The free radical homopolymerization and copolymerization of 3‐tri‐n‐butylstannylstyrene (3‐BTS) with styrene (ST), ethyl acrylate (EA), methyl methacrylate (MMA), vinyl acetate (VA), and acrylonitrile (AN) were carried out using 2,2′‐azobisisobutyronitrile (AIBN) at 60°C. It was found that the yield of conversion to poly(3‐BTS) increased with the molar ratio of initiator to monomer as well as with polymerization time. The conversion at equilibrium after 50 h was about 40%. The compositions of copolymer samples were determined from elemental analyses. Monomer reactivity ratio and Q‐e values were calculated. The copolymers of 3‐BTS‐MMA and 3‐BTS‐AN were found to be alternating. The copolymers of 3‐BTS with MMA, EA and AN were not soluble in any of a large number of organic solvents tested. The insolubility is believed to be due to formation of intermolecular coordination among the tributylstannyl moiety and the carbonyl or cyano groups of the polymer. These copolymers, however, were “soluble” in trihaloacetic acid, but this solubility was due to a cleavage of the trialkyltin moiety from the phenyl groups. The glass temperatures, Tg, and melting temperatures Tm, of the various polymers were also studied.
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