Studies of the polymerization of diallyl compounds—XLIII. Microheterogeneous copolymerization of diallyl terephthalate with vinyl monomers having long-chain alkyl groups

Abstract

Diallyl terephthalate (DAT) was radically copolymerized in benzene with vinyl monomers having long-chain alkyl groups, including lauryl methacrylate (LMA), stearyl methacrylate (SMA) and vinyl laurate (VL). In the DAT-LMA copolymerizations, the initial rate was quite high because of high polymerizability of LMA compared with DAT. The gel point was at a higher conversion than in DAT homopolymerization. The LMA content in the copolymer decreased rapidly with the conversion up to the gel point; beyond the gel point, the LMA content in the soluble portion increased markedly with the progress of gelation. These tendencies were more pronounced in the DAT-SMA copolymerization. The reversed conversion dependence of the composition of precopolymer and sol at the gel point and the delayed gelation were not observed in the DAT-VL copolymerization. The change of the composition distribution of copolymer with progress of copolymerization was followed by comparison of r.i.- and u.v.-monitored GPC curves. These results are discussed from the standpoint of microheterogeneous copolymerization.