The free radical copolymerization and multipolymerization of olefins with acrylic monomers in the presence of acids has been studied. It was found that Bronsted acids are as suitable complexing agents for the acrylic comonomer as the up to now exclusively used Lewis acids.The effectiveness of the Bronsted acids, e.g. carboxylic acids, for obtaining alternating copolymers increased with the pKs value, and trifluoroacetic acid turned out to be the acid of choice. The variation of the Lewis acid-type complexation agents was extended by the zinc chloride diethylether complex which is advantageous over ZnCI, or other Lewis acids because of its good solubility and recycling practicability, which is also a feature of the Bronsted acids.The versatility of the new complexing agent systems was demonstrated in a series of co-and multipolymerizations, and ethyl cyanoacrylate was employed for the first time as electron acceptor comonomer. The properties of the copolymers with periodic comonomer sequences varied systematically with their composition, e.g. the glass transition temperature and the degree of crystallinity.
The free radical copolymerization and terpolymerization of acrylic monomers with olefins in the presence of Lewis acid complexing agent for the acrylic monomer has been investigated. The course of the polyreaction is in agreement with the features of a radical chain growth reaction, and the polymer properties can be varied by changing the composition of the reaction mixture and the reaction conditions. The alternating copolymers are usually amorphous materials, and only the alternating ethylene/acrylonitrile copolymer can be obtained as a material of relatively high crystallinity. The degree of crystallinity can be varied through terpolymerization of complexed acrylonitrile with ethylene/propylene comonomers. The basic features of the polyreaction and the polymer structures as well as some of the physical and material properties of the copolymers have been studied.
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