4-Methyl-1-Vinylnaphthalene과 Styrene의 양이온 공중합

신흥건; 강동필; 하창식; 이진국; 조원제

Polymer(Korea), Vol.16, No.1, 44-50, January, 1992

Export Citation

4-Methyl-1-Vinylnaphthalene과 Styrene의 양이온 공중합

Cationic Copolymerization of 4-Methyl-1-Vinylnaphthalene and Styrene

신흥건, 강동필, 하창식, 이진국, 조원제

초록

4-Methyl-1-vinylnaphthalene(4-MeV₁N)은 4-methyl-1-(1-naphthylethyl)chloride (4-MeN₁EC)를 탈염소화 반응시켜 합성하였다. 4-MeN₁EC는 1-methylnaphthalene을 출발물질로 하여 4-methyl-1-acetonaphthone, 4-methyl-1-(1-naphthyl)ethanol을 합성하고 4-methyl-1-(1-naphthyl)ethanol과 PCI₅를 반응시켜 합성하였다. -7O℃, -5O℃, -25℃ 및 0℃에서 TiCl₄를 개시제로 하여 4-MeV₁N의 양이 온중합에 대한 전환률 그리고 pol(4-methyl-1-vinylnaphthalene)의 고유점도와 T_g를 구하였다. 4-MeV₁N의 전환률과 얻어진 중합체의 고유점도 값은 온도가 증가할수록 감소하였으며 중합체의 T_g값은 148℃이었다. 또한, -50℃에서 TiC1₄를 사용하여 CH₂Cl₂에서 4-MeV₁N과 styrene의 양이온 공중합반응에 대한 단량체반응성을 구하였다. 공중합체 조성은 UV spectroscopy를 사용하여 구하였으며, Kelen-T d s식에 의해 구한 단량체 반응성비 값은 r_l(4-MeV₁N)=4.00이고 r₂(styrene) = 1.75이었다.

4-Methyl-1-vinylnaphthalene (4-MeV₁N) was synthesized by the dehydrochlorination of 4-methyl-1-(1-naphthylethyl)chloride, which had been prepared from 1-methylnaphthalene through the formation of intermediates, 4-methyl-1-acetonaphthone and 4-methyl-1-(1-naphthyl) ethanol. Cationic homopolymerization of 4-MeV₁N was carried out with titanium tetrachloride as a catalyst in dichloromethane at four different temperatures, ranging from -70℃ to 0℃. The conversion and the intrinsic viscosity were increased as the temperature decreased. The observed glass transition temperature of the homopolymer was 148℃. Copolymerization of 4-MeV₁N and styrene was also carried out at -50℃ under the same experimental condition. The copolymer composition was determined by UV spectroscopy. The reactivity ratios of 4-MeV₁N and styrene were estimated as r_l(4-MeV₁N)=4.00 and r₂(St)=1.75, respectively, by the Kelen-T d s method.

[References]

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[2] Jenkins AD, Ledwith A, "Reactivity, Mechanism and Structure in Polymer Chemistry," John Wiley & Sons, p. 16 (1974)

[3] Dainton FS, Sutherland GBBM, J. Polym. Sci., 4, 37 (1949)

[4] Kennedy JP, Thomas RM, J. Polym. Sci. A: Polym. Chem., A1, 331 (1963)

[5] Imanishi Y, Imamura H, Higashimura T, Kobunshi Kagaku, 27, 247 (1970)

[6] Imamura H, Higashimura T, Okamura S, J. Polym. Sci. A: Polym. Chem., 3, 2455 (1965)

[7] Okamura S, Higashimura T, Imanishi Y, Yamamoto R, Kimira K, J. Polym. Sci. C: Polym. Lett., 16, 2365 (1967)

[8] Marechal E, Bull. Soc. Chim. Fr., 268C, 1121 (1969)

[9] Zaffran C, Marechal E, Bull. Soc. Chim. Fr., 3521 (1971)

[10] Tortai J, Marechal E, Bull. Soc. Chim. Fr., 2673 (1971)

[11] Anton A, Marechal E, Bull. Soc. Chim. Fr., 3772 (1971)

[12] Zweggers J, Marechal E, Bull. Soc. Chim. Fr., 1157 (1972)

[13] Yuki H, Hadata K, Takeshita M, J. Polym. Sci. A: Polym. Chem., 1, 667 (1969)

[14] Overberger CG, Kamath VG, J. Am. Chem. Soc., 85, 446 (1963)

[15] Overberger CG, Amold LH, Taylor JJ, J. Am. Chem. Soc., 73, 5541 (1951)

[16] Overberger CG, Ehring RJ, Tanner D, J. Am. Chem. Soc., 76, 772 (1954)

[17] Anton A, Marechal E, Bull. Soc. Chim. Fr., 268C, 3753 (1971)

[18] Monomura Y, Mitch M, Macromol. Chem., 86, 119 (1968)

[19] Marechal E, Bit C, Sigwalt P, Bull. Soc. Chim. Fr., 11, 3487 (1966)

[20] Cho WJ, Ph.D. Thesis, The University of Paris VI (1978)

[21] Cho WJ, Bunnel CB, Marechal E, J. Polym. Sci., 18, 1991 (1980)

[22] Oh ST, Lee H, Cho WJ, Polym.(Korea), 10(7), 699 (1986)

[23] Ivin KJ, Spensley RH, J. Macromol. Sci.-Chem., 1, 653 (1967)

[24] Kovacs AJ, J. Polym. Sci., 30, 131 (1958)

[25] Martin GM, Rogers SS, Mandelkern L, J. Polym. Sci., 20, 579 (1956)

[26] Dunhan KR, Faber JW, Vandenberghe J, Fowler WF, J. Appl. Polym. Sci., 7, 897 (1963)

[27] Davies TE, Br. Plast., 32, 283 (1959)

[28] Frosini V, Magagnini PL, Eur. Polym. J., 2, 129 (1968)

[29] Corrado LC, J. Chem. Phys., 50, 2260 (1969)

[30] Kang DP, Ha CS, Cho WJ, J. Polym. Sci. A: Polym. Chem., 27, 1401 (1989)

[31] Price CC, Halpern BD, Voong ST, J. Polym. Sci., 6, 575 (1953)

[32] Meehan EJ, J. Polym. Sci. A: Polym. Chem., 1, 175 (1946)

[33] Kelen T, Tudos F, J. Macromol. Sci.-Chem., 9, 1 (1975)