Method and composition for improving adhesion of metathesis compositions to substrates

Abstract

A method of improving the adhesion of metathesis compositions, such as ring-opening metathesis polymerization (ROMP) compositions, to a substrate is disclosed, in which an adhesion promoter is added to a polymerizable resin composition in order to improve the adhesion of the polymerizing resin to a substrate material. The addition of the adhesion promoter has been found to provide beneficial improvements in the adhesion of metathesis, especially ROMP, compositions to substrates, particularly glass surfaces, leading to improved characteristics in ROMP materials formed therefrom. The adhesion promoter generally comprises a functionalized silane compound and a peroxide compound. A ROMP composition is further disclosed comprising a cyclic olefin, a ROMP metathesis catalyst, and the adhesion promoter. Polymer products produced via metathesis (ROMP) reactions of the invention may be utilized to provide a wide range of materials and in a variety of composite applications. The invention has utility in the fields of catalysis, organic synthesis, and polymer and materials chemistry and manufacture.

What is claimed is: 
     
         1 . A ROMP composition, comprising:
 a cyclic olefin metathesis catalyst;   a cyclic olefin, which may be functionalized or unfunctionalized, and may be substituted or unsubstituted;   a functionalized silane; and   a peroxide.   
     
     
         2 . The composition of  claim 1 , wherein the functionalized silane is of the formula Fn-(A) n -Si(OR) 3 , wherein Fn is a functional group; A is a divalent linking group; n is 0 or 1; and R is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl. 
     
     
         3 . The composition of  claim 2 , wherein the functional group of the functionalized silane is selected from acrylate, methacrylate, allyl, vinyl, alkene, cycloalkene, or norbornene. 
     
     
         4 . The composition of  claim 2 , wherein the functional group of the functionalized silane is selected from methacrylate or norbornene. 
     
     
         5 . The composition of  claim 2 , wherein the functionalized silane is a C 1 -C 12  alkoxy silane or C 1 -C 12  alkoxy silane having a C 1 -C 12  alkylene divalent linking group, the functionalized silane having a functional group selected from acrylate, methacrylate, allyl, vinyl, alkene, cycloalkene, or norbornene. 
     
     
         6 . The composition of  claim 2 , wherein the functionalized silane is selected from allyltrimethoxysilane, allyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, butenyltrimethoxysilane, butenyltriethoxysilane, hexenyltrimethoxysilane, hexenyltriethoxysilane, norbornenyltrimethoxysilane, norbornenyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, norbornenylethyltrimethoxysilane, or norbornenylethyltriethoxysilane. 
     
     
         7 . The composition of  claim 2 , wherein the functionalized silane is selected from gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane, gamma-acryloxypropyltrimethoxysilane, or gamma-acryloxypropyltriethoxysilane. 
     
     
         8 . The composition of  claim 2 , wherein the divalent linking group is selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene. 
     
     
         9 . The composition of  claim 8 , wherein the divalent linking group is 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. 
     
     
         10 . The composition of  claim 2 , wherein R is selected from C 1 -C 20  alkyl, C 5 -C 20  aryl, C 6 -C 20  aralkyl, C 5 -C 12  cycloalkyl, C 2 -C 20  alkoxyalkyl, or C 1 -C 20  acyl. 
     
     
         11 . The composition of  claim 1 , wherein the peroxide is selected from dialkyl and diaryl peroxides. 
     
     
         12 . The composition of  claim 11 , wherein the peroxide is selected from di-tert-butyl peroxide and dicumyl peroxide. 
     
     
         13 . The composition of  claim 1 , wherein the cyclic olefin is selected from strained cyclic olefins, unstrained cyclic olefins, acyclic olefins, dienes, and unsaturated polymers, or combinations 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, aryloxy, 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, or a combination thereof. 
     
     
         14 . The composition of  claim 13 , wherein the cyclic olefin is selected from cyclobutene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cyclooctadiene, cyclononadiene, cyclododecatriene, norbornene, dicyclopentadiene, tricyclopentadiene, tetracyclododecene, tetracyclododecadiene, substituted norbornenes, substituted dicyclopentadienes, or combinations thereof. 
     
     
         15 . The composition of  claim 1 , wherein the catalyst is a Group 8 transition metal complex having the structure 
       
         
           
           
               
               
           
         
         wherein, 
         M is a Group 8 transition metal; 
         L 1 , L 2 , and L 3  are independently selected from 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; 
         X 1  and X 2  are independently selected from 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 one or both of R 1  and R 2  may have the structure —(W) n —U + V − , 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, 
         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, and further wherein any one or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2  may be attached to a support. 
       
     
     
         16 . The composition of  claim 15 , wherein at least one of L 1 , L 2 , and L 3  is an N-heterocyclic carbene ligand. 
     
     
         17 . The composition of  claim 15 , wherein the catalyst has the structure 
       
         
           
           
               
               
           
         
         wherein, 
         M is a Group 8 transition metal; 
         n is zero or 1; 
         m is 0, 1, or 2; 
         X 1  and X 2  are independently selected from anionic ligands; 
         L 2  and L 3  are independently selected from neutral electron donor ligands, or may be taken together to form a single bidentate neutral electron-donating ligand; 
         R 1  and R 2  are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, or may be taken together to form an indenylidene moiety; 
         X and Y are independently selected from 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 1 , Q 2 , Q 3 , and Q 4  are independently selected from 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 3 , R 3A , R 4 , and R 4A  are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl, 
         wherein any two or more of X 1 , X 2 , L 2 , L 3 , R 1 , R 2 , Q 1 , Q 2 , Q 3 , Q 4 , R 3 , R 3A , R 4 , and R 4A  can be taken together to form a cyclic group, and further wherein any one or more of X 1 , X 2 , L 2 , L 3 , Q 1 , Q 2 , Q 3 , Q 4 , R 1 , R 2 , R 3 , R 3A , R 4 , and R 4A  may be attached to a support. 
       
     
     
         18 . The composition of  claim 17 , wherein M is ruthenium, w, x, y, and z are zero, X and Y are N, and R 3A  and R 4A  are linked to form -Q-, such that the complex has the structure 
       
         
           
           
               
               
           
         
         wherein Q is a hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene linker, and further wherein two or more substituents on adjacent atoms within Q may be linked to form an additional cyclic group. 
       
     
     
         19 . The composition of  claim 18 , wherein:
 X 1  and X 2  are halide;   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 aromatic.   
     
     
         20 . The composition of  claim 19 , wherein:
 Q is —CR 11 R 12 —CR 13 R 14 — wherein R 11 , R 12 , R 13 , and R 14  are independently selected from hydrogen, C 1 -C 12  alkyl, substituted C 1 -C 12  alkyl, C 1 -C 12  heteroalkyl, substituted C 1 -C 12  heteroalkyl, phenyl, and substituted phenyl; 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.   
     
     
         21 . The composition of  claim 17 , wherein the cyclic group is formed from R 1  and/or R 2  taken together with one or more of L 2 , L 3 , R 3 , R 3A , R 4 , and R 4A . 
     
     
         22 . The composition of  claim 16 , 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. 
       
     
     
         23 . The composition of  claim 1 , wherein the catalyst comprises a chelating alkylidene ligand. 
     
     
         24 . The composition of  claim 1 , wherein the catalyst has the structure 
       
         
           
           
               
               
           
         
         wherein, 
         M is a Group 8 transition metal; 
         X 1  and X 2  are independently anionic ligands; 
         L 1  is selected from neutral electron donor ligands; 
         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, or borate; and any combination of R 5 , R 6 , R 7 , and R 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 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; and wherein any combination or combinations of X 1 , X 2 , L 1 , Y, Z, R 5 , R 6 , R 7 , and R 8  may be linked to a support. 
       
     
     
         25 . An adhesion promoter composition, comprising:
 a functionalized silane of the formula
   Fn-(A) n -Si(OR) 3    
   wherein,   Fn is a functional group selected from acrylate, methacrylate, allyl, vinyl, alkene, cycloalkene, or norbornene;   A is a divalent linking group selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene;   n is 0 or 1; and   R is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; and   a peroxide selected from dialkyl and diaryl peroxides.   
     
     
         26 . The composition of  claim 17 , wherein the neutral electron donor is selected from an electron donating heterocyclic ligand. 
     
     
         27 . A method for improving the adhesion of a ROMP composition to a substrate material, comprising:
 combining a functionalized silane and a peroxide with a cyclic olefin and a cyclic olefin metathesis catalyst to form the ROMP composition, wherein the cyclic olefin may be functionalized or unfunctionalized, and may be substituted or unsubstituted;   contacting the ROMP composition with a substrate material, or adding a substrate material to the ROMP composition; and   subjecting the ROMP composition to conditions effective to promote a ROMP reaction of the cyclic olefin in the presence of the cyclic olefin metathesis catalyst, the functionalized silane, the peroxide, and the substrate material.   
     
     
         28 . The method of  claim 27 , wherein the functionalized silane and the peroxide are added in an amount effective to increase the adhesion of the metathesis catalyzed ROMP composition to a substrate material.