Polymers with peroxidic functional groups. I. Copolymers of di(t‐butylperoxy) fumarate

Abstract

SynopsisDi(t-butylperoxy) fumarate was copolymerized with styrene, butadiene, acrylonitrile, methyl methacrylate, vinyl chloride and vinyl acetate to give copolymers containing pendant peroxyester functions. Another peroxide was generally used for initiating polymerization: however, experiments were carried out with di(t-butylperoxy) fumarate as both initiating species and comonomer. The active oxygen contents and intrinsic viscosities were determined for these copolymers. A copolymer of styrene and di(t-butylperoxy) fumarate synthesized from monomers in equal weight ratio had an active oxygen content of 5.3% and a peroxide halflife of 7.7 hr. at 85OC. in benzene. This peroxide was used as a catalyst for the curing of polyester resins and as an initiator for styrene bulk polymerization. The monomer reactivity ratios for the monomer pair styrene-di(t-butylperoxy) fumarate were determined. Graft copolymers were made by grafting methyl methacrylate on a styrene-di(t-butylperoxy) fumarate copolymer and also by grafting styrene on a vinyl acetate-di(t-butylperoxy) fumarate copolymer. These graft copolymers were used to enhance the stability of homopolymer-solvent mixtures. A novel ABS type of resin was synthesized by grafting styrene and acrylonitrile on the copolymer system butadiene-di(t-butylperoxy) fumarate. Another novel resin was synthesized by grafting butadiene on the terpolymer system styrene-acrylonitrile-di(t-butylperoxy) fumarate. A homopolymer of di(t-butylperoxy) fumarate was also prepared and used as a catalyst for the curing of polyester resins.