Photo-crosslinking of polystyrenes having pendant epoxy groups

Vinylbenzyl glycidyl ether (VBGE), vinylbenzyl 2-methylglycidyl ether (VBMG E), vinylphenethyloxirane (VPO), 2-methyl-2-vinylphenethyloxirane (MVPO) an d vinylbenzyl 3,4-epoxycyclohexylmethyl ether (VBECE) were prepared as styr ene-type monomers having various pendant epoxides and polymerized by the us e of AIBN to afford the corresponding polymers and copolymers with styrene (St). Poly[[2 -(3,4-epoxycyclohexyl)ethyl]dimethyl-4-vinylbenzylsilane](pol y-(MVBS)) and poly(EMVBS-co-St) having silicon atoms in pendant groups were synthesized by the hydrosilation of poly(dimethyl-4-vinylbenzylsilane) (po ly(MVBS)) and poly(MVBS-co-St), respectively, with 4-vinyl-1-cyclohexene 1, 2-poxide in the presence of catalytic amount of RhCl(PPh3)(3). Poly [[4-oxa -5-(3,-epoxycyclohexyl)pentyl]dimethyl-4-vinylbenzylsilane-co--styrene] (po ly(OEMVBS-co-St)) containing ether linkage between silicon and epoxy group was also prepared by the hydrosilation of poly(MVBS-co-St) with allyl 3,4-e poxycyclohexylmethyl ether. The obtained polymers were casted with photo-ac id generator, irradiated by UV light and the degree of insolubilization of the resulting films was examined. Polymers having cyclohexene oxide unit co nnected to aromatic ring by -SiCH2CH2-linkage (poly(EMVBS) and poly(EMVBS-c o-St)) showed highest crosslinking reactivity, while poly(VBECE) and poly(V BECE-co-St) containing cyclohexene oxide unit and ether linkage in pendant group showed lowest. Polymers having 2-methylglycidyl structure at pendant group had higher crosslinking reactivity than those containing the correspo nding glycidyl structure. Ether linkage between epoxy group and aromatic ri ng lowered the reactivity of the epoxide compared to the polymers without s uch linkage. (C) 2001 Elsevier Science BY All rights reserved.