Terpolymerization of vinyl compounds in the presence of lewis acids

Abstract

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.

Studies on alternating radical copolymerization: analysis of microstructures of styrene-maleic anhydride, styrene-acrylonitrile, and styrene-methyl methacrylate copolymers by fluorescence spectroscopy

“…The difference in the compositions of the resulting copolymers between the St-AN-ZnCl2 and St-MMA-ZnCl2 radical copolymerization systems may be due to the complexing ability of ZnCl2 being reportedly much higher for nitriles than for esters. 41 The characterization of copolymers by fluorescence spectroscopy needs only a few milligrams of samples for the measurement and provides useful information on the monomer sequence length of copolymers with aryl vinyl monomers as one component.…”