Synthesis and reactions of self-crosslinkable epoxy- and anhydride-containing macromolecules

Synthesis of ternary copolymers of some unsaturated electron-donor epoxide monomers (UEM) such as 4-methyl-4,5-epoxypentene-1 (MEP), vinyl-(AGE), ally l- (AGE) and p-isopropenylphenyl (PhGE) glycidyl ethers, maleic anhydride ( IMA) and styrene (St) was carried out in methylethyl ketone (MEK) in the pr esence of benzoyl peroxide as an initiator at 50-80 C. Constants of charge- transfer complex (CTC) formation (K-c) for MEP...MA (K-c = 0.10 Lmol(-1)), VGE...MA (K-c = 0.17 L mol(-1)), AGE...MA (K-c = 0.09 Lmol(-1)), PhGE...MA (K-c = 0.14 Lmol(-1)) and St...MA (K-c = 0.29 Lmol(-1)) donor-acceptor comp lexes in deuterated acetone at 37 C were determined by H-1 NMR spectroscopy . Constants of copolymerization for monomer and complexed monomer pairs wer e determined by the Kelen-Tudos and Seiner-Litt methods. Kinetic parameters together with ratios of chain growth rates for the participation of monome r CTC and free monomers were obtained for all monomer systems studied. The results showed that terpolymerization was carried out through a primary 'co mplex' mechanism in the state close to binary copolymerization of UEM...MA and MA...St complexes. The synthesized terpolymers with free anhydride and epoxide reactive groups easily underwent cross-linking by thermotreatment a nd by UV-irradiation, as confirmed by DTA and FTIR analyses. (C) 2001 Socie ty of Chemical Industry.