테레프탈산 공중합체의 화학구조 연구

유희열; 김상욱; Okui N

Journal of the Korean Industrial and Engineering Chemistry, Vol.4, No.4, 770-775, December, 1993

테레프탈산 공중합체의 화학구조 연구

Chemical Structure Study on Copolyterephthalates Based on Ethylene Glycol and 1, 4-cyclohexane Dimethanol by High Resolution NMR Analysis

유희열, 김상욱, Okui N

초록

에틸렌글리콜과 1, 4-시클로헥산디메탄올의 테레프탈산 공중합체인, poly(ethylene terephthalate-co-1, 4-cyelohexylene dimethylene terephthalate), p(ET-CT)의 화학 구조를 고분해능 NMR 분석을 통하여 조사하였다. ¹H NMR 분석에서 메칠렌기에 의한 chemical shift가 ET, 트란스 CT, 및 시스 CT로 분리됨에 따라 공중합조성 및 이성질체의 비율을 구할 수 있었다. ¹³C NMR 분석에서 카르보닐기에 연결된 벤젠기의 탄소가 diad로 분리됨에 따라 공중합 연쇄 분포(co-polymer sequence distribution)를 구한 결과, p(ET-CT) 공중합체는 랜덤공중합체임이 판명되었다. 아울러 랜덤 통계식을 이용하여 공중합 연쇄의 분포 및 평균길이를 구할 수 있었다.

Chemical structure of poly(ethylene terephthalate-co-1, 4-cyclohexylene dimethylene terephthalate), p(ET-CT) copolyesters was investigated by High Resolution NMR analysis. The copolymer composition and isomeric ratio were determined by methylene resonance peaks which were separated into three peaks corresponding to ET, trans CT and cis CT units, respectively. The copolymer sequence distribution was evaluated from the carbon resonance peaks connected to carbonyl groups in benzene, indicating died distribution. According to statistics model, these copolyesters are almost random copolymers. The copolymer sequence distribution could be simulated and its averaged length was calculated by random copolymer statistics.

[References]

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Aspy PA, Denison EE, Modern Plast., Aug., 74 (1982)
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Yoo HY, submitted in Polymer (1993)
Yoo HY, accepted in Polymer (1993)

[1] Kibler CJ, Bell A, Smith JG, U.S. Patent, 2,901,466 (1959)

[2] Martin EV, Text. Res. J., 32, 619 (1962)

[3] Aspy PA, Denison EE, Modern Plast., Aug., 74 (1982)

[4] Benavente R, Perena JM, Polym. Eng. Sci., 27, 913 (1987)

[5] Golvoy A, Cheung MF, J. Appl. Polym. Sci., 37, 1019 (1989)

[6] Nadkarni VM, Shingkali VL, Jog JP, J. Macromol. Sci.-Phys., 26, 341 (1987)

[7] Benavente R, Perena JM, Rev. Plast. Moderos, 394, 585 (1989)

[8] Benavante R, Perena JM, Makromol. Chem., 189, 1207 (1989)

[9] Wunderich B, "Macromolecular Physics," Vol. 1, Chap. 2. 4. 8, Academic Press (1973)

[10] Kamiya N, Yamamoto Y, Inoue Y, Jujo R, Doi Y, Macromolecules, 22, 1676 (1989)

[11] Chujo R, Koyama K, Ando I, Inoue Y, Polym. J., 3, 394 (1972)

[12] Murano M, Polym. J., 1, 660 (1970)

[13] Yamadera R, Murano M, J. Polym. Sci. A: Polym. Chem., 1, 3183 (1963)

[14] Yoo HY, Umemoto S, Kikutani T, Okui N, Polym. Prepr., 41, 1359 (1992)

[15] Wahl GH, Peterson MR, Chem. Commun., 1167 (1970)

[16] Bovey FA, Tiers GBD, J. Polym. Sci., 44, 173 (1960)

[17] Miyake A, Sakibara M, Pepts. Prog. Polym. Phys., 5, 257 (1962)

[18] Yoo HY, submitted in Polymer (1993)

[19] Yoo HY, accepted in Polymer (1993)