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Cationic copolymerization of cyclic ketene acetals: The effect of substituents on reactivity
Authors:Zhihong Wu  Liwei Cao  Charles U Pittman
Abstract:Cationic copolymerizations of 4-methyl-2-methylene-1,3-dioxane, 2 (M1), with 2-methylene-1,3-dioxane, 1 (M2); of 4,4,6-trimethyl-2-methylene-1,3-dioxane, 3 (M1), with 2-methylene-1,3-dioxane, 1 (M2); of 4-methyl-2-methylene-1,3-dioxolane, 5 (M1), with 2-methylene-1,3-dioxolane, 4 (M2); and of 4,5-dimethyl-2-methylene-1,3-dioxolane, 6 (M1), with 2-methylene-1,3-dioxolane, 4 (M2) were conducted. The reactivity ratios for these four types of copolymerizations were r1 = 1.73 and r2 = 0.846; r1 = 2.26 and r2 = 0.310; r1 = 1.28 and r2 = 0.825; r1 = 2.23 and r2 = 0.515, respectively. The relative reactivities of these monomers towards cationic polymerization are: 3 > 2 > 1; and 6 > 5 > 4. With both five- and six-membered ring cyclic ketene acetals, the reactivity increased with increasing methyl substitution on the ring. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 861–871, 1998
Keywords:2-methylene-1  3-dioxane  4-methyl-2-methylene-1  3-dioxane  4  4  6-trimethyl-2-methylene-1  3-dioxane  2-methylene-1  3-dioxolane  4-methyl-2-methylene-1  3-dioxolane  4  5-dimethyl-2-methylene-1  3-dioxolane  cationic copolymerization  reactivity ratio  relative reactivity  ring-retained polymerization  cyclic ketene acetals
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