The terpolymerization of the three monomers (3-vinyl phenylazo)methylmalodinitrile (1), (3-vinyl phenylazo)phenylsulfid (2) or 1-(3-vinylphenylazo)-1,1′-diphenyl methylacetate (3) with methyl methacrylate and butanediol-1,4-dimethyacrylate leads to networks in which the thermolabile azo groups remain intact. Both, the azo monomer and the crosslinking agent are essentially quantitatively incorporated into the network before the conversion of the third monomer is complete. The networks have been characterized in terms of their swelling in benzene, chlorobenzene, and methacrylonitrile. Die Terpolymerisation der drei Monomeren (3-Vinylphenylazo)-methylmalodinitril (1), (3-Vinylphenylazo)phenyls…

In order to graft methacrylonitrile onto preformed networks containing thermolabile azo groups, the monomer was used to swell the networks and then the temperature raised to the decomposition temperature for the azo groups. The unusually high grafting efficiencies yields (e) achieved are explained in terms of both the differences in the reactivities of the primary radicals formed and side reactions, which lead to additional grafting sites. As an aid to understand the dependence of monomer conversion on that of the initiator a kinetic model is discussed, which involves the consideration of the polymerization taking place both in the homogeneous phase and within the polymer pearls, which can …