Study on the preirradiation polymerization of vinyl monomers

Abstract

This paper presents mainly the polymerization, copolymerization and crosslinking of monomers off-source induced by peroxides which are formed by high energy irradiation of vinyl monomers such as styrene (St), acrylonitrile (AN), methylmethacrylate (MMA), vinyl acetate (VAc) and 2-hydroxyethyl methacrylate (HEMA). The peroxides produced by irradiation of the above-mentioned monomers can not only induce the monomers themselves, but also another non-irradiated monomer to carry out copolymerization efficiently. The activation energy of peroxide formation, the apparent activation energy of polymerization and the activation energy of peroxide initiation by irradiation of vinyl monomers are: E f(MMA) = 11, E f(St) = 9.6, E f(AN) = 8.5, E MMA = E VA = 11.4, E i(MMA) = E i(VA) = 13 kcal/mol. The rate of decomposition of monomer peroxides is smoother than that of BPO during the polymerization and so a smooth kinetic progress is obtained. The initiating ability of forming peroxides by irradiation of the vinyl monomers depends mainly on the chemical structure of the monomers. For instance, the main structure of peroxides formed during preirradiation MMA are: alternating peroxy-copolymer ▪ and random peroxy-copolymer ▪ Owing to the peroxy-bond which is unstable and in which homolytic breakage easily occurs to yield a pair of radicals, RO . is formed within the above-mentioned structural compounds, so that they possess stronger initiating reactivity. It is quite evident that the initiating reactivity of AN peroxide will be greatly reduced because of the conjugate double bond. In other words, the initiating ability of AN peroxide is lower than MMA peroxide and St peroxide.