In-mold coating of ROMP polymers
The present invention relates to in-mold coating of a cyclic olefin polymer. More particularly, the present invention relates to methods and compositions for in-mold coating cyclic olefin polymers prepared by ring opening metathesis polymerization (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 polymer and material chemistry and manufacture.
1. A method of in-mold coating a ROMP polymer comprising:
providing a urethane-based paint;
applying the urethane-based paint to a mold surface to form a painted mold surface;
providing a urethane-based primer;
applying the urethane-based primer to the painted mold surface;
contacting the painted and primed mold surface with a resin composition comprising at least one cyclic olefin, at least one olefin metathesis catalyst, and at least one in-mold coating adhesion compound; and
subjecting the resin composition to conditions to polymerize the resin composition forming an in-mold coated ROMP polymer,
wherein the in-mold coated ROMP polymer comprises the polymerized resin composition and an adherent coating thereon, wherein the adherent coating is formed by the urethane-based paint and the urethane-based primer.
2. The method of 1 , wherein the at least one olefin metathesis catalyst is a Group 8 transition metal complex having the structure of formula (V)
n is zero;
k is 1;
Q is a two-atom linkage having the structure —CR 11 R 12 —CR 13 R 14 —, 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;
R 3 and R 4 are the same and are each unsubstituted phenyl or phenyl substituted with up to three 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;
L 2 is selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, substituted pyridine, imidazole, substituted imidazole, pyrazine, substituted pyrazine, and thioether;
X 1 and X 2 are halide; and
R 1 is hydrogen and R 2 is selected from C 1 -C 20 alkyl, C 2 -C 20 alkenyl, and C 5 -C 24 aryl; or
R 1 and R 2 form a substituted indenylidene.
3. The method of claim 1 , wherein the at least one in-mold coating adhesion compound is selected from the group consisting of 5-norbornene-2-methanol; 2-hydroxyethyl bicycle[2.2.1]hept-2-ene-carboxylate; 2-hydroxyethyl acrylate; allyl alcohol; oleyl alcohol; 9-decen-1-ol; allyl alcohol; cis-13-dodecenol; trans-9-octadecenol; norbornyl alcohol; 2-cycloocten-1-ol; 2-cyclooctadiene-1-ol; p-vinyl phenol; 2-hydroxyethyl methacrylate; 2-hydroxy-3-acryloxypropyl methacrylate; ethoxylated hydroxyethyl acrylate; ethoxylated hydroxyethyl methacrylate; polypropyleneglycol monomethacrylate; polypropylene glycol monoacrylate; phenol acrylate; phenol methacrylate; bisphenol A type epoxy acrylate; novolac type epoxy acrylate; brominated bisphenol A type epoxy acrylate; allyl amine; diallyl amine; olelyl amine; bicyclo[2.2.1]hept-2-ene-5-methylamine; 5-norbornenyl-2-methylamine (NBMA), and mixtures thereof.
4. The method of claim 1 , wherein the at least one cyclic olefin is selected from the group consisting of mono-unsaturated cyclic olefins, monocyclic dienes, bicyclic olefins, polycyclic olefins, and mixtures thereof.
5. The method of claim 1 , wherein the at least one cyclic olefin is selected from the group consisting of 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-ethoxycarbonyl-1-norbornene; 5-methyl-5-methoxycarbonylnorbornene; 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; cyclopentadiene tetramer, cyclopentadiene pentamer; 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 mixtures thereof.
6. The method of claim 1 , wherein the at least one 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, 5-butenyl-2-norbornene, and mixtures thereof.