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

Abstract

Synthesis of ternary copolymers of some unsaturated electron-donor epoxide monomers (UEM) such as 4-methyl-4,5-epoxypentene-1 (MEP), vinyl- (VGE), allyl- (AGE) and p-isopropenyl-phenyl (PhGE) glycidyl ethers, maleic anhydride (MA) and styrene (St) was carried out in methylethyl ketone (MEK) in the presence of benzoyl peroxide as an initiator at 50–80 °C. Constants of charge-transfer complex (CTC) formation (Kc) for MEP…MA (Kc = 0.10 L mol−1), VGE…MA (Kc = 0.17 L mol−1), AGE…MA (Kc = 0.09 L mol−1), PhGE…MA (Kc = 0.14 L mol−1) and St…MA (Kc = 0.29 L mol−1) donor–acceptor complexes in deuterated acetone at 37 °C were determined by 1H NMR spectroscopy. Constants of copolymerization for monomer and complexed monomer pairs were determined by the Kelen–Tudos and Seiner–Litt methods. Kinetic parameters together with ratios of chain growth rates for the participation of monomer CTC and free monomers were obtained for all monomer systems studied. The results showed that terpolymerization was carried out through a primary ‘complex’ 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 crosslinking by thermotreatment and by UV-irradiation, as confirmed by DTA and FTIR analyses. © 2001 Society of Chemical Industry