Method and composition for improving adhesion of metathesis compositions to substrates
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.
1. A method for manufacturing a glass composite laminate via vacuum assisted resin transfer molding, comprising, infusing a glass substrate material with a ROMP composition, wherein the ROMP composition comprises combining a cyclic olefin, a cyclic olefin metathesis catalyst, a functionalized silane and a peroxide.
2. The method according to claim 1 , wherein the glass substrate material is selected from glass fabric and silane treated glass fabric.
3. The method according to claim 2 , wherein the glass composite laminate has improved mechanical properties.
4. The method according to claim 3 , wherein the cyclic olefin is functionalized or unfunctionalized, and is substituted or unsubstituted.
5. The method according to claim 4 , wherein the cyclic olefin is selected from cyclobutene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cyclooctadiene, cyclononadiene, cyclododecatriene, norbornene, dicyclopentadiene, tricyclopentadiene, tetracyclododecene, tetracyclododecadiene, substituted norbornenes, substituted dicyclopentadienes, and combinations thereof.
6. The method according to claim 4 , wherein the cyclic olefin metathesis catalyst is a Group 8 transition metal complex having 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, and 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;
Z is a group selected from hydrogen, alkyl, aryl, functionalized alkyl, functionalized aryl where the functional group(s) is/are independently 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.
7. The method according to claim 4 , wherein the cyclic olefin metathesis 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;
m is 0, 1, or 2;
X 1 and X 2 are independently anionic ligands;
R l is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups;
R 2 is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional group; 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
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.
8. The method according to claim 7 , wherein at least one of L 1 , L 2 , and L 3 is an N heterocyclic carbene ligand of 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, and halide.
9. The method according to claim 7 , 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, and substituted heteroatom-containing hydrocarbyl.
10. The method according to claim 9 , wherein the peroxide is selected from dialkyl and diary peroxides.
11. The method according to claim 10 , wherein the peroxide is selected from di-tert-butyl peroxide and dicumyl peroxide.
12. The method according to claim 9 , wherein Fn is selected from acrylate, methacrylate, allyl, vinyl, alkene, cycloalkene, and norbornene.
13. The method according to claim 9 , wherein the functionalized silane is selected from allyltrimethoxysilane, allyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, butenyltrimethoxysilane, butenyltriethoxysilane, hexenyltrimethoxysilane, hexenyltriethoxysilane, norbornenyltrimethoxysilane, norbornenyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, norbornenylethyltrimethoxysilane, norbornenylethyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane, gamma-acryloxypropyltrimethoxysilane, and gamma-acryloxypropyltriethoxysilane.