Abstract
Polymeric hydroperoxides could not be prepared from poly(styrene-co-methyl methacrylate) through tertiary alcohol side-groups and subsequent hydroperoxidation with hydrogen peroxide due to lack of reaction in the first step between Grignard reagents and the methyl methacrylate units. The reaction between succinic anhydride and t-butyl hydroperoxide has been utilised to produce partial t-butyl peresters of poly(styrene-alt-maleic anhydride) and the products have been employed to initiate the polymerisation in solution of n-butyl methacrylate, methacrylic acid, vinylidene chloride, acrylonitrile and methyl methacrylate. In the case of acrylonitrile the polymeric initiator was rendered water-soluble by partial neutralisation of carboxylic acid groups with alkali. Polymerisation in aqueous solution was effected by "redox" initiation, and the polymer was precipitated as formed. With methyl methacrylate 'thermal" initiation was employed in acetone solution, the system remaining homogeneous. Graft copolymerisation of the secondary monomers to the initiating polymer was evidenced by physical behaviour in some cases, and for acrylonitrile and methyl methacrylate was established by fractionation and analytical examination of the fractions. Acrylonitrile graft copolymers were fractionated by selective elution, while the methyl methacrylate graft copolymers were subjected to fractional precipitation. The fractions were characterised by infra-red analysis, and also, in the case of methyl methacrylate graft copolymer, by pyrolysis in conjunction with gas-liquid chromatography.