LIVING CATIONIC HOMOPOLYMERIZATION AND COPOLYMERIZATION OF VINYL ETHERS BEARING A PERFLUOROALKYL PENDANT

Two vinyl ethers with a perfluoroalkyl group, CH//2 equals CH-OCH//2CH//2N(n-C//3H//7)-SO//2C//8F//1//7 (1) or CH//2 equals CH-OCH//2CF//2CF//2H (2), were polymerized with boron trifluoride etherate (BF//3OEt//2) and hydrogen iodide/iodine (HI/I//2) as initiators at minus 15 degree C in methylene chloride or 1,1,2-trichloro-1,1,1,2-trichloro-1,2,2-trifluoroethane. With both initiators, vinyl ether 1 was quantitatively polymerized. The polymers obtained with H1/1//2 at conversions below 50% were soluble, and in this range their number-average molecular weight increased with monomer conversion, indicating the involvement of a long-lived growing species. In contrast, monomer 2 gave insoluble products with BF// 3OEt//2, and it could not be polymerized with HI/I//2 above 30% conversion. The HI/I//2-initiated copolymerization of 1 and 2 with 2-chloroethyl vinyl ether (CEVE) showed that the reactivity of these monomers are in the order CEVE greater than 1 greater than 2.