Abstract
A method to prepare soluble intramolecularly crosslinked copolymers (microgel) by radical copolymerization of vinyl monomer and divinyl compound was developed. Methyl methacrylate (MMA) and p-divinylbenzene (p-DVB) was copolymerized in the presence of a high concentration of transfer agent (CBr4) in benzene. As the ratios of p-DVB and CBr4 to MMA increased, the number average molecular weight decreased and the structure of the microgel became tighter. The soluble polymer was obtained with very high conversion (70—88%). It was confirmed by the characterization of fractionated product that about 50% of the soluble polymers were intramolecularly crosslinked copolymer. The reactivity ratio r (=k13/k12) (M1 = MMA, M2 = p-DVB, M3 = pendant double bond) was not constant throughout the course of all the reactions, and became progressively small with time. rM (k11/k12), however, was always constant (0.27). This can be explained if we assume that the intramolecular crosslink is more rapidly formed than that of the intermolecular and a large amount of loops are formed at the early stage of copolymerization.
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Chen, H., Won, Y., Ishizu, K. et al. Preparation of Soluble Poly(methyl methacrylate–p-divinylbenzene) in the Presence of Tetrabromomethane. Polym J 17, 687–692 (1985). https://doi.org/10.1295/polymj.17.687
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DOI: https://doi.org/10.1295/polymj.17.687