Polymerization of methyl methacrylate by charge‐transfer mechanism with 2,2′‐bipyridine and iron (III) complex

Abstract

Polymerization of methyl methacrylate (MMA) by the charge-transfer complex formed by the interaction of 2,2′-bipyridine (bpy), MMA, and carbon tetrachloride (CCl4) was studied in dimethylsulfoxide (DMSO) at 60°C. The rate of polymerization (Rp) is sensitive to the [CCl4] at low concentration of CCl4, but at a higher concentration it is practically independent of [CCl4]. Rp is proportional to [MMA]1.45±0.04 and [bpy]0.52±0.04 when [CCl4] > [bpy], and the average rate constant, k, at 60°C for the polymerization of MMA was 7.14 ± 0.40 × 10−6 L mol−1s−1. Kinetic studies showed that the polymerization proceeds through free radical intermediates. This article also reports the polymerization of MMA initiated by bpy and CCl4 and accelerated by Lewis acid, hexakis (dimethylsulfoxide)iron(III) perchlorate [Fe(DMSO)6](ClO4)3 at 60°C. The glass transition temperature and molecular weights of the samples were investigated by using differential scanning calorimetry and gel permeation chromatography techniques, respectively. Probable reaction mechanisms are proposed to explain the observed results. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2097–2103, 1997