Complexed copolymerization of vinyl compounds with alkylaluminum halides

Abstract

synopaisThe monomer reactivity in the complexed copolymerization of vinyl compounds with alkylaluminum halides has been extensively surveyed. Equirnolar copolymers were obtained in various combinations of monomers which are classified into two monomer groups, A and B. The group B monomers are conjugated vinyl compounds having nitrile or carbonyl groups in the conjugated position and form complexes with alkylaluminum halides. The group A monomers are donor monomers having low e values, such as olefins, haloolefins, dienes, and unsaturated esters. These A monomers belong to the same group of monomers which give alternating copolymers in conventional radical copolymerization with rnaleic anhydride, SOz, and so on. In addit.ion the complexed copolymerization has the same specific characteristics as the conventional alternating copolymerization, i.e., high reactivities of allyl-resonance monomers and inner olefins and no transfer of halogen atom to the copolymers in CCl,. These features suggest little or no participation of the A monomer radical. The &-e scheme is also discussed in terms of the monomer reactivity. More than two monomers selected from groups A and B give multicomponent copolymers in which alternating sequential structures hold with respect to A and B. Anomalous mutual reactivities between two B monomers in the terpolymerization were observed and indicate that the nature of radical in the complexed copolymerization may be different from that expected by the Lewis-Mayo equation. The complexed radical mechanism previously proposed is discussed in connection with the specific behavior mentioned above. EXPERIMENTAL MaterialsMonomers. Ethylene, propylene, butadiene, vinyl chloride, and acrylonitrile were polymerization-grade reagents of the Sumitomo Chemical

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