Article
  • Cationic Copolymerization of 4-Methyl-1-Vinylnaphthalene and Styrene
  • Shin HK, Kang DP, Ha CS, Lee JK, Cho WJ
  • 4-Methyl-1-Vinylnaphthalene과 Styrene의 양이온 공중합
  • 신흥건, 강동필, 하창식, 이진국, 조원제
Abstract
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 rl(4-MeV1N)=4.00 and r2(St)=1.75, respectively, by the Kelen-T d s method.

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 Tg를 구하였다. 4-MeV1N의 전환률과 얻어진 중합체의 고유점도 값은 온도가 증가할수록 감소하였으며 중합체의 Tg값은 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 rl(4-MeV1N)=4.00이고 r2(styrene) = 1.75이었다.

References
  • 1. Brunovollmert BPolymer Chemistry, Springer Verlag, New York, p. 44 (1973)
  •  
  • 2. Jenkins AD, Ledwith AReactivity, 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 WJPh.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)
  •  
  • Polymer(Korea) 폴리머
  • Frequency : Bimonthly(odd)
    ISSN 0379-153X(Print)
    ISSN 2234-8077(Online)
    Abbr. Polym. Korea
  • 2022 Impact Factor : 0.4
  • Indexed in SCIE

This Article

  • 1992; 16(1): 44-50

    Published online Jan 25, 1992