hydroperoxide concentration is advantageously between 0.01 and 1000
equivalents with respect to catalyst. In other embodiments the
hydroperoxide concentration may be between 0.1 and 20 equivalents
with respect to catalyst. Generally, higher concentrations of
hydroperoxide will lead to longer pot life. Additionally, in other
embodiments the hydroperoxide concentration may be between 0.05 and
100 equivalents with respect to catalyst. Additionally, in other
embodiments the hydroperoxide concentration may be between 0.1 and
50 equivalents with respect to catalyst.
[0068] Modification of highly active polymerizations (due to higher
resin temperatures, highly active metathesis catalyst, or other
factors) typically requires addition of higher concentrations of
hydroperoxide compounds. However, if the concentration of
gel-modification agent is too high for a given catalyst or the
reaction conditions, the polymerization may be incomplete, and the
resin may fail to cure properly. This could result in lower
exotherm temperatures or reduced mechanical properties.
[0069] The use of hydroperoxide allows for the time to the onset of
the gel state to be controlled based on the concentration of added
hydroperoxide gel modifier. In general, the gel time (e.g., as
tracked by the time of the exotherm) can be controllably delayed by
about 2 minutes or up to about 12 hours. In more specific aspects,
the gel time (or time to exotherm) may be delayed for about 10
minutes up to about 6 hours, or, even more particularly, from about
20 minutes up to about 2 hours. The time to the onset of the gel
state is impacted by the choice of olefin, catalyst,
olefin/catalyst ratio and temperature among other factors. The
desired time to the onset of the gel state is frequently dependent
on the manufacturing type conditions. Under some conditions,
delaying the onset of the gel state by 10-60 minutes, so the resin
can be poured without trapped air or other defects, is typically
sufficient. In other applications, such as the vacuum assisted
resin transfer molding of large parts, delaying the onset of the
gel state by 6-12 hours may be desirable.
Cyclic Olefin
[0070] In addition to the adhesion promoter and/or hydroperoxide
compound, described hereinabove, resin compositions disclosed
herein include 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, optionally functionalized,
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 comonomer 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.
[0071] In general, the cyclic olefin may be represented by the
structure of formula (A)
##STR00001##
wherein J and R.sup.A are as follows:
[0072] R.sup.A is selected 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 aryl sulfanyl,
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, 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.A 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.A
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. Additionally, functional groups
("Fn") may be thiocyanato, isocyanate, or thioisocyanate.
[0073] 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.
[0074] Mono-unsaturated cyclic olefin reactants 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.A is as defined above,
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
other of the R.sup.B1, R.sup.B2, R.sup.B3, R.sup.B4, R.sup.B5, and
R.sup.B6 moieties to provide a bicyclic or polycyclic olefin, and
the linkage may include heteroatoms or functional groups, e.g., the
linkage may include an ether, ester, thioether, amino, alkylamino,
imino, or anhydride moiety.
[0075] 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-methylsulfanyl-cyclopentene, 3-methylcyclohexene,
1-methylcyclooctene, 1,5-dimethylcyclooctene, etc.
[0076] 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.A is as defined above, 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,
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.
[0077] Bicyclic and polycyclic olefinic reactants encompassed by
structure (A) may be generally represented by the structure (D)
##STR00004##
wherein 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, lower alkenylene,
generally substituted or unsubstituted methyl or ethyl, or
heteroatom, generally oxygen, sulfur, or nitrogen optionally
substituted by lower alkyl or lower alkylene, R.sup.A is as defined
above, and R.sup.D1, R.sup.D2, R.sup.D3, and R.sup.D4 are as
defined for R.sup.B1 through R.sup.B6. Preferred olefinic reactants
within this group are in the norbornene and oxanorbornenes
families, having the structure (E) and (F), respectively
##STR00005##
wherein R.sup.A and T are as defined above, R.sup.E1, R.sup.E2,
R.sup.E3, and R.sup.E6 have the same definitions as R.sup.B1
through R.sup.B6, and R.sup.E4 and R.sup.E5 are defined as for
R.sup.E2 and R.sup.E3, respectively. Additionally, any of the
R.sup.E1, R.sup.E2, R.sup.E3, R.sup.E4, R.sup.E5, and R.sup.E6
moieties can be linked to any other of the R.sup.E1, R.sup.E2,
R.sup.E3, R.sup.E4, R.sup.E5, R.sup.E6 moieties to provide a
bicyclic or polycyclic olefin, 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.
[0078] Examples of bicyclic and polycyclic olefinic reactants thus
include, without limitation, 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-ethoxycarbony-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, and the like.
Additional examples of bicyclic and polycyclic olefins include,
without limitation, 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.
[0079] 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 cyclooctene, cyclododecene, and
(c,t,t)-1,5,9-cyclododecatriene.
[0080] 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, and 5-ethylidene-2-norbornene.
[0081] 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
2-hydroxymethyl-5-norbornene,
2-[(2-hydroxyethyl)carboxylate]-5-norbornene, cydecanol,
5-n-hexyl-2-norbornene, 5-n-butyl-2-norbornene.
[0082] Cyclic olefins incorporating any combination of the
abovementioned features (i.e., heteroatoms, substituents, multiple
olefins, multiple rings) are suitable for the invention disclosed
herein.
[0083] The cyclic olefins useful in the invention 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.
[0084] 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.
[0085] 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.
[0086] Further preferred cyclic olefins encompassed by structure
(D) that are in the norbornene family may be generally represented
by the structure (G):
##STR00006##
wherein R.sup.A and T are as defined above, R.sup.F1, R.sup.F2,
R.sup.F3, R.sup.F4, R.sup.F5, R.sup.F6, R.sup.F7, and R.sup.F8 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.F5,
R.sup.F6 and one of R.sup.F7, R.sup.F8 is not present. Furthermore,
any of the R.sup.F5, R.sup.F6, R.sup.F7, and R.sup.F8 moieties can
be linked to any of the other R.sup.F5, R.sup.F6, R.sup.F7, and
R.sup.F8 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, alkyl amino,
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, functional groups (Fn), heteroatom-containing
hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and
--(Z*).sub.n-Fn where n is zero or 1, Z*, and Fn are as defined
above.
[0087] More preferred cyclic olefins possessing at least one
norbornene moiety have the structure (H)
##STR00007##
wherein, R.sup.G1, R.sup.G2, R.sup.G3, and R.sup.G4 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.G1, R.sup.G2 and one of R.sup.G3, R.sup.G4
is not present. Furthermore any of the R.sup.G1, R.sup.G2,
R.sup.G3, and R.sup.G4 moieties can be linked to any of the other
R.sup.G1, R.sup.G2, R.sup.G3, and R.sup.G4 moieties to provide a
substituted or unsubstituted alicyclic group containing 4 to 30
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,
functional groups (Fn), heteroatom-containing hydrocarbyl,
substituted heteroatom-containing hydrocarbyl, and --(Z*).sub.n-Fn
where n is zero or 1, Z*, and Fn are as defined above.
[0088] 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:
##STR00008##
wherein R.sup.G1 to R.sup.G4 are as defined above.
[0089] 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:
##STR00009##
wherein g is an integer from 0 to 5, and R.sup.G1 to R.sup.G4 are
as defined above.
[0090] 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 is Scheme 3:
##STR00010##
wherein g is an integer from 0 to 5, R.sup.G1 and R.sup.G4 are as
defined above.
[0091] 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-ethoxycarbony-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 Catalyst
[0092] The olefin metathesis catalyst complex according to the
invention is preferably a Group 8 transition metal complex having
the structure of formula (I)
##STR00011##
in which:
[0093] M is a Group 8 transition metal;
[0094] L.sup.1, L.sup.2, and L.sup.3 are neutral electron donor
ligands;
[0095] n is 0 or 1, such that L.sup.3 may or may not be
present;
[0096] m is 0, 1, or 2;
[0097] k is 0 or 1;
[0098] X.sup.1 and X.sup.2 are anionic ligands; and
[0099] 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,
[0100] 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.
[0101] 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.
[0102] Preferred catalysts contain Ru or Os as the Group 8
transition metal, with Ru particularly preferred.
[0103] 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.
[0104] 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 and m are as
described above, 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.
[0105] 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, amine, amide, imine, sulfoxide, carboxyl, nitrosyl,
pyridine, substituted pyridine, imidazole, substituted imidazole,
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, 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 (PnBu.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), triisobutylphosphine (P-i-Bu.sub.3),
trioctylphosphine (POct.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 are independently selected from
phosphbicycloalkane (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.
[0106] X.sup.1 and X.sup.2 are anionic ligands, and may be the same
or different, or are linked together to form a cyclic group,
typically although not necessarily a five- to eight-membered ring.
In preferred embodiments, X.sup.1 and X.sup.2 are each
independently hydrogen, halide, or one of the following groups:
C.sub.1-C.sub.20 alkyl, C.sub.5-C.sub.24 aryl, C.sub.1-C.sub.20
alkoxy, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.20 alkoxycarbonyl,
C.sub.6-C.sub.24 aryloxycarbonyl, C.sub.2-C.sub.24 acyl,
C.sub.2-C.sub.24 acyloxy, C.sub.1-C.sub.20 alkylsulfonato,
C.sub.5-C.sub.24 arylsulfonato, C.sub.1-C.sub.20 alkylsulfanyl,
C.sub.5-C.sub.24 arylsulfanyl, C.sub.1-C.sub.20 alkylsulfinyl, 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.
Alternatively X.sup.1 and X.sup.2 are independently NO.sub.3,
--N.dbd.C.dbd.O, or --N.dbd.C.dbd.S.
[0107] 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.
[0108] 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 --C.dbd.C(CH.sub.3).sub.2.
[0109] 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.
[0110] 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)
##STR00012##
such that the complex may have the structure of formula (III)
##STR00013##
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;
[0111] 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;
[0112] 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
[0113] 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. Also, L.sup.2 and L.sup.3 may be taken together to
form a single bidentate electron-donating heterocyclic ligand.
Furthermore, R.sup.1 and R.sup.2 may be taken together to form a
indenylidene moiety. Moreover, X.sup.1, X.sup.2, L.sup.2, L.sup.3,
X, and Y is further coordinated to boron or to a carboxylate.
[0114] 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.
[0115] 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)
##STR00014##
wherein R.sup.3 and R.sup.4 are defined 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.
[0116] 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 is diisopropylphenyl and
Mes is 2,4,6-trimethylphenyl:
##STR00015##
[0117] Additional examples of NHC ligands and acyclic
diaminocarbene ligands suitable as L.sup.1 thus include, but are
not limited to the following:
##STR00016##
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.
[0118] Additional examples of 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 disclosures of
which are incorporated herein by reference.
[0119] 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.
[0120] When M is ruthenium, then, the preferred complexes have the
structure of formula (V)
##STR00017##
[0121] In a more preferred embodiment, Q is a two-atom linkage
having the structure --CR.sup.11R.sup.12--CR.sup.13R.sup.14-- or
--CR.sup.11.dbd.CR.sup.13--, preferably
--CR.sup.11R.sup.12--CR.sup.13R.sup.14--, wherein R.sup.11,
R.sup.12, R.sup.13, and R.sup.14 are independently selected from
hydrogen, hydrocarbyl, substituted hydrocarbyl,
heteroatom-containing hydrocarbyl, substituted
heteroatom-containing hydrocarbyl, and functional groups. Examples
of functional groups here include 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, L.sup.2 may be
L.sup.2.sub.(k), wherein k is zero or 1. 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.
[0122] 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).
[0123] 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.
[0124] 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.
[0125] 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.
The nitrogen-containing heterocycles may be optionally substituted
on a non-coordinating heteroatom with a non-hydrogen
substituent.
[0126] 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 thianthrene.
[0127] 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.
[0128] 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.
[0129] 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.
[0130] In general, any substituents present on L.sup.2 and/or
L.sup.3 are selected from halo, C.sub.1-C.sub.20 alkyl, substituted
C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 heteroalkyl, substituted
C.sub.1-C.sub.20 heteroalkyl, C.sub.5-C.sub.24 aryl, substituted
C.sub.5-C.sub.24 aryl, C.sub.5-C.sub.24 heteroaryl, substituted
C.sub.5-C.sub.24 heteroaryl, C.sub.6-C.sub.24 alkaryl, substituted
C.sub.6-C.sub.24 alkaryl, C.sub.6-C.sub.24 heteroalkaryl,
substituted C.sub.6-C.sub.24 heteroalkaryl, C.sub.6-C.sub.24
aralkyl, substituted C.sub.6-C.sub.24 aralkyl, C.sub.6-C.sub.24
heteroaralkyl, substituted C.sub.6-C.sub.24 heteroaralkyl, and
functional groups, with suitable functional groups including,
without limitation, C.sub.1-C.sub.20 alkoxy, C.sub.5-C.sub.24
aryloxy, C.sub.2-C.sub.20 alkylcarbonyl, C.sub.6-C.sub.24
arylcarbonyl, C.sub.2-C.sub.20 alkylcarbonyloxy, C.sub.6-C.sub.24
arylcarbonyloxy, C.sub.2-C.sub.20 alkoxycarbonyl, C.sub.6-C.sub.24
aryloxycarbonyl, halocarbonyl, C.sub.2-C.sub.20 alkylcarbonato,
C.sub.6-C.sub.24 arylcarbonato, carboxy, carboxylato, carbamoyl,
mono-(C.sub.1-C.sub.20 alkyl)-substituted carbamoyl,
di-(C.sub.1-C.sub.20 alkyl)-substituted carbamoyl,
di-N--(C.sub.1-C.sub.20 alkyl), N--(C.sub.5-C.sub.24
aryl)-substituted carbamoyl, mono-(C.sub.5-C.sub.24
aryl)-substituted carbamoyl, di-(C.sub.6-C.sub.24 aryl)-substituted
carbamoyl, thiocarbamoyl, mono-(C.sub.1-C.sub.20 alkyl)-substituted
thiocarbamoyl, di-(C.sub.1-C.sub.20 alkyl)-substituted
thiocarbamoyl, di-N--(C.sub.1-C.sub.20 alkyl)-N--(C.sub.6-C.sub.24
aryl)-substituted thiocarbamoyl, mono-(C.sub.6-C.sub.24
aryl)-substituted thiocarbamoyl, di-(C.sub.6-C.sub.24
aryl)-substituted thiocarbamoyl, carbamido, formyl, thioformyl,
amino, mono-(C.sub.1-C.sub.20 alkyl)-substituted amino,
di-(C.sub.1-C.sub.20 alkyl)-substituted amino,
mono-(C.sub.5-C.sub.24 aryl)-substituted amino,
di-(C.sub.5-C.sub.24 aryl)-substituted amino,
di-N--(C.sub.1-C.sub.20 alkyl),N--(C.sub.5-C.sub.24
aryl)-substituted amino, C.sub.2-C.sub.20 alkylamido,
C.sub.6-C.sub.24 arylamido, imino, C.sub.1-C.sub.20 alkylimino,
C.sub.5-C.sub.24 arylimino, nitro, and nitroso. In addition, two
adjacent substituents may be taken together to form a ring,
generally a five- or six-membered alicyclic or aryl ring,
optionally containing 1 to 3 heteroatoms and 1 to 3 substituents as
above.
[0131] 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.
[0132] 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.).
[0133] 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)
##STR00018##
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.
[0134] 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.10carboxylate, C.sub.2-C.sub.10 alkoxycarbonyl,
C.sub.1-C.sub.10alkoxy, 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.
[0135] 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)
##STR00019##
wherein,
[0136] M is a Group 8 transition metal, particularly Ru or Os, or,
more particularly, Ru;
[0137] X.sup.1, X.sup.2, and L.sup.1 are as previously defined
herein;
[0138] Y is a heteroatom selected from N, O, S, and P; preferably Y
is O or N;
[0139] R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are each,
independently, selected from the group consisting of hydrogen,
halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom
containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy,
aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio,
aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl,
alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl,
perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano,
isocyanate, hydroxyl, ester, ether, amine, imine, amide,
halogen-substituted amide, trifluoroamide, sulfide, disulfide,
sulfonate, carbamate, silane, siloxane, phosphine, phosphate,
borate, or -A-Fn, wherein "A" and Fn have been defined above; and
any combination of Y, Z, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 can
be linked to form one or more cyclic groups;
[0140] 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
[0141] 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, and R.sup.8 may
independently be thioisocyanate, cyanato, or thiocyanato.
Additionally, Z may independently be thioisocyanate, cyanato, or
thiocyanato.
[0142] In general, Grubbs-Hoveyda complexes useful in the invention
contain a chelating alkylidene moiety of the formula (VIII)
##STR00020##
[0143] wherein Y, n, Z, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are
as previously defined herein;
[0144] Y, Z, and R.sup.5 can optionally be linked to form a cyclic
structure; and
[0145] R.sup.9 and R.sup.10 are each, independently, selected from
hydrogen or a substituent group selected from alkyl, aryl, alkoxy,
aryloxy, C.sub.2-C.sub.20 alkoxycarbonyl, or C.sub.1-C.sub.20
trialkylsilyl, wherein each of the substituent groups is
substituted or unsubstituted; and wherein any combination or
combinations of Z, Y, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9,
and R.sup.10 may be linked to a support. The chelating alkylidene
moiety may be derived from a ligand precursor having the
formula
##STR00021##
[0146] Examples of complexes comprising Grubbs-Hoveyda ligands
suitable in the invention include:
##STR00022##
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).
[0147] 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:
##STR00023## ##STR00024##
[0148] 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:
##STR00025## ##STR00026##
[0149] 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:
[0150] 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);
[0151] 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);
[0152] 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
[0153] 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)
##STR00027##
wherein:
[0154] 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 groups of
catalysts;
[0155] r and s are independently zero or 1;
[0156] t is an integer in the range of zero to 5;
[0157] k is an integer in the range of zero to 1;
[0158] Y is any non-coordinating anion (e.g., a halide ion,
BF.sub.4--, etc.);
[0159] 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)--, and
--S(.dbd.O).sub.2--;
[0160] 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
[0161] 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. Additionally, Z.sup.1 and Z.sup.2 may also
be an optionally substituted and/or optionally
heteroatom-containing C.sub.1-C.sub.20 hydrocarbylene linkage.
[0162] 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):
##STR00028##
wherein M is a Group 8 transition metal, particularly ruthenium or
osmium, or more particularly ruthenium;
[0163] 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
[0164] R.sup.J1, R.sup.J2, R.sup.J3, R.sup.J4, R.sup.J5, and
R.sup.J6 are each independently selected from the group consisting
of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl,
heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy,
alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino,
alkylthio, aminosulfonyl, monoalkylaminosulfonyl,
dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl,
trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde,
nitrate, cyano, isocyanate, thioisocyanate, cyanato, thiocyanato,
hydroxyl, ester, ether, thioether, amine, alkylamine, imine, amide,
halogen-substituted amide, trifluoroamide, sulfide, disulfide,
sulfonate, carbamate, silane, siloxane, phosphine, phosphate,
borate, or -A-Fn, wherein "A" is a divalent hydrocarbon moiety
selected from alkylene and arylalkylene, wherein the alkyl portion
of the alkylene and arylalkylene groups can be linear or branched,
saturated or unsaturated, cyclic or acyclic, and substituted or
unsubstituted, wherein the aryl portion of the arylalkylene can be
substituted or unsubstituted, and wherein hetero atoms and/or
functional groups may be present in either the aryl or the alkyl
portions of the alkylene and arylalkylene groups, and Fn is a
functional group, or any one or more of the R.sup.J1, R.sup.J2,
R.sup.J3, R.sup.J4, R.sup.J5, and R.sup.J6 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, and R.sup.J6 may be
attached to a support.
[0165] Additionally, one preferred embodiment of the Group 8
transition metal complex of formula (XIII) is a Group 8 transition
metal complex of formula (XIV):
##STR00029##
wherein M, X.sup.1, X.sup.2, L.sup.1, L.sup.2, are as defined above
for Group 8 transition metal complex of formula XIII; and
[0166] 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 and R.sup.J16 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 XIII
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 and R.sup.J16
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 and R.sup.J16 may be
attached to a support.
[0167] Additionally, another preferred embodiment of the Group 8
transition metal complex of formula (XIII) is a Group 8 transition
metal complex of formula (XV):
##STR00030##
wherein M, X.sup.1, X.sup.2, L.sup.1, L.sup.2, are as defined above
for Group 8 transition metal complex of formula (XIII).
[0168] 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):
##STR00031##
wherein M is a Group 8 transition metal, particularly ruthenium or
osmium, or more particularly, ruthenium;
[0169] X.sup.1 and L.sup.1 are as defined for the first and second
groups of catalysts defined above;
[0170] Z is selected from the group consisting of oxygen, sulfur,
selenium, NR.sup.K11, PR.sup.K11 AsR.sup.K11, and SbR.sup.K11;
and
[0171] R.sup.K1, R.sup.K2, R.sup.K3, R.sup.K4, R.sup.K5, R.sup.K6,
R.sup.K7, R.sup.K8, R.sup.K9, R.sup.K10, and R.sup.K11 are each
independently selected from the group consisting of hydrogen,
halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom
containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy,
aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio,
aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl,
alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl,
perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano,
isocyanate, thioisocyanate, cyanato, thiocyanato, hydroxyl, ester,
ether, thioether, amine, alkylamine, imine, amide,
halogen-substituted amide, trifluoroamide, sulfide, disulfide,
sulfonate, carbamate, silane, siloxane, phosphine, phosphate,
borate, or -A-Fn, wherein "A" is a divalent hydrocarbon moiety
selected from alkylene and arylalkylene, wherein the alkyl portion
of the alkylene and arylalkylene groups can be linear or branched,
saturated or unsaturated, cyclic or acyclic, and substituted or
unsubstituted, wherein the aryl portion of the arylalkylene can be
substituted or unsubstituted, and wherein hetero atoms and/or
functional groups may be present in either the aryl or the alkyl
portions of the alkylene and arylalkylene groups, and Fn is a
functional group, or any one or more of the R.sup.K1, R.sup.K2,
R.sup.K3, R.sup.K4, R.sup.K5, R.sup.K6, R.sup.K7, R.sup.K8,
R.sup.K9, R.sup.K10, and R.sup.K11 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, R.sup.K5, R.sup.K6, R.sup.K7, R.sup.K8,
R.sup.K9, R.sup.K10, and R.sup.K11 may be attached to a
support.
[0172] 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):
##STR00032##
[0173] wherein M, X.sup.1, L.sup.1, Z, R.sup.K7, R.sup.K8,
R.sup.K9, R.sup.K10, and R.sup.K11 are as defined above for Group 8
transition metal complex of formula XVI; and
[0174] R.sup.K12, R.sup.K13, R.sup.K14, R.sup.K15, R.sup.K16,
R.sup.K17, R.sup.K18, R.sup.K19, R.sup.K20, and R.sup.K21are as
defined above for R.sup.K1, R.sup.K2, R.sup.K3, R.sup.K4, R.sup.K5,
and R.sup.K6 for Group 8 transition metal complex of formula XVI,
or any one or more of the R.sup.K7, R.sup.K8, R.sup.K9, R.sup.K10,
R.sup.K11, R.sup.K12, R.sup.K13, R.sup.K14, R.sup.K15, R.sup.K16,
R.sup.K17, R.sup.K18, R.sup.K19, R.sup.K20, and R.sup.K21 may be
linked together to form a cyclic group, or any one or more of the
R.sup.K7, R.sup.K8, R.sup.K9, R.sup.K10, R.sup.K11, R.sup.K12,
R.sup.K13, R.sup.K14, R.sup.K15, R.sup.K16, R.sup.K17, R.sup.K18,
R.sup.K19, R.sup.K20, and R.sup.K21 may be attached to a
support.
[0175] 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):
##STR00033##
wherein M, X.sup.1, L.sup.1, Z, R.sup.K7, R.sup.K8, R.sup.K9,
R.sup.K10, and R.sup.K11, are as defined above for Group 8
transition metal complex of formula XVI.
[0176] 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):
##STR00034##
wherein M is a Group 8 transition metal, particularly ruthenium or
osmium, or more particularly, ruthenium;
[0177] 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;
[0178] Z is selected from the group consisting of oxygen, sulfur,
selenium, NR.sup.V5, PR.sup.V5, AsR.sup.V5, and SbR.sup.V5;
[0179] m is 0, 1, or 2; and
[0180] R.sup.V1, R.sup.V2, R.sup.V3, R.sup.V4, and R.sup.V5 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.V1, R.sup.V2,
R.sup.V3, R.sup.V4, and R.sup.V5 may be linked together to form a
cyclic group, or any one or more of the R.sup.V1, R.sup.V2,
R.sup.V3, R.sup.V4, and R.sup.V5 may be attached to a support.
[0181] 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.1-7
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.1-20 alkyl, C.sub.3-C.sub.10
cycloalkyl, aryl, benzyl and C.sub.2-7 alkenyl; and silicon
compounds represented by the formula
SiR.sup.Y6R.sup.Y7R.sup.Y8R.sup.Y9 wherein each of R.sup.Y6,
R.sup.Y7, R.sup.Y8, R.sup.Y9 is independently selected from the
group consisting of hydrogen, halogen, C.sub.1-20 alkyl, halo,
C.sub.1-7 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,
naphthalenesulfonic 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.
[0182] 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. U.S. 2007/0043188); and Ser. No. 11/465,651
(Publication No. U.S. 2008/0293905 Corrected Publication); and
European Pat. Nos. EP1757613B land EP1577282B1.
[0183] 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:
##STR00035## ##STR00036## ##STR00037## ##STR00038## ##STR00039##
##STR00040## ##STR00041## ##STR00042##
[0184] Additional non-limiting examples of catalysts that may be
used to prepare supported complexes and in the reactions disclosed
herein include the following,
##STR00043##
[0185] In the foregoing molecular structures and formulae, Ph
represents phenyl, Cy represents cyclohexyl, Me represents methyl,
Bu represents n-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, MiPP represents 2-isopropylphenyl.
Additionally, t-Bu represents tert-butyl, and Cp represents
cyclopentyl.
[0186] 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), and ruthenium (II)
dichloro (phenylvinylidene) bis(tricyclohexylphosphine) (C835);
ruthenium (II) dichloro (tricyclohexylphosphine)
(o-isopropoxyphenylmethylene) (C601), and ruthenium (II)
(1,3-bis-(2,4,6,-trimethylphenyl)-2-imidazolidinylidene) dichloro
(phenylmethylene) bis-(3-bromopyridine) (C884)).
[0187] 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:
##STR00044##
[0188] Additional, non-limiting examples of catalysts that may be
used to prepare supported complexes and in the reactions disclosed
herein include the following
##STR00045##
[0189] 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., filed Apr. 16, 2002, for "Group 8 Transition Metal Carbene
Complexes as Enantioselective Olefin Metathesis Catalysts,"
International Patent Publication No. WO 02/079208, and U.S. Pat.
No. 6,613,910 to Grubbs et al., filed Apr. 2, 2002, for "One-Pot
Synthesis of Group 8 Transition Metal Carbene Complexes Useful as
Olefin Metathesis Catalysts," the disclosures of each of which are
incorporated herein by reference. Preferred synthetic methods are
described in International Patent Publication No. WO 03/11455A1 to
Grubbs et al. for "Hexacoordinated Ruthenium or Osmium Metal
Carbene Metathesis Catalysts," published Feb. 13, 2003, the
disclosure of which is incorporated herein by reference.
[0190] Preferred olefin metathesis catalysts are Group 8 transition
metal complexes having the structure of formula (I) commonly called
"First Generation Grubbs" catalysts, formula (II) commonly called
"Second Generation Grubbs" catalysts, or formula (VII) commonly
called "Grubbs-Hoveyda" catalysts.
[0191] More preferred olefin metathesis catalyst has the structure
of formula (I)
##STR00046##
in which:
[0192] M is a Group 8 transition metal;
[0193] L.sup.1, L.sup.2, and L.sup.3 are neutral electron donor
ligands;
[0194] n is 0 or 1;
[0195] m is 0, 1, or 2;
[0196] k is 0 or 1;
[0197] X.sup.1 and X.sup.2 are anionic ligands; and
[0198] 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,
[0199] 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.
[0200] Most preferred olefin metathesis catalyst has the structure
of formula (I)
##STR00047##
in which:
[0201] M is ruthenium;
[0202] n is 0;
[0203] m is 0;
[0204] k is 1;
[0205] 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)-4,5-dihydroimidazol-2-ylidene,
1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene,
1,3-bis(2,6-di-isopropylphenyl)-4,5-dihydroimidazol-2-ylidene, and
1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene 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);
[0206] X.sup.1 and X.sup.2 are chloride; and
[0207] R.sup.1 is hydrogen and R.sup.2 is phenyl or
--C.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.
[0208] 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.
[0209] 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.
[0210] 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.
[0211] 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 reaction
medium as a solid, or as a suspension wherein the catalyst is
suspended in an appropriate liquid. 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. Additionally, the
catalyst may be added to the reaction medium or resin composition
as a solution. Additionally, when the catalyst is added to the
reaction medium or resin composition as a suspension, the catalyst
is suspended in an appropriate liquid, such as a dispersing carrier
such as mineral oil, paraffin oil, soybean oil,
triisopropylbenzene, 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 it does not act as a
low-boiling impurity in the olefin metathesis reaction.
[0212] 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.
[0213] When expressed as the molar ratio of monomer to catalyst,
the catalyst (the "monomer to catalyst ratio"), loading will
generally be present in an amount that ranges from a low of about
10,000,000:1, 1,000,000:1, or 200,00:1, to a high of about
100,000:1 66,667:1, 40,000:1, 20,000:1, 10,000:1, 5,000:1, or
1,000:1.
Cyclic Olefin (Resin) Compositions and Articles
[0214] Cyclic olefin resin, particularly ROMP, compositions
according to the invention, generally comprise one or more cyclic
olefins, an olefin metathesis catalyst, an adhesion promoter, and a
substrate material, such as, for example, a glass substrate
material; one or more cyclic olefins, an olefin metathesis
catalyst, an adhesion promoter, and a hydroperoxide gel modifier;
or one or more cyclic olefins, an olefin metathesis catalyst, and a
hydroperoxide gel modifier. In another embodiment, cyclic olefin
resin, particularly ROMP, compositions according to the invention,
generally comprise one or more cyclic olefins, an olefin metathesis
catalyst, an adhesion promoter, and a 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 the
adhesion promoter is present in an amount effective to increase the
adhesion of the ROMP composition to a substrate material when the
ROMP composition is subjected to metathesis catalysis conditions in
the presence of a substrate material. Additionally, cyclic olefin
resin compositions according to the invention may also comprise one
or more cyclic olefins and an adhesion promoter, where the resin
composition is combined with an olefin metathesis catalyst, and the
resulting resin composition is applied to a substrate, such as, for
example, a glass substrate. Additionally, cyclic olefin resin
compositions according to the invention may also comprise one or
more cyclic olefins and an adhesion promoter, where the resin
composition is combined with an olefin metathesis catalyst, and the
resulting resin composition is applied to a substrate, wherein the
substrate may be a functionalized substrate, such as, for example,
a heteroatom-functionalized substrate, such as, for example, an
amino-functionalized substrate. Furthermore, cyclic olefin resin
compositions according to the invention may also comprise one or
more cyclic olefins, an adhesion promoter, and a hydroperoxide gel
modifier, where the resin composition is combined with an olefin
metathesis catalyst, and the resulting resin composition is applied
to a substrate. In addition, cyclic olefin resin compositions
according to the invention may also comprise one or more cyclic
olefins and a hydroperoxide gel modifier, where the resin
composition is combined with an olefin metathesis catalyst, and the
resulting resin composition is applied to a substrate.
[0215] The amounts of the adhesion promoter in the resin
composition may vary over a wide range and may vary depending on
the manufacturing operation or the particular end-use application.
Generally, any level of adhesion promoter which produces a desired
increase in mechanical properties is of particular interest. When
formulated or combined with a resin composition, the concentration
of the adhesion promoter typically ranges from 0.05-10 phr, more
particularly, from 0.5-4.0 phr. In a preferred aspect of the
invention, increased mechanical properties may be obtained for
resin compositions comprising the adhesion promoter and substrate
materials, or resin compositions comprising the adhesion promoter
that are applied to substrate materials, compared to resin
compositions without the adhesion promoter. For example, the
inclusion of the adhesion promoter in resin compositions according
to the invention may provide an improvement in mechanical
properties, such as interlaminar shear strength (ILSS), of at least
about 10% compared to the same resin composition that does not
contain the adhesion promoter. Preferably, the use of the adhesion
promoter provides at least a 2% improvement in an adhesion property
(e.g., ILSS, as described in the examples), more particularly at
least a 5%, or 10%, or 15%, or 20%, or 30%, or 40%, or 50%, or 80%
improvement in the adhesion property compared to the adhesion
property value (e.g., ILSS) obtained for the same resin composition
that does not include the adhesion promoter. In particular aspects
of the invention, substrate materials may advantageously comprise
an aminosilane-treated substrate.
[0216] The amounts of hydroperoxide gel modifier 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 hydroperoxide gel modifier which delays the
onset of the gel-state of a particular metathesis polymerization is
of particular interest. When formulated or combined with a resin
composition, the concentration of the hydroperoxide gel modifier
typically ranges between 0.01 and 1000 equivalents with respect to
catalyst, such as, for example, between 0.05 and 100 equivalents
with respect to catalyst, such as, for example, between 0.1 and 50
equivalents with respect to catalyst, such as, for example, between
0.1 and 20 equivalents with respect to catalyst.
[0217] Resin compositions of the invention may be optionally
formulated with additives. 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. Suitable additives
include, but are not limited to, additional gel modifiers, hardness
modulators, antioxidants, stabilizers, fillers, binders,
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.
[0218] Resin compositions of the invention may be optionally
formulated without a crosslinker, for example, a crosslinker
selected from dialkyl peroxides, diacyl peroxides, and
peroxyacids.
[0219] Additionally, suitable impact modifiers or elastomers
include without limitation natural rubber, butyl rubber,
polyisoprene, polybutadiene, polyisobutylene, ethylene-propylene
copolymer, styrene-butadiene-styrene triblock rubber, random
styrene-butadiene rubber, styrene-isoprene-styrene triblock rubber,
styrene-ethylene/butylene-styrene copolymer,
styrene-ethylene/propylene-styrene copolymer,
ethylene-propylene-diene terpolymers, ethylene-vinyl acetate, and
nitrile rubbers. Preferred impact modifiers or elastomers are
polybutadiene Diene 55AC10 (Firestone), polybutadiene Diene 55AM5
(Firestone), EPDM Royalene 301T, EPDM Buna T9650 (Bayer),
styrene-ethylene/butylene-styrene copolymer Kraton G1651H, Polysar
Butyl 301 (Bayer), polybutadiene Taktene 710 (Bayer),
styrene-ethylene/butylene-styrene Kraton G1726M, Ethylene-Octene
Engage 8150 (DuPont-Dow), styrene-butadiene Kraton D 1184, 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.
[0220] Additionally, 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 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 53 and Permanax WSO;
2,2'-ethylidenebis(4,6-di-tert-butylphenol); 2,2'-methylenebi
s(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.
[0221] 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.RTM. trade name). Reinforcing materials containing surface
finishes, sizings, or coatings are particularly suitable for the
described invention including Ahlstrom glass roving (R338-2400),
Johns Manville glass roving (Star ROV.RTM.-086), Owens Corning
rovings (OCV 366-AG-207, R25H-X14-2400, SE1200-207, SE1500-2400,
SE2350-250), PPG glass rovings (Hybon.RTM. 2002, Hybon.RTM. 2026),
Toho Tenax.RTM. carbon fiber tow (HTR-40), and Zoltek carbon fiber
tow (Panex.RTM. 35). Furthermore, any fabrics prepared using
reinforcing materials containing surface finishes, sizings or
coatings are suitable for the invention. Advantageously, the
invention does not require the expensive process of removing of
surface finishes, sizings, or coatings from the reinforcing
materials. Additionally, glass fibers or fabrics may include
without limitation A-glass, E-glass or S-glass, S-2 glass, C-glass,
R-glass, ECR-glass, M-glass, D-glass, and quartz, and
silica/quartz. Preferred glass fiber reinforcements are those with
finishes formulated for use with epoxy, vinyl ester, and/or
polyurethane resins. When formulated for use with a combination of
these resin types, the reinforcements are sometimes described as
"multi-compatible." Such reinforcements are generally treated
during their manufacture with organosilane coupling agents
comprising vinyl, amino, glycidoxy, or methacryloxy functional
groups (or various combinations thereof) and are coated with a
finish to protect the fiber surface and facilitate handling and
processing (e.g., spooling and weaving). Finishes typically
comprise a mixture of chemical and polymeric compounds such as film
formers, surfactants, and lubricants. Especially preferred glass
reinforcements are those containing some amount of
amino-functionalized silane coupling agent. Especially preferred
finishes are those comprising and epoxy-based and/or
polyurethane-based film formers. Examples of preferred glass-fiber
reinforcements are those based on Hybon.RTM. 2026, 2002, and 2001
(PPG) multi-compatible rovings; Ahlstrom R338 epoxysilane-sized
rovings; StarRov.RTM. 086 (Johns Manville) soft silane sized
multi-compatible rovings; OCV.TM. 366, SE 1200, and R25H (Owens
Corning) multi-compatible rovings; OCV.TM. SE 1500 and 2350 (Owens
Corning) epoxy-compatible rovings; and Jushi Group multi-compatible
glass rovings (752 type, 396 type, 312 type, 386 type). Additional
suitable polymer fibers and fabrics may include without limitation
one or more of polyester, polyamide (for example, NYLON polamide
available from E.I. DuPont, aromatic polyamide (such as KEVLAR
aromatic polyamide available from E.I. DuPont, or P84 aromatic
polyamide available from Lenzing Aktiengesellschaft), polyimide
(for example KAPTON polyimide available from E.I. DuPont,
polyethylene (for example, DYNEEMA polyethylene from Toyobo Co.,
Ltd.). Additional suitable carbon fibers may include without
limitation AS2C, AS4, AS4C, AS4D, AS7, IM6, IM7, IM9, and PV42/850
from Hexcel Corporation; TORAYCA T300, T300J, T400H, T600S, T700S,
T700G, T800H, T800S, T1000G, M35J, M40J, M46J, M50J, M55J, M60J,
M30S, M30G and M40 from Toray Industries, Inc.; HTS12K/24K, G30-500
3k/6K/12K, G30-500 12K, G30-700 12K, G30-7000 24K F402, G40-800
24K, STS 24K, HTR 40 F22 24K 1550tex from Toho Tenax, Inc.; 34-700,
34-700WD, 34-600, 34-600WD, and 34-600 unsized from Grafil Inc.;
T-300, T-650/35, T-300C, and T-650/35C from Cytec Industries.
[0222] 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.
[0223] The invention is also directed to articles manufactured from
a resin composition comprising a cyclic olefin, an olefin
metathesis catalyst, such as a ROMP catalyst, the adhesion
promoter, and a substrate material, such as, for example, a glass
substrate material; a cyclic olefin, an olefin metathesis catalyst,
such as a ROMP catalyst, the adhesion promoter, and the
hydroperoxide gel modifier; and a cyclic olefin, an olefin
metathesis catalyst, such as a ROMP catalyst, and the hydroperoxide
gel modifier. 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).
[0224] Additionally, the invention is also directed to articles
manufactured from a resin composition comprising a cyclic olefin
and an adhesion promoter, 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.
[0225] Furthermore, the present invention also allows for the
molding 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, an industrial component, medical 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, a pylon, a pylon fairing, an acoustic panel, a trust
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, tower, 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 stiffener. 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 bed, 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, 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 of electric motors. 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.
[0226] 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.
[0227] 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.
[0228] 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.
[0229] 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).
[0230] 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.
[0231] The film former may also comprise polyolefins or
polyolefin-acrylic copolymers, polyvinylacetates, modified
polyvinylacetates, or polyolefin-acetate copolymers. Suitable
polyolefins include, but are not limited to, polyethylenes,
polypropylenes, polybutylenes, and copolymers thereof, and the
polyolefins may be oxidized, maleated, or otherwise treated for
effective film former use. Examples of suitable products include
emulsions produced by Michelman, including Michem.RTM. Emulsion
91735, Michem.RTM. Emulsion 35160, Michem.RTM. Emulsion 42540,
Michem.RTM. Emulsion 69230, Michem.RTM. Emulsion 34040M1,
Michem.RTM. Prime 4983R, and Michem.RTM. Prime 4982SC. Examples of
suitable products include emulsions produced by HB Fuller,
including PD 708H, PD 707, and PD 0166. Additional suitable
products include emulsions produced by Franklin International,
including Duracet.RTM. 637. Additional suitable products include
emulsions produced by Celanese, including Vinamul.RTM. 8823
(plasticized polyvinylacetate), Dur-O-Set.RTM. E-200
(ethylene-vinyl acetate copolymer), Dur-O-Set.RTM. TX840
(ethylene-vinyl acetate copolymer), and Resyn.RTM. 1971
(epoxy-modified polyvinylacetate).
[0232] 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.
[0233] 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.
[0234] 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.
[0235] 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.
[0236] 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.
[0237] 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.
[0238] 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.
[0239] 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.
[0240] 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.
[0241] 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.
[0242] 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.
EXPERIMENTAL
[0243] 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 C. and
pressure is at or near atmospheric.
[0244] 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 and
gel modification compositions of the invention and the methods for
their use.
EXAMPLES
Materials and Methods
[0245] 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.
[0246] 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 as
generally described in U.S. Pat. No. 4,899,005.
[0247] Solid MDI (4,4'-methylene diphenyl diisocyanate) was used as
received from Sigma Aldrich (98% purity). Liquid MDI (50/50 mixture
of 4,4'-MDI and 2,4'-MDI) was used as received from Bayer Material
Science (Mondur.RTM. ML). Hexamethylenediisocyanurate
(hexamethylenediisocyanatetrimer, HDIt, CAS#3779-63-3) was used as
received from Bayer Material Science (Desmodur.RTM. N3300A). HDI
(hexamethylenediisocyanate or diisocyanatohexane, CAS#822-06-0) was
used as received from Sigma Aldrich (98% purity), Acros Organics
(99+% purity), TCI America (98% purity), or Bayer Material Science
(Desmodur.RTM. H, 99.5% purity). Isophorone diisocyante (IPDI) was
used as received from Sigma Aldrich (98% purity).
Meta-tetramethylxylylene diisocyanate (TMXDI.RTM.) was used as
received from Cytec. H12MDI (4,4'-Methylenebis(cyclohexyl
isocyanate), was used as received from Sigma Aldrich (90% purity).
Polymeric MDI (PM200) was used as received from Yantai Wanhua
Polyurethane Company. Lupranate.RTM. 5080 (MDI prepolymer),
Lupranate.RTM. MI (liquid MDI), and Lupranate.RTM. MM103 (liquid
carbodiimide modified 4,4'-MDI) were used as received from BASF.
Additionally, 4-Benzylphenyl isocyanate (CAS#1823-37-6, purity 97%)
and 2-biphenylyl isocyanate (CAS#17337-13-2, purity 98%) were used
as received from Sigma Aldrich.
[0248] NB-MeOH (5-Norbornene-2-methanol, CAS#95-12-5) was used as
received from Sigma Aldrich or prepared by literature methods. HENB
(2-hydroxyethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate) was
prepared by literature methods. Allyl alcohol, 2-ethyl hexanol, and
1-octanol were used as received from Sigma Aldrich. DCPD-OH
(dicyclopentadiene alcohol) was used as received from Texmark.
[0249] 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), ruthenium (II) dichloro
(tricyclohexylphosphine) (o-isopropoxyphenylmethylene) (C601),
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(benzylide-
ne)(tri(n-butyl)phosphine) ruthenium (II) (C771), and
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylind-
enylidene)(tri(n-butyl)phosphine) ruthenium (II) (C871).
Ethanox.RTM. 4702 antioxidant (4,4'methylenebis
(2,6-di-tertiary-butylphenol), Albemarle Corporation) was used
where indicated.
[0250] 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. tert-Butyl hydroperoxide was used as received from Sigma
Aldrich (5.5M solution in decane). mCPBA (3-chloroperoxybenzoic
acid), benzoyl peroxide (97% purity), di-tert-butyl peroxide (98%
purity), and tri-n-butylphosphine (TNBP) were used as received from
Sigma Aldrich. Triphenyl phosphine (TPP) was used as received from
Arkema. Additionally, mineral oil used to prepare the catalyst
suspensions was Crystal Plus 70FG.
[0251] Glass rovings and fabrics were used as supplied by Ahlstrom
(R338-2400), Johns Manville (Star ROV.RTM.-086), Owens Corning (OCV
366-AG-207, R25H-X14-2400, SE1200-207, SE1500-2400, SE2350-250),
and PPG (Hybon.RTM. 2002, Hybon.RTM. 2026). Toho Tenax.RTM. HTR40
carbon fiber roving was used as received.
[0252] 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.
[0253] Roving wrap composites were prepared using a small-scale
variation of a hand layup technique. Glass roving was saturated
with catalyzed dicyclopentadiene resin and layered into a
1/4''.times.6'' bar mold under moderate tension. The bar mold was
compressed to achieve approximately 50% fiber volume at 1/8''
thickness, and held with C-clamps during the oven cure process.
Roving wrap composites were heated from room temperature to
120.degree. C. at 1.degree. C./min, and held at 120.degree. C. for
two hours.
[0254] Glass composite laminates were prepared using the VARTM
process. The laminate was constructed by cutting and arranging
plies of glass fabric on an aluminum tool to achieve approximately
50% fiber volume at 1/8'' thickness. A rigid plate was placed on
top of the ply stack to ensure that pressure was applied evenly
across the surface. Using braided tubing, an infusion inlet and
outlet vent were positioned appropriately near the glass fabric. A
sheet of vacuum bagging film and tacky tape was used to create an
air-tight cover on the glass and the tubing and evacuated to a
vacuum level of between 25 inches-Hg to 28 inches-Hg. A mixture of
resin and catalyst was degassed in vacuo for 15 minutes and then
back-filled with argon. The mixture was then infused in to the
glass fabric, driven by the pressure gradient between the ambient
pressure and the evacuated glass fabric assembly. After the
infusion was complete, the composite laminate was heated from room
temperature to 75.degree. C. at a heating rate of 1.degree. C./min,
and then the composite laminate was heated to 120.degree. C. and
held at that temperature for two hours.
[0255] Gel modifier ppm is defined as the grams of gel modifier per
million grams of resin. Corrections for gel modifier purity were
made. With regard to other formulation additives, PHR is defined as
the weight of the additive per hundred grams of base resin.
[0256] Viscosity profiles were measured on a Brookfield LVDVII
viscometer, and data was analyzed by Wingather V3.0-1 software.
Measurements were made with Spindle #1 set to 50 RPM on 400 g
samples equilibrated to 20-25.degree. C. Data points were logged at
two-second to two-minute intervals, depending on experimental
timescale. Temperatures were measured using J-type thermocouples,
sampling at five second intervals and collected by Omega 2.0 OM-CP
series data logging software.
[0257] The mechanical properties were measured using standard
techniques. All values reported are the average of 3 samples.
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. 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 has having ILSS values less than about 3000 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 3000 psi to
about 6000 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 6000 psi suggesting a higher degree of covalent
adhesion between the polymer matrix and fiber reinforcement. Heat
deflection temperature was measured according to ASTM D648 on
5''.times.1/2''.times.1/4'' samples. Flexural peak strength and
flexural modulus were tested according to ASTM D790 using
5''.times.1/2''.times.1/4'' samples. Izod pendulum impact
resistance was tested according to ASTM D526 using
2.5''.times.1/2''.times.1/4'' samples. All samples were stored and
tested at ambient room conditions.
Synthesis of HENB (2-hydroxyethyl
bicyclo[2.2.1]hept-2-ene-5-carboxylate)
[0258] 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 a condenser. The
3 L flask containing HEA and toluene was connected to the
condenser. The DCPD was heated to >160.degree. C. under an inert
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 (1004 g, quantitative
yield, approx. 98% purity).
Examples 1(a-1)-4(a-1)
Roving Composites Prepared with Isocyanate Adhesion Agents
[0259] Resin was prepared using the modified DCPD (containing
20-25% tricyclopentadiene), 20 ppm CHP, 2 phr Ethanox.RTM. 4702
antioxidant, and 2 phr of the appropriate isocyanate adhesion
promoter. The resin was catalyzed by the addition of C827 (monomer
to catalyst ratio 30,000:1) in a suspension of mineral oil. Roving
wrap composites based on glass roving (Examples 1(a-1) PPG2002;
Examples 2(a-1) PPG2026; Examples 3(a-1) Ahlstrom R338-2400;
Examples 4(a-1) Star ROV.RTM.-086) were saturated with the
catalyzed dicyclopentadiene resin and layered into a
1/4''.times.6'' bar mold under moderate tension. The bar mold was
compressed to achieve approximately 50% fiber volume at 1/8''
thickness, and held with C-clamps during the oven cure process.
Roving wrap composites were heated from room temperature to
120.degree. C. at 1.degree. C./min, and held at 120.degree. C. for
two hours. The ILSS of the resulting composites were measured
(Table 1). Samples without adhesion promoter (Examples 1a, 2a, 3a,
4a) all had poor mechanical properties. Generally, all the tested
adhesion promoters improved the mechanical properties of the
PPG2026 composites. Several adhesion promoters improved the
mechanical properties of all four composites testing: 4,4'-MDI (c),
the 4,4'-MDI/2,4'-MDI mixture (b), and hexamethylenediisocyanurate
(HDIt, d) (Table 1).
TABLE-US-00001 TABLE 1 ILSS for Roving Composites Prepared with
Isocyanate Adhesion Promoter ILSS (psi) 3 4 Ahlstrom Star Adhesion
1 2 R338- ROV .RTM.- Example Promoter PPG 2002 PPG2026 2400 086 a
None 1376 3574 1464 1347 b 4,4'-MDI/ 6760 7886 6313 6499 2,4'-MDI c
4,4'-MDI 7012 6890 6417 6279 d HDIt 5461 6714 5129 4933 e H12MDI
not tested 6931 not tested 1837 f HDI 2604 7007 3719 2837 g IPDI
not tested 6811 2730 2329 h TMXDI .RTM. not tested 5622 1888 1848 i
PM200 7124 7985 7318 7052 PolyMDI j Lupranate .RTM. 5075 7083 6105
4957 5080 k Lupranate .RTM. 6974 8683 7168 6484 MI l Lupranate
.RTM. 6822 7609 6948 6009 MM103 "Not tested" samples were damaged
during fabrication so ILSS could not be evaluated.
Examples 5(a-h)-8(a-h)
Roving Composites Prepared with Isocyanate Adhesion Agents and
HENB
[0260] Resin was prepared using the modified DCPD (containing
20-25% tricyclopentadiene), 20 ppm CHP, 2 phr Ethanox.RTM. 4702
antioxidant, 2 phr of the appropriate diisocyanate adhesion
promoter, and 2 phr of HENB. The resin was catalyzed by the
addition of C.sub.827 (monomer to catalyst ratio 30,000:1) in a
suspension of mineral oil. Roving wrap composites based on glass
rovings (Examples 5(a-h) PPG2002; Examples 6(a-h) PPG2026; Examples
7(a-h) Ahlstrom R338-2400; Examples 8(a-h) Star ROV.RTM.-086) were
prepared as described in Example 1. The ILSS of the resulting
composites were measured (Table 2). In most cases the addition of
HENB further improved the mechanical properties of the resulting
composites compared with those using the diisocyanate adhesion
promoter alone (1b-1h, 2b-2h, 3b-3h, and 4b-4h from Table 1). HENB
alone did not improve adhesion (5h-8h).
TABLE-US-00002 TABLE 2 ILSS for Roving Composites Prepared with
Isocyanate Adhesion Promoter and HENB ILSS (psi) 7 8 5 Ahlstrom
Star Adhesion PPG 6 R338- ROV .RTM.- Example Promoter 2002 PPG2026
2400 086 a 4,4'-MDI/ 7895 8052 8330 8093 2,4'-MDI b 4,4'-MDI 7334
6736 7596 7450 c HDIt 7489 7525 7848 7143 d H12MDI not tested 6153
not tested 2524 e HDI 6570 7307 7468 6966 f IPDI 4367 7002 4912
4376 g TMXDI .RTM. 2102 5809 3186 3160 h HENB 1047 2263 not tested
1269 with no adhesion promoter
Examples 10(a-f); 11(a-f)
Roving Composites Prepared with Isocyanate Adhesion Agents
[0261] Resin was prepared using the modified DCPD (containing
20-25% tricyclopentadiene), 20 ppm CHP, 2 phr Ethanox.RTM. 4702
antioxidant, and either 2 phr of 4,4'-MDI/2,4'-MDI (Examples
10(a-f)) or HDIt (examples 11(a-f)) diisocyanate adhesion promoter.
The resin was catalyzed by the addition of C827 (monomer to
catalyst ratio 30,000:1) in a suspension of mineral oil. Roving
wrap composites based on glass rovings were prepared as described
in Example 1. The ILSS of the resulting composites were measured
(Tables 3 and 4). 4,4'-MDI/2,4'-MDI and HDIt are effective adhesion
promoters for all rovings tested, which were indicated for use with
epoxy resins.
TABLE-US-00003 TABLE 3 ILSS for Glass Rovings Prepared with
4,4'-MDI/2,4'-MDI Example Glass Roving Adhesion promoter ILSS 1b
PPG 2002 4,4'-MDI/2,4'-MDI 6760 2b PPG 2026 4,4'-MDI/2,4'-MDI 7886
3b Ahlstrom 4,4'-MDI/2,4'-MDI 6313 R338-2400 4b Star ROV .RTM.-086
4,4'-MDI/2,4'-MDI 6499 10a OCV 366-AG-207 4,4'-MDI/2,4'-MDI 7462
10b OCV R25H-X14-2400 4,4'-MDI/2,4'-MDI 6004 10c OCV SE1200-207
4,4'-MDI/2,4'-MDI 7776 10d OCV SE1500-2400 4,4'-MDI/2,4'-MDI 8071
10e OCV SE2350-250 4,4'-MDI/2,4'-MDI 6611 10f OCV SE8380-113
4,4'-MDI/2,4'-MDI 2061
TABLE-US-00004 TABLE 4 ILSS for Glass Rovings Prepared with HDIt
Adhesion Example Glass Roving promoter ILSS 1d PPG 2002 HDIt 5461
2d PPG 2026 HDIt 6714 3d Ahlstrom HDIt 5129 R338-2400 4d Star ROV
.RTM.-086 HDIt 4933 11a OCV 366-AG-207 HDIt 5039 11b OCV
R25H-X14-2400 HDIt 5666 11c OCV SE1200-207 HDIt 4846 11d OCV
SE1500-2400 HDIt 4894 11e OCV SE2350-250 HDIt 5360 11f OCV
SE8380-113 HDIt 1711
Examples 12(a-g)-15(a-g)
Roving Composites Prepared with HDIt Adhesion Promoter and Various
Alcohols
[0262] Resin was prepared using the modified DCPD (containing
20-25% tricyclopentadiene), 20 ppm CHP, 2 phr Ethanox.RTM. 4702
antioxidant, 2 phr of HDIt adhesion promoter, and 2 phr of various
alcohols. The resin was catalyzed by the addition of C827 (monomer
to catalyst ratio 30,000:1) in a suspension of mineral oil. Roving
wrap composites based on glass rovings (Examples 12(a-g) PPG2002;
Examples 13(a-g) PPG2026; Examples 14(a-g) Ahlstrom R338-2400;
Examples 15(a-g) Star ROV.RTM.-086) were prepared as described in
Example 1. The ILSS of the resulting composites were measured
(Table 5).
TABLE-US-00005 TABLE 5 ILSS for Roving Composites prepared with
HDIt Adhesion promoter and Various Alcohols ILSS (psi) 14 15
Ahlstrom Star 12 13 R338- ROV .RTM.- Example Alcohol PPG 2002
PPG2026 2400 086 a None 5461 6714 5129 4933 b HENB 7489 7525 7848
7143 c NBMeOH 6882 7011 7244 6658 d Allyl alcohol 6487 4611 7344
6337 e DCPD-OH 2902 6715 4104 2741 f 2-ethyl 1630 4616 2000 1601
hexanol g 1-octanol 1543 3272 1663 1419
Examples 16(a-f)-19(a-f)
Composite Rovings with 1 phr Adhesion Promoter
[0263] Resin was prepared using DCPD (containing 20-25%
tricyclopentadiene), 20 ppm CHP, 2 phr Ethanox.RTM. 4702
antioxidant, 1 phr of the 4,4'-MDI/2,4'-MDI or HDIt adhesion
promoter, and 1 phr of optional alcohol compounds. The resin was
catalyzed by the addition of C827 (monomer to catalyst ratio
30,000:1) in a suspension of mineral oil. Roving wrap composites
based on glass rovings (Examples 16(a-f) PPG2002; Examples 17(a-f)
PPG2026; Examples 18(a-f) Ahlstrom R338-2400; Examples 19(a-f) Star
ROV.RTM.-086) were prepared as described in Example 1. The ILSS of
the resulting composites were measured (Table 6). At 1 phr,
4,4'-MDI/2,4'-MDI was an effective adhesion promoter, and the
addition of 1 phr HENB or NBMeOH improved the performance of the
adhesion promoter. HDIt improved the properties of the composite
significantly for PPG 2026 and Ahlstrom R338-2400 and slightly for
two rovings (PPG 2002 and Star-ROV-086). The addition of HENB and
NBMeOH improved the efficacy of the adhesion promoter (Table
6).
TABLE-US-00006 TABLE 6 ILSS for Composite Rovings with 1 phr
Adhesion Promoter ILSS (psi) 16 17 18 19 Adhesion PPG PPG Ahlstrom
Star Example Promoter Alcohol 2002 2026 R338-2400 ROV .RTM.-086 a
4,4'-MDI/ None 6760 6550 4912 5309 2,4'-MDI b 4,4'-MDI/ HENB 7560
7065 6798 7431 2,4'-MDI c 4,4'-MDI/ NBMeOH 7368 7089 6782 6857
2,4'-MDI d HDIt None 2767 6378 4687 2567 e HDIt HENB 6034 7030 6528
5546 f HDIt NBMeOH 5296 5585 6451 4514
Examples 20(a-k)-23(a-k)
Composite Rovings with Various Loadings of Adhesion Promoter and
HENB
[0264] Resin was prepared using the modified DCPD (containing
20-25% tricyclopentadiene), 20 ppm CHP, 2 phr Ethanox.RTM. 4702
antioxidant, 0.1, 0.5, or 2 phr of the MDI adhesion promoter
(4,4'-MDI/2,4'-MDI), and 0, 0.1, 0.5, 1, or 2 phr of HENB. The
resin was catalyzed by the addition of C827 (monomer to catalyst
ratio 30,000:1) in a suspension of mineral oil. Roving wrap
composites based on glass rovings (Examples 20(a-k) PPG2002;
Examples 21(a-k) PPG2026; Examples 22(a-k) Ahlstrom R338-2400;
Examples 23(a-k) Star ROV.RTM.-086) were prepared using a
small-scale variation of a hand layup technique. Glass roving was
saturated with catalyzed dicyclopentadiene resin and layered into a
1/4''.times.6'' bar mold under moderate tension. The bar mold was
compressed to achieve approximately 58% fiber volume at 1/8''
thickness, and held with C-clamps during the oven cure process.
Roving wrap composites were heated from room temperature to
120.degree. C. at 1.degree. C./min, and held at 120.degree. C. for
two hours. The ILSS of the resulting composites were measured
(Table 7).
TABLE-US-00007 TABLE 7 ILSS for Composite Rovings with Various
Adhesion Promoter and HENB Loadings phr Adhesion ILSS (psi)
Promoter 20 21 22 23 (4,4'-MDI/ phr PPG PPG Ahlstrom Star Example
2,4'-MDI) HENB 2002 2026 R338-2400 ROV .RTM.-086 a 0.1 0 1331 4556
1814 1370 b 0.1 0.1 1585 2452 3186 2232 c 0.1 2.0 2616 4476 4303
3245 d 0.5 0 3760 7086 3603 3205 e 0.5 0.5 5816 5523 6170 5087 f
0.5 2.0 6325 6755 6603 5969 g 2.0 0 6760 7886 6313 6499 h 2.0 0.1
7439 7561 7790 7466 i 2.0 0.5 7317 6948 7684 7692 j 2.0 1.0 7244
7487 7704 7392 k 2.0 2.0 7895 8052 8330 8093
Examples 24(a-d)-26(a-d)
VARTM with Adhesion Promoter and Commercial Fabrics
[0265] The modified DCPD (containing 20-25% tricyclopentadiene) was
formulated with 20 ppm CHP, 2 phr Ethanox.RTM. 4702 antioxidant, 2
phr 4,4'-MDI/2,4'-MDI, and with and without 2 phr HENB (24(a,b),
25(a,b), 26(a,b)). The resin was catalyzed by the addition of C827
(monomer to catalyst ratio 30,000:1) in a suspension of mineral
oil. VARTM samples were prepared using commercial unidirectional
fabrics including Vectorply ELR 2410 fabric (made from PPG 2026
roving), fabric based on Ahlstrom R338, and fabric based on OC
SE-1500. The composite laminates were cured for 120.degree. C. for
2 hours. The ILSS of the resulting composites were measured (Table
8). The modified DCPD (containing 20-25% tricyclopentadiene) was
formulated with 20 ppm CHP, 2 phr Ethanox.RTM. 4702 antioxidant,
and 2 phr 2-biphenylyl isocyanate (24 (c)) or 2 phr 4-benzylphenyl
isocyanate (24 (d)). The resin was catalyzed by the addition of
C827 (monomer to catalyst ratio 30,000:1) in a suspension of
mineral oil. VARTM samples were prepared using commercial
unidirectional fabric Vectorply ELR 2410 fabric (made from PPG 2026
roving). The ILSS of the resulting composites were measured (Table
8). The diisocyanate containing compositions (24(a,b), 25(a,b),
26(a,b)) showed superior adhesion, while the compositions
containing the monoisocyanates (24c, 24d) demonstrated poor
adhesion.
TABLE-US-00008 TABLE 8 ILSS for VARTM with Adhesion Promoter and
Commercial Fabrics ILSS (psi) 25 26 24 Ahlsrom OC SE PPG 2026 R338
1500 Example Adhesion promoter Fabric Fabric Fabric a
4,4'-MDI/2,4'-MDI 8452 8468 8538 b 4,4'-MDI/2,4'-MDI 8512 8429 8819
and HENB c 2-biphenylyl 3494 not tested not tested isocyanate d
4-benzylphenyl 3806 not tested not tested isocyanate
Example 27(a-c)
Unidirectional Composite Wraps with Carbon Fiber
[0266] Resin was prepared using the modified DCPD (containing
20-25% tricyclopentadiene), 20 ppm CHP, and 2 phr Ethanox.RTM. 4702
antioxidant. Samples with no adhesion promoter (a), 2 phr
4,4'-MDI/2,4'-MDI (b), and 2 phr 4,4'-MDI/2,4'-MDI and 2 phr HENB
(c) were prepared. The resin was catalyzed by the addition of C827
(monomer to catalyst ratio 30,000:1) in a suspension of mineral
oil. Carbon-fiber tow composites based on Toho Tenax.RTM. HTR40
were prepared as described in Example 1. The ILSS of the resulting
composites were measured (Table 9). The isocyanate adhesion
promoter is effective for carbon rovings.
TABLE-US-00009 TABLE 9 ILSS for Carbon Roving Composites Example
Adhesion promoter ILSS (psi) a None 1844 b 4,4'-MDI/2,4'-MDI 5399 c
4,4'-MDI/2,4'-MDI 7907 and HENB
Example 28(a-e)
VARTM with Adhesion Promoter and a Range of Catalysts
[0267] The modified DCPD (containing 20-25% tricyclopentadiene) was
formulated with 2 phr 4702 Ethanox.RTM., 2 phr 4,4'-MDI/2,4'-MDI,
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 45,000:1 as listed
in Table 10) in a suspension of mineral oil. VARTM samples were
prepared using commercial fabric Vectorply ELR 2410 (made from PPG
2026 roving). The ILSS of the resulting composites were measured
(Table 10). For a range of catalysts, the adhesion promoter
improves the physical properties of the composites when compared to
Example 2(a).
TABLE-US-00010 TABLE 10 ILSS for VARTM with MDI and Various
Catalysts Monomer to Example Catalyst Catalyst Ratio Inhibitor ILSS
(psi) a C771 30,000:1 none 8755 b C801 5,000:1 TPP (0.1 phr) 7104 c
C871 45,000:1 none 8168 d C601 5,000:1 none 4715 e C827 30,000:1
CHP (20 ppm) 8452
Example 29 (a-h)
VARTM with Adhesion Promoter and Carbon Fabric
[0268] Resin was prepared using the modified DCPD (containing
20-25% tricyclopentadiene), 20 ppm CHP, and 2 phr Ethanox.RTM. 4702
antioxidant. Samples with varying isocyanate adhesion promoter
compositions were prepared. The resin was catalyzed by the addition
of C827 (monomer to catalyst ratio 30,000:1) in a suspension of
mineral oil. VARTM samples were prepared using Zoltek UD500 carbon
fabric. The ILSS of the resulting composites were measured (Table
11).
TABLE-US-00011 TABLE 11 ILSS for Zoltek UD500 Carbon Fabric
Composites Example Adhesion promoter HENB ILSS (psi) a None None
1634 b 2phr 4,4'-MDI/2,4'- None 4945 MDI c 4phr 4,4'-MDI/2,4'- None
5615 MDI d None 2 phr 1563 e 2 phr 4,4'-MDI/2,4'- 2 phr 8664 MDI f
4phr 4,4'-MDI/2,4'- 2 phr 8807 MDI g 2 phr HDIt None 4639 h 2 phr
HDIt 2 phr 7156
Examples 30(a-f)-32(a-f)
Roving Composites Prepared with 4,4'-MDI/2,4'-MDI Adhesion Promoter
and Various Alcohols
[0269] Resin was prepared using the modified DCPD (containing
20-25% tricyclopentadiene), 20 ppm CHP, 2 phr Ethanox.RTM. 4702
antioxidant, 2 phr of 4,4'-MDI/2,4'-MDI adhesion promoter, and 2
phr of various alcohols. The resin was catalyzed by the addition of
C827 (monomer to catalyst ratio 30,000:1) in a suspension of
mineral oil. Roving wrap composites based on glass rovings
(Examples 30(a-f) PPG2002; Examples 31(a-f) PPG2026; Examples
32(a-f) Star ROV.RTM.-086) were prepared as described in Example 1.
The ILSS of the resulting composites were measured (Table 12).
TABLE-US-00012 TABLE 12 ILSS for Roving Composites prepared with
4,4'-MDI/2,4'- MDI Adhesion promoter and Various Alcohols ILSS
(psi) 32 Star 30 31 ROV .RTM.- Example Alcohol PPG 2002 PPG2026 086
a None 6760 7886 6499 b HENB 7093 7392 7460 c NBMeOH 5804 5603 6280
d Allyl alcohol 2407 2270 2454 e DCPD-OH 2736 4367 2698 f 1-octanol
1966 2244 1461
Example 33
Effect of Cumene Hydroperoxide on the Onset of the Gel State
[0270] A plastic 250 mL beaker was charged with 100 g of
dicyclopentadiene base resin (containing 20-25% tricyclopentadiene)
and 0-100 ppm cumene hydroperoxide (CHP) was added as a 1000 ppm
concentration stock solution in resin. The beaker was placed in an
oil bath, and a temperature probe was placed in the reaction
vessel. Once the sample was equilibrated to the test temperature
(30.degree. C.) the metathesis catalyst was added. Polymerizations
33a-33h were catalyzed by the addition of 9.6 mg of catalyst C827
dissolved in a mixture of 1 g of toluene and 2 g of mineral oil
(monomer to catalyst ratio 60,000:1). Polymerizations 33i-33m were
catalyzed by the addition 19.2 mg of catalyst C827 suspended in 2 g
of mineral oil (monomer to catalyst ratio 30,000:1). The
temperatures of the reaction mixtures were monitored over the
course of the polymerizations. The exotherm time is related to the
onset of polymerization. Peak exotherm temperature is related to
the completeness of the polymerization reaction. Lowered peak
temperatures are an indication of incomplete polymerization. The
exotherm times and peak temperatures for the unmodified and
modified polymerizations can be seen in Table 13. Increasing
concentrations of CHP in the resin resulted in increased time to
reach polymerization exotherm, with no significant drop in exotherm
peak temperature. At both catalyst concentrations, addition of CHP
effectively modifies the onset of polymerization, and the delay
time can be controlled over several hours by controlling the amount
of CHP added. FIG. 1 shows the temperature profiles of examples
33a-33c with 0, 2.5, and 5 ppm CHP. The gel-modification of the
invention is particularly useful, because it increases the workable
pot life of the catalyzed resin without otherwise necessarily
changing the overall temperature profile of the polymerization.
TABLE-US-00013 TABLE 13 Gel Modification by Cumene Hydroperoxide
(CHP) CHP Exotherm Peak concentration CHP:catalyst Exotherm
Temperature Example (ppm) molar ratio Time (min) (.degree. C.) 33a
0 0.00 11.4 183 33b 2.5 0.14 28.6 182 33c 5 0.28 43.3 180 33d 10
0.57 67.0 179 33e 25 1.42 121.9 184 33f 50 2.84 167.4 184 33g 75
4.26 179.2 182 33h 100 5.68 209.0 180 33i 0 0.00 8.5 199 33j 10
0.26 37.1 197 33k 20 0.52 67.1 196 33l 40 1.04 110.3 192 33m 50
1.30 137.7 191 33a-33h: monomer/C827 = 60,000:1 33i-33m:
monomer/C827 = 30,000:1
Example 34
Effect of Cumene Hydroperoxide (CHP) on DCPD Polymerization
Viscosity Profile
[0271] Dicyclopentadiene base resin (containing 20-25%
tricyclopentadiene) was filtered through activated alumina and
silica gel to remove any contaminants. A plastic 500 mL beaker was
charged with 400 g of the filtered resin as a control. Additional
plastic 500 mL beakers were charged with 400 g of the filtered
resin and 4, 25, or 100 ppm cumene hydroperoxide (CHP) was added as
a 1000 ppm concentration stock solution in resin. Each resin sample
was equilibrated at 23-25.degree. C., and catalyzed by addition of
9.6 mg of C827 suspended in 2 g of mineral oil. Viscosity profiles
are shown in FIG. 2, in which the cure profile of the filtered
control sample is shown along with the cure profiles of
CHP-modified resin compositions having CHP concentrations of 4, 25
and 100 ppm. The reaction modification of the invention is
particularly useful because it increases the workable pot life of
the catalyzed resin and allows for low viscosity characteristics to
be retained for a longer period of time.
Example 35
Mechanical Properties of Unmodified and Modified polyDCPD
Plaques
[0272] To evaluate mechanical properties of polydicyclopentadiene
(polyDCPD) formulations, 200 g of dicyclopentadiene base resin
(containing 20-25% tricyclopentadiene) was formulated with 2 PHR
Ethanox.RTM. 4702 antioxidant and 0-100 ppm cumene hydroperoxide,
equilibrated to 30.degree. C. and catalyzed by the addition of 19.2
mg of C827 suspended in 2 g of mineral oil. After mixing, the
catalyzed resin was poured into a 10.times.10.times.0.5'' glass and
aluminum mold and placed in a 40.degree. C. oven until exotherm
(Example 35a-d). After cure, the polyDCPD panels were cut into
samples for measurement of Heat Deflection Temperature (HDT, ASTM
D648), Izod Pendulum Impact Resistance (ASTM D526), and Flexural
properties (ASTM D790). As shown in Table 14, there is no
significant deviation in panel mechanical properties over a range
of hydroperoxide-to-catalyst ratios.
TABLE-US-00014 TABLE 14 Effect of hydroperoxide gel modification on
polyDCPD mechanical properties CHP concen- Izod Flex. Flex. Exam-
tration CHP CHP:catalyst HDT (ft- Peak Mod. ple (ppm) moles molar
ratio .degree. C. lb/in) (ksi) (ksi) 35a 0 0.00E+00 0.00 138.0 1.1
13.0 304 35b 20 2.63E-05 1.04 140.7 1.1 12.9 307 35c 50 6.57E-05
2.61 140.0 1.0 13.0 306 35d 100 1.31E-04 5.21 142.1 1.2 12.7
302
Example 36
Storage Stability of Phosphine Gel Modifier
[0273] A stock resin formulation was prepared by mixing
dicyclopentadiene base resin (containing 20-25% tricyclopentadiene)
with 2 PHR Ethanox.RTM. 4702 antioxidant and 0.5 PHR of a 0.15 wt %
solution of TNBP in