Synthesis of Sterically Hindered Trivinyl Ethers Containing an Electron-Acceptor and Their Polymerization Behavior

Lee JY; Kim JH; Kim MJ; Jin MK

Korea Polymer Journal, Vol.7, No.4, 229-236, August, 1999

2,3,4-Tri-(2''-vinyloxyethoxy)benzylidenemalononitrile(2a), methyl2,3,4-tri-(2''-vinyloxyethoxy)benzylidenecyanoacetate(2b), 2,4,6-tri-(2''-vinyloxyethoxy)benzylidenemalononitrile(4a), and methyl 2,4,6-tri-(2''-vinyloxyethoxy)benzylidenecyanoacetate(4b) were prepared and investigated their polymerization behavior was investigated. Compounds2a-b and 4a-b were prepared by the condensation of 2,3,4-tri-(2''-vinyloxyethoxy)benzaldehyde(1) and 2,4,6-tri-(2''-vinyloxyethoxy)benzaldehyde(3) with malononitrile or methyl cyanoacetate, respectively. The electron-deficient terminal olefin group participated in the vinyl ether polymerization and radical polymerization of2a and 2b led to optically transparent crosslinked polymers 5a and 5b in high yields. However, compounds 4a and 4b did not polymerize by radical initiators due to the steric hindrance. The trivinyl ether compounds2a-b and 4a-b were polymerized by cationic initiators to give crosslinked poly(vinyl ether) 7a-b and 8a-b containing oxybenzylidenemalononitrile or oxycyanocinnamate, which may be effective NLO-chromophore for secondorder nonlinear optical applications in the side chain. Polymers5-8 were not soluble in common organic solvents such as acetone and DMSO due to crosslinking. Polymers5-8 showed a thermal stability up to 300℃ in TGA thermostats.

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[2] Cho I, Lee JY, J. Polym. Sci. C: Polym. Lett., 18, 639 (1980)

[3] Cho I, Lee JY, Macromolecules, 16, 150 (1983)

[4] Cho I, Lee JY, Macromolecules, 16, 1245 (1983)

[5] Lee JY, Cho I, J. Polym. Sci. A: Polym. Chem., 25, 3089 (1987)

[6] Cho I, Lee JY, J. Polym. Sci. C: Polym. Lett., 21, 389 (1983)

[7] Florianczyk T, Sullivan C, Janovic Z, Vogl O, Polym. Bull., 5, 521 (1981)

[8] Xi F, Bassett W, Vogl O, J. Polym. Sci. A: Polym. Chem., 21, 891 (1983)

[9] Williams JK, Wiley DW, McKusick BC, J. Am. Chem. Soc., 84, 2210 (1962)

[10] Hall HK, Ykman P, J. Am. Chem. Soc., 97, 800 (1975)

[11] Hall HK, Rasoul HAA, Gillard M, Abdelkader M, Nogues P, Sentman RC, Tetrahedron Lett., 23, 603 (1982)

[12] Hall HK, Padias AB, Acc. Chem. Res., 23, 3 (1990)

[13] Kresel M, Garbratski U, Kohn DH, J. Polym. Sci. A: Polym. Chem., 2, 105 (1964)

[14] Gilath A, Ronel SH, Shmueli M, Kohn DH, J. Appl. Polym. Sci., 14, 1491 (1970)

[15] Ronel SH, Shmueli M, Kohn DH, J. Polym. Sci. A: Polym. Chem., 7, 2209 (1969)

[16] Lieberson A, Kohn DH, J. Polym. Sci. A: Polym. Chem., 12, 2435 (1974)

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[19] Angelorici MM, Kohn DH, J. Appl. Polym. Sci., 40, 485 (1990)

[20] Tanaka H, Trends Polym. Sci., 1, 361 (1993)

[21] Tanaka H, Trends Polym. Sci., 4, 106 (1996)

[22] Lee JY, Polym. Bull., 36(5), 525 (1996)

[23] Lee JY, Kim MY, Ahn KD, Bull. Korean Chem. Soc., 18, 318 (1997)

[24] Corson BB, Stoughton RW, J. Am. Chem. Soc., 50, 2825 (1928)

[25] Lee JY, Lee HJ, Kim MY, Polym. Bull., 38(1), 27 (1997)

[26] Lee JY, Polym. Bull., 33(6), 635 (1994)