Adhesion promoter compositions for cyclic olefin resin compositions

Abstract

This invention relates to compositions and methods for improving the adhesion of resin compositions to substrate materials. More particularly, the invention relates to compositions and methods for improving the adhesion of ROMP compositions to substrate materials using an adhesion promoter composition, where the adhesion promoter composition comprises a pre-reacted mixture comprising at least one compound containing at least two isocyanate groups and at least one compound comprising a heteroatom-containing functional group and a metathesis active olefin, where the adhesion promoter composition is storage stable and/or possesses in-resin storage stability when added to a resin composition, particularly a cyclic olefin resin composition, such as a ROMP composition. The polymer products produced via ROMP reactions of the invention may be utilized for a wide range of materials and composite applications. The invention has utility in the fields of polymer and materials chemistry and manufacture.

1 . A resin composition, comprising:
 at least one cyclic olefin;   at least one olefin metathesis catalyst; and   at least one adhesion promoter composition, where the at least one adhesion promoter composition comprises a pre-reacted mixture of at least one compound containing at least two isocyanate groups and at least one compound comprising at least one heteroatom-containing functional group and at least one metathesis active olefin,   wherein the at least one compound comprising at least one heteroatom-containing functional group and at least one metathesis active olefin have the following structure:
   (O M )-(Q*) n -(X*)—H
 
 wherein O M , Q*, and X* are as follows: 
 O M  is a metathesis active olefin fragment selected from cyclic olefins and acyclic olefins, where the carbon-carbon double bond is not tetra-substituted; 
 Q* is an optional linker group selected from the group consisting of a hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene; 
 n=0 or 1; and 
 X* is oxygen, sulfur, or a heteroatom-containing fragment selected from the group consisting of N(R X ), P(R X ), OP(R X ), OP(R X )O, OP(OR X )O, P(═O)(R X ), OP(═O)(R X ), OP(═O)(R X )O, OP(═O)(OR X )O, Si(R X ) 2 , Si(R X ) 2 O, Si(OR X ) 2 O, and Si(R X )(OR X )O, wherein each R X  is, independent of one another, a hydrogen, an aryl, and a lower alkyl group, 
   wherein the mol ratio of the at least one compound comprising at least one heteroatom-containing functional group and at least one metathesis active olefin relative to the at least one compound containing at least two isocyanate groups ranges from 0.01:1 to 0.5:1.   
     
     
         2 . The resin composition of  claim 1 , wherein the at least one compound containing at least two isocyanate groups is selected from the group consisting of methylene diphenyl diisocyanate and hexamethylene diisocyanate and the at least one compound comprising at least one heteroatom containing functional group and at least one metathesis active olefin is selected from the group consisting of 2-hydroxyethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate (HENB), 2-hydroxyethyl acrylate (HEA), oleyl alcohol, and 9-decen-1-ol. 
     
     
         3 . The resin composition of  claim 2 , wherein the pre-reacted mixture of 2-hydroxyethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate (HENB) and methylene diphenyl diisocyanate comprises 
       
         
           
           
               
               
           
         
       
     
     
         4 . The resin composition of  claim 1 , wherein the adhesion promoter is present in an amount ranging from 0.001-50 phr. 
     
     
         5 . The resin composition of  claim 1 , wherein the at least one adhesion promoter composition is storage stable. 
     
     
         6 . The resin composition of  claim 1 , wherein the at least one adhesion promoter composition is in-resin storage stable. 
     
     
         7 . The resin composition of  claim 1 , further comprising:
 at least one substrate material.   
     
     
         8 . The resin composition of  claim 7 , wherein the substrate material is a glass substrate or a carbon substrate. 
     
     
         9 . The resin composition of  claim 1 , wherein the at least one olefin metathesis catalyst is a Group 8 transition metal complex having the structure of Formula (I): 
       
         
           
           
               
               
           
         
       
       wherein
 M is a Group 8 transition metal selected from ruthenium and osmium; 
 L 1 , L 2 , and L 3  are neutral electron donor ligands; 
 n is 0 or 1, such that L 3  may or may not be present; 
 m is 0, 1, or 2; 
 k is 0 or 1; 
 X 1  and X 2  are anionic ligands; and 
 R 1  and R 2  are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, 
 wherein any two or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2  can be taken together to form one or more cyclic groups. 
 
     
     
         10 . The resin composition of  claim 9 , wherein the at least one of 12, L 2 , and L 3  is an N-heterocyclic carbene ligand. 
     
     
         11 . The resin composition of  claim 10 , wherein the N-heterocyclic carbene ligand has the structure 
       
         
           
           
               
               
           
         
       
       wherein,
 Q is —CR 11 R 12 —CR 13 R 14 — or —CR 11 ═CR 13 —, wherein R 11 , R 12 , R 13 , and R 14  are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, or wherein any two of R 11 , R 12 , R 13 , and R 14  may be linked together to form a substituted or unsubstituted, saturated or unsaturated ring; and 
 R 3  and R 4  are unsubstituted phenyl or phenyl substituted with one or more substituents selected from C 1 -C 20  alkyl, substituted C 1 -C 20  alkyl, C 1 -C 20  heteroalkyl, substituted C 1 -C 20  heteroalkyl, C 5 -C 24  aryl, substituted C 5 -C 24  aryl, C 5 -C 24  heteroaryl, C 6 -C 24  aralkyl, C 6 -C 24  alkaryl, or halide. 
 
     
     
         12 . The resin composition of  claim 1 , wherein the at least one olefin metathesis catalyst is a Group 8 transition metal complex having the structure of Formula (VII), wherein: 
       
         
           
           
               
               
           
         
         M is ruthenium; 
         X 1  and X 2  are anionic ligands; 
         L 1  is a neutral electron donor ligand; 
         Y is a heteroatom selected from N, O, S, and P; 
         R 5 , R 6 , R 7 , and R 8  are each, independently, selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, halogen-substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, and borate; 
         n is 0, 1, or 2, such that n is 1 for the divalent heteroatoms O or S, and n is 2 for the trivalent heteroatoms N or P; and 
         Z is a group selected from hydrogen, alkyl, aryl, functionalized alkyl, functionalized aryl where the functional group(s) may independently be one or more or the following: alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, or borate; methyl, isopropyl, sec-butyl, t-butyl, neopentyl, benzyl, phenyl and trimethylsilyl. 
       
     
     
         13 . The resin composition of  claim 1 , wherein the at least one olefin metathesis catalyst has the structure of Formula (I): 
       
         
           
           
               
               
           
         
       
       wherein:
 M is ruthenium; 
 n is 0; 
 m is 0; 
 k is 1; 
 L 1  and L 2  are trisubstituted phosphines independently selected from the group consisting of tri-n-butylphosphine (Pn-Bu 3 ), tricyclopentylphosphine (PCp 3 ), tricyclohexylphosphine (PCy 3 ), triisopropylphosphine (P-i-Pr 3 ), triphenylphosphine (PPh 3 ), methyldiphenylphosphine (PMePh 2 ), dimethylphenylphosphine (PMe 2 Ph), and diethylphenylphosphine (PEt 2 Ph); or L 1  is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene and L 2  is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu 3 ), tricyclopentylphosphine (PCp 3 ), tricyclohexylphosphine (PCy 3 ), triisopropylphosphine (P-i-Pr 3 ), triphenylphosphine (PPh 3 ), methyldiphenylphosphine (PMePh 2 ), dimethylphenylphosphine (PMe 2 Ph), and diethylphenylphosphine (PEt 2 Ph); 
 L 3  is not present; 
 X 1  and X 2  are chloride; and 
 R 1  is hydrogen and R 2  is phenyl or —CH═C(CH 3 ) 2  or thienyl; or R 1  and R 7  are taken together to form phenylindenylidene. 
 
     
     
         14 . The resin composition of  claim 1 , wherein the at least one olefin metathesis catalyst has the structure of Formula (I): 
       
         
           
           
               
               
           
         
       
       wherein:
 M is ruthenium; 
 n is 0; 
 m is 0; 
 k is 1; 
 L 1  is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene and 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; 
 L 2  is a trisubstituted phosphine independently selected from the group consisting of tri-n-butylphosphine (Pn-Bus); tricyclopentylphosphine (PCp 3 ), tricyclohexylphosphine (PCy 3 ), triisopropylphosphine (P-i-Pr 3 ), triphenylphosphine (PPh 3 ), methyldiphenylphosphine (PMePh 2 ), dimethylphenylphosphine (PMe 2 Ph), and diethylphenylphosphine (PEt 2 Ph); 
 L 3  is not present; 
 X 1  and X 2  are chloride; and 
 R 1  is hydrogen and R 2  is phenyl or —CH═C(CH 3 ) 2  or thienyl; or R 1  and R 2  are taken together to form phenylindenylidene. 
 
     
     
         15 . The resin composition of  claim 1 , wherein the cyclic olefin is selected from the group consisting of dicyclopentadiene; tricyclopentadiene; cyclopentadiene tetramer; cyclopentadiene pentamer; dicyclohexadiene; norbornene; 5-methyl-2-norbornene; 5-ethyl-2-norbornene; 5-isobutyl-2-norbornene; 5,6-dimethyl-2-norbornene; 5-phenyl norbornene; 5-benzylnorbornene; 5-acetylnorbornene; 5-methoxycarbonylnorbornene; 5-ethoxycarbonyl-1-norbornene; 5-methyl-5-methoxy-carbonylnorbornene; 5-cyanonorbornene; 5,5,6-trimethyl-2-norbornene; cyclo-hexenylnorbornene; endo, exo-5,6-dimethoxynorbornene; endo, endo-5,6-dimethoxynorbornene; endo, exo-5-6-dimethoxycarbonylnorbornene; endo, endo-5,6-dimethoxycarbonylnorbornene; 2,3-dimethoxynorbornene; norbornadiene; tricycloundecene; tetracyclododecene; 8-methyltetracyclododecene; 8-ethyl-tetracyclododecene; 8-methoxycarbonyltetracyclododecene; 8-methyl-8-tetracyclo-dodecene; 8-cyanotetracyclododecene; pentacyclopentadecene; pentacyclohexadecene; 5-butyl-2-norbornene; 5-hexyl-2-norbornene; 5-octyl-2-norbornene; 5-decyl-2-norbornene; 5-dodecyl-2-norbornene; 5-vinyl-2-norbornene; 5-ethylidene-2-norbornene; 5-isopropenyl-2-norbornene; 5-propenyl-2-norbornene; and 5-butenyl-2-norbornene. 
     
     
         16 . The resin composition of  claim 1 , wherein the cyclic olefin is selected from the group consisting of dicyclopentadiene; tricyclopentadiene; cyclopentadiene tetramer; cyclopentadiene pentamer; tetracyclododecene; norbornene; 5-butyl-2-norbornene; 5-hexyl-2-norbornene; 5-octyl-2-norbornene; 5-decyl-2-norbornene; 5-dodecyl-2-norbornene; 5-vinyl-2-norbornene; 5-ethylidene-2-norbornene; 5-isopropenyl-2-norbornene; 5-propenyl-2-norbornene; and 5-butenyl-2-norbornene. 
     
     
         17 . The resin composition of  claim 1 , wherein the resin composition further comprises at least one additive. 
     
     
         18 . The resin composition of  claim 1 , wherein the resin composition further comprises at least one crosslinker. 
     
     
         19 . The resin composition of  claim 18 , wherein the at least one crosslinker is selected from the group consisting of dialkyl peroxides, diacyl peroxides, peroxyacids, and mixtures thereof. 
     
     
         20 . An article of manufacture comprising at least one resin composition of  claim 1 . 
     
     
         21 . A method for improving the adhesion of a resin composition to a substrate material, comprising:
 combining at least one cyclic olefin, at least one olefin metathesis catalyst,   and the at least one adhesion promoter composition of  claim 1  to form a resin composition,   contacting the resin composition with the substrate material, and   subjecting the resin composition to conditions effective to promote an olefin metathesis reaction of the cyclic olefin.