입체 장애 구조를 가진 이중 기능성 2-(2'-비닐옥시에톡시)-1-나프틸메틸리덴말로노니트릴의 합성 및 중합거동

이주연; 김무용

Polymer(Korea), Vol.21, No.6, 955-960, November, 1997

Synthesis of Sterically Hindered Bifunctional 2-(2'-Vinyloxyethoxy)-1-naphthylmethylidenemalononitrile and Its Polymerization Behaviors

이주연, 김무용

초록

2-(2'-비닐옥시에톡시)-1-나프탈데히드 (1)를 말로노:니트릴파 축합반응시켜 2-(2'-비닐옥시에톡시)-1-나프틸메틸리덴말로노니트릴 (2)를 합성하였다. 이중 기능성 비닐 에테르 단량체 2는 입체방해효과 때문에 자유라디칼 개시제에 의해서는 호모중합 또는 전자가 풍부한 게틸 비닐 에테르와 전자가 부족한 벤질리덴말로노니트릴과의 공중합은 진행되지 않았다. 그러나 화합물 2는 양이온 개시제에 의해서는 중합이 잘 진행되어 효과적인 비선형광학 발색단으로 예상되는 2-옥시-1-나프틸메틸리덴말로노니트릴을 측쇄에 포함하는 중합체 3을 형성하였다. 중합체 3은 아세톤같은 상용 용애에 잘 녹았으며 고유점도는 0.25-0.30 dL/g을 보였다. 아세톤 용액으로부터 얻어진 중합체 필름은 불투명하고 취약성을 보였다. 중합체 3은 300 ℃ 까지 열안정성을 보였으며 DSC로부터 얻어진 유리전이온도는 82 ℃였다.

2-(2'-Vinyloxyethoxy)-1-naphthylmethylidenemalononitrile (2) was prepared by the condensation of 2-(2'-vinyloxyethoxy)-1-naphthaldehyde (1) with malononitrile. Bifunctional vinyl ether monomer 2 did not homo- or copolymerize with electron-rich ethyl vinyl ether and electron-pooir benzylidenemalononitrile by free radical initiators due to the steric hindrance. However, compound 2 polymerized well by cationic initiators to give polymer 3 having 2-oxy-1-naphthylmethylidenemalononitrile, which is presumably effective NLO-chromophore for second order nonlinear optical applications. Polymer 3 was soluble in common solvents such as acetone and DMSO, and the inherent viscosities of the polymers were in the range of 0.25-0.30 dL/g. Films cast from acetone solution were cloudy and brittle. Polymer 3 showed a thermal stability up to 300 ℃ with a T_g of 82 ℃ in DSC thermogram.

Keywords:2-(2'-Vinyloxyethoxy)-1-naphthylmethylidenemalononitrile;bifumctional monomer;steric hindrance;cationic initiatr;NLO-chromophore

[References]

Stille JK, Chung DC, Macromolecules, 8, 114 (1975)
Cho I, Lee JY, J. Polym. Sci. C: Polym. Lett., 18, 639 (1980)
Cho I, Lee JY, Macromolecules, 16, 150 (1983)
Cho I, Lee JY, Macromolecules, 16, 1245 (1983)
Lee JY, Cho I, J. Polym. Sci. A: Polym. Chem., 25, 3089 (1987)
Cho I, Lee JY, J. Polym. Sci. C: Polym. Lett., 21, 389 (1983)
Florianczyk T, Sullivan C, Janovic Z, Vogl O, Polym. Bull., 5, 521 (1981)
Xi F, Bassett W, Vogl O, J. Polym. Sci. A: Polym. Chem., 21, 891 (1983)
Williams JK, Wiley DW, McKusick BC, J. Am. Chem. Soc., 84, 2210 (1984)
Hall HK, Ykman P, J. Am. Chem. Soc., 97, 800 (1975)
Hall HK, Rasoul HAA, Gillard M, Abdelkader M, Nogues P, Sentman RC, Tetrahedron Lett., 23, 603 (1982)
Hall HK, Padias AB, Accounts Chem. Res., 23, 3 (1990)
Kresel M, Garbratski U, Kohn DH, J. Polym. Sci. A: Polym. Chem., 2, 105 (1964)
Gilath A, Ronel SH, Shmueli M, Kohn DH, J. Appl. Polym. Sci., 14, 1491 (1970)
Ronel SH, Shmueli M, Kohn DH, J. Polym. Sci. A: Polym. Chem., 7, 2209 (1969)
Lieberson A, Kohn DH, J. Polym. Sci. A: Polym. Chem., 12, 2435 (1974)
Kharas G, Kohn DH, J. Polym. Sci. A: Polym. Chem., 21, 1457 (1983)
Kharas G, Kohn DH, J. Polym. Sci. A: Polym. Chem., 22, 583 (1984)
Angelorici MM, Kohn DH, J. Appl. Polym. Sci., 40, 485 (1990)
Tanaka H, Trends Polym. Sci., 31, 361 (1993)
Tanaka H, Trends Polym. Sci., 4, 106 (1996)
Lee JY, Polym. Bull., 36(5), 525 (1996)
Lee JY, Lee HJ, Kim MY, Bull. Korean Chem. Soc., 17, 257 (1996)
Lee JY, Kim MY, Ahn KD, Bull. Korean Chem. Soc., 18, 318 (1997)
Lee JY, Lee HJ, Kim MY, Polym. Bull., 38(1), 27 (1997)
Moore AHF, Org. Syn. Coll., 4, 84 (1963)
Griffin AC, Bhatti AM, Hung RS, "Nonlinear Optical and Electroactive Polymers," P.N. Prasad and D.R. Ulrich, Eds., p. 375, Plenum Press, New York (1987)
Corson BB, Stoughton RW, J. Am. Chem. Soc., 50, 2825 (1928)

[1] Stille JK, Chung DC, Macromolecules, 8, 114 (1975)

[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 (1984)

[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, Accounts 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)

[17] Kharas G, Kohn DH, J. Polym. Sci. A: Polym. Chem., 21, 1457 (1983)

[18] Kharas G, Kohn DH, J. Polym. Sci. A: Polym. Chem., 22, 583 (1984)

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

[20] Tanaka H, Trends Polym. Sci., 31, 361 (1993)

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

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

[23] Lee JY, Lee HJ, Kim MY, Bull. Korean Chem. Soc., 17, 257 (1996)

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

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

[26] Moore AHF, Org. Syn. Coll., 4, 84 (1963)

[27] Griffin AC, Bhatti AM, Hung RS, "Nonlinear Optical and Electroactive Polymers," P.N. Prasad and D.R. Ulrich, Eds., p. 375, Plenum Press, New York (1987)

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