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 preparing a syntactic foam, comprising the steps of:
combining at least one cyclic olefin, at least one type of microparticulate density modulator, and an adhesion promoter comprising a functionalized silane and a peroxide to form a resin composition;
wherein the combined concentration of the functionalized silane and the peroxide present in the resin composition range from 0.5-3.5 phr and the amount of the peroxide present is equal to or greater than the amount of functionalized silane present;
adding at least one cyclic olefin metathesis catalyst to the resin composition to form a catalyzed resin composition; and
curing the catalyzed resin composition to form the syntactic foam,
wherein the at least one type of microparticulate density modulator is borosilicate glass microspheres, wherein the at least one cyclic olefin is a mixture of dicyclopentadiene and tricyclopentadiene, the functionalized silane is y-methacryloxypropyl-trimethoxy silane, and the peroxide is di-tert-butyl peroxide.
2. The method according to claim 1 , wherein the cyclic olefin metathesis catalyst is a Group 8 transition metal complex having the structure:
wherein:
M is a Group 8 transition metal selected from ruthenium or osmium;
L 1 , L 2 , and L 3 are independently selected from neutral electron donor ligands;
n is 0 or 1 for L 3 ;
m is 0, 1, or 2;
X 1 and X 2 are independently anionic ligands;
R 1 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;
n is 0 or 1 for the -(W) n -U + V − moiety; 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.
3. The method according to claim 2 , 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, or halide.
4. The method according to claim 1 , wherein the cyclic olefin metathesis catalyst is a Group 8 transition metal complex having the structure:
wherein:
M is a Group 8 transition metal selected from ruthenium or osmium;
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; 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 , RE, R 7 , and R 8 may be linked to a support.
5. The method according to claim 1 , wherein at least one further type of microparticulate density modulator is combined with the at least one cyclic olefin.
6. The method according to claim 1 , wherein the steps of preparing the syntactic foam are carried out without the use of a solvent.
7. The method according to claim 1 , wherein the combined concentration of the functionalized silane and the peroxide present in the resin composition range from 1-3 phr.
8. The method according to claim 1 , wherein the combined concentration of the functionalized silane and the peroxide present in the resin composition is about 3 phr.
9. The method according to claim 8 , wherein the steps of preparing the syntactic foam are carried out without the use of a solvent.
10. The method according to claim 1 , wherein the combined concentration of the functionalized silane and the peroxide present in the resin composition range from 1.5-2 phr.
11. The method according to claim 1 , wherein the combined concentration of the functionalized silane and the peroxide present in the resin composition range from 3-3.5 phr.