Cationic Ring-opening Polymerization of 2-Isopropenyl-4-methylene-1,3-dioxolane at Ambient Temperature

Park JK; Choi HK; Endo T

Korea Polymer Journal, Vol.3, No.2, 106-110, October, 1995

Monomer of an unsaturated cyclic acetal having two carbon-carbon double bonds, 2-isopropenyl-4-methylene-1,3-dioxolane (I) has been synthesized from methacrolein and epichlorohydrin using tert-butoxide as a catalyst, and polymerized via cationic mechanism at ambient temperature. Linear soluble polymer containing pendant isopropenyl group II. was obtained from the cationic polymerization systems initiated by CH₃SO₃H at temperatures ranging from 0 to 60 ℃ in the presence of various nucleophilic additives or in the nucleophilic solvents. However, only crosslinked polymer, which is the product of simultaneous propagation of two carbon-carbon double bonds in I, was obtained without nucleophilic additive. This behavior was explained in terms of the stabilization of cationic species due to the interaction of cationic species with nucleophile.

[References]

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[1] Odian G, Principles of Polymerization, 2nd ed., John Wiley & Sons, New York (1984)

[2] Yokozawa T, Hayashi R, Endo T, Macromolecules, 25, 3313 (1992)

[3] Nagasaki Y, Ito H, Tsuruta T, Makromol. Chem., 187, 23 (1986)

[4] Park J, Yokozawa T, Endo T, J. Polym. Sci. A: Polym. Chem., 31, 1141 (1993)

[5] Park J, Kihara N, Ikeda T, Endo T, J. Polym. Sci. A: Polym. Chem., 31, 1083 (1993)

[6] Higashimura T, Aoshima S, Sawamoto M, Makromol. Chem. Makromol. Symp., 13-14, 457 (1988)

[7] Cho C, Feit B, Webster O, Macromolecules, 23, 1918 (1990)

[8] Lin CH, Matyjaszewski K, Polym. Prepr., 31, 599 (1990)

[9] Gutmann V, Electrochim. Acta, 21, 661 (1976)

[10] March, in Advanced Organic Chemistry, 3rd Ed., John Wiley & Sons, New York (1985)

[11] Gutmann V, Chem. Br., 7, 102 (1971)

[12] Gutmann V, Angew. Chem.-Int. Edit., 82, 858 (1970)

[13] Gutmann V, Mayer U, Mh. Chem., 100, 248 (1969)

[14] Gutmann V, Cood. Chem. Rev., 18, 225 (1976)

[15] Henderson WA, Streuli CA, J. Am. Chem. Soc., 82, 5791 (1960)

[16] Arnett EM, Wu CY, J. Am. Chem. Soc., 84, 1684 (1962)

[17] Deno NC, Turner JO, J. Org. Chem., 31, 1969 (1966)