Radical polymerizations of acrylonitrile, methacrylonitrile, methyl acrylate, and methyl methacrylate in the presence of Lewis acid type complexing agents like ZnC12, SnC14, or (C2HS),A1Cl3-, (n = 1,2,3) were investigated. The accelerating or inhibiting effects of the complexing agents on the polymerization of individual monomers were observed depending on the concentration and the character of the complexing agent. These effects were found to be also influenced by the monomer structure. The polymerization mechanism is discussed.
The terpolymerization of polar vinyl monomers, such as acrylonitrile or methacrylonitrile and methyl acrylate or methyl methacrylate with butadiene or styrene in the presence of ethylaluminium, aluminium, zinc(II), or stannum(1V) chlorides has been investigated. The yield and composition of the terpolymers as well as the yield of the Diels-Alder reaction by-products were determined. The copolymerization between two polar vinyl monomers in the presence of ethylaluminium dichloride or zinc(I1) chloride was also carried out and the yield and composition of the copolymers produced were determined. The effect of the complexation of polar vinyl monomers by Lewis acids on the yield and monomer composition of the terpolymers produced in the investigated ternary systems is discussed in terms of the reactivities of these monomers (complexed by Lewis acids in alternating copolymerization) and competitive Diels-Alder reactions with butadiene, as well as in terms of the copolymerization reactions between them.
The copolymerization of acrylonitrile (AN), methacrylonitrile (MAN), methyl acrylate (MA), and methyl methacrylate (MMA) with butadiene (BD) in the presence of ethylaluminium dichloride, zinc chloride, and stannic chloride was investigated. The reactivity of polar monomers in the copolymerization was found to decrease in the following order: AN>MAN>MMA>MA. It was also found that AN and MAN form with BD copolymers of essentially 1 : 1 composition; MMA, and particularly MA were found, however, to form with BD copolymers of a composition different from 1 : I.In competition with the copolymerization, a Diels-Alder reaction was shown to occur in the investigated systems. The reactivity of polar monomers in the Diels-Alder reaction was found to increase in the following order: MAN < AN < MMA < MA. In the presence
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