Abstract
Three vinyl ethers with a p-substituted phenoxyl group in the pendant, CH2=CH-O-CH2CH2-O-C6H4X (p) (X: 1, H; 2, OCH3; 3, Cl), formed living polymers with a narrow molecular weight distribution in the polymerization initiated by a mixture of hydrogen iodide and iodine (HI/I2) either in toluene at −15°C or in methylene chloride at −40°C. The number-average molecular weight of the polymers increased in direct proportion to monomer conversion, and their molecular weight distribution stayed narrow (Mw/Mn=1.1–1.3) independent of conversion. The rate of the homopolymerizations depended clearly on the p-substituents in the monomers and decreased in the order OCH3(2)>H(1)>Cl(3). A similar but smaller dependence was observed in the copolymerizations of 1 with 2 and 3 initiated by HI/I2 in toluene at −15°C where living random copolymers with a narrow molecular weight distribution were obtained. According to a model reaction and 13C NMR analysis of the monomers, their p-substituents affect not their reactivities but those of the propagating species, thereby resulting in great changes in the homopolymerization rates. In contrast to 1–3, the corresponding nitro derivative (4; X=NO2) did not form a living homopolymer, but did give a living copolymer with 1 when polymerized by HI/I2 in toluene at −15°C.
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Choi, W., Sawamoto, M. & Higashimura, T. Living Cationic Polymerization of 2-Phenoxyethyl Vinyl Ether and Its Ring-Substituted Derivatives: Effects of para-Substituents. Polym J 19, 889–896 (1987). https://doi.org/10.1295/polymj.19.889
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DOI: https://doi.org/10.1295/polymj.19.889
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