The synthesis and reactivity of ω‐(P‐vinylbenzyl ether) macromonomer of poly(2,6‐dimethyl‐1,4‐phenylene ether)

Abstract

AbstractThis paper describes the synthesis and reactivity of ω‐(p‐vinylbenzyl ether) macromonomer of poly(2,6‐dimethyl‐1,4‐phenylene ether) (PPE‐VBE). The reactivity of PPE‐VBE macromonomer, as determined from the free radical copolymerization of PPE‐VBE with either methyl methacrylate (MMA) or n‐butyl methacrylate (BMA), is influenced by the molecular weight of PPE‐VBE, by the concentration of the macromonomer or total comonomers, and by the nature of the polymerization solvent. The dependence of the reactivity on the molecular weight of the PPE‐VBE macromonomer was interpreted based on the kinetic excluded volume theory and by a micelle formation model. This paper demonstrates that the reactivity of PPE‐VBE macromonomers can be explained by the micelle formation model alone. Thus the influence of both the concentration and the nature of the polymerization solvent on the reactivity was satisfactorily interpreted based on this micelle model. The formation of micelles was caused by the difference between the solubility of the PPE‐VBE macromonomer segment and the homopolymer of MMA or BMA which comprises the propagating chains in the polymerization solvent. The analysis of all the reactivity data of PPE‐VBE macromonomers can now be correlated with respect to the extents of the micelle formation as characterized by the partition coefficient, k. The value of k represents the concentration difference of both the PPE‐VBE macromonomer and its comonomer between the bulk of the free solvent and around the growing chain. The determined reactivity ratio is a product of the real reactivity ratio and the partition coefficient.