용융 에스테르 교환반응에 의해 제조된 폴리부틸렌테레프탈레이트/파라아세톡시벤조산 공중합체의 서열구조와 열적 성질

김도경; 박수영; 박종래; Do-Gyung Kim; Soo Young Park; Chong Rae Park

Polymer(Korea), Vol.24, No.1, 58-64, January, 2000

Sequence Structure and Thermal Property of Poly(butylene terephthalate) (PBT)/p-Acetoxybenzoic Acid(ABA) Copolymers Obtained Through Melt Trans-esterification Reaction

김도경, 박수영^†, 박종래

서울대학교 섬유고분자공학과

Do-Gyung Kim, Soo Young Park^†, and Chong Rae Park

Department of Fiber and Polymer Science, Seoul National University, Seoul 151-742, Korea

E-mail:

초록

폴리부틸렌테레프탈레이트(poly(butylene terephthalate), PBT)와 파라아세톡시벤조산(p-acetoxybenzoic acid, ABA)의 조성비를 4/6, 5/5, 6/4로 하고, 온도를 각각 250, 260, 270°C로 하여 용융 에스테르 교환반응시킴으로써 poly(butylene terephthalate-co-oxybenzoate)(PBOT)를 합성하였다. 이에 대한 양성자 핵자기 공명 분광(¹H FT-NMR)분석을 통해서 분자내 서열 분석을 해본 결과 연속된 oxybenzoate단위의 수는 1.2에서 1.5사이의 값을 가졌다. 이 값은 같은 조성비 및 같은 반응온도에서 합성된 폴리에틸렌테레프탈레이트(poly(ethylene terephthalate), PET/ABA(PEOT)쌍에 비해 상대적으로 큰 값임을 알 수 있었다. 이와 같은 블록길 이상의 차이는 열분해 거동에 영향을 미치며 그 결과 폴리옥시벤조에이트(PBO), PBT 및 PEOT가 1단계의 열분해를 하는 반면 PBOT는 2단계의 열분해 거동을 나타내었다. 또한 PBOT는 PBT-rich 상, PBT와 ABA의 랜덤분포 상 및 ABA-rich상의 3상 구조를 가지는 것으로 추측되었다.

Poly(butylene terephthalte-co-oxybenzoate) (PBOT) was synthesized by melt trans-esterification of poly(butyldne terephthalate(PBT) and p-acetoxybenzoic acid(ABA)at 250, 260, and 270 ℃ with the compositions of PBT/ABA of 4/6, 5/5, 6/4. The sequence analysis of PBOT with a ¹H FT-NMR indicated that the number of consecutive oxybenzoate units range from 1.2 to 1.5, which is larger than that of the corresponding poly(ethylene terephthalate)(PET)/ABA(PEOT) obtained at the same reaction conditions as the PBOT. The difference in the block length influenced the thermal degradation behavior: Polyoxybenzoate(POB), PBT and PBOT showed one-step degradation whereas PBOT exhibited two-step degradation. THe results suggested that PBOT consisted of three phases of PBT-rich phase, random phase of PBT andABA, and ABA-rich phase.

[References]

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[Referenced By]

[1] Jackson WJ, Kuhfuss HF, J. Polym. Sci. A-Polym. Chem., 14, 2043 (1976)

[2] Zachariades A, Economy EJ, Logan JA, J. Appl. Polym. Sci., 27, 2009 (1982)

[3] Zachariades A, Logan JA, Polym. Eng. Sci., 23, 797 (1983)

[4] Joseph E, Wilkes GL, Baird DG, Polymer, 26, 688 (1985)

[5] Sawyer LC, J. Polym. Sci. C-Polym. Lett., 22, 347 (1984)

[6] Blackwell J, Lieser G, Gutierrez GA, Macromolecules, 16, 1418 (1983)

[7] Sun T, Porter RS, Polym. Commun., 31, 70 (1990)

[8] Hedmark PG, Westdah M, Werner PE, Gedde UW, Polymer, 30, 2068 (1989)

[9] Nicely VA, Dogherty JT, Renfro LW, Macromolecules, 20, 573 (1987)

[10] Qanch L, Hornbogen E, Volksen W, Economy J, J. Polym. Sci. A-Polym. Chem., 27, 775 (1989)

[11] Chung CL, Su AC, Chu CF, Macromolecules, 28(21), 7121 (1995)

[12] Gedde UW, Buerger D, Boyd RH, Macromolecules, 20, 988 (1987)

[13] Chen MS, Chang NH, Chang BC, Tsai HB, Lee C, Polymer, 30, 1472 (1989)

[14] Goranov K, Fakirov S, Zheliaskova A, Hinov HP, Mol. Cryst. Liq. Cryst., 173, 31 (1989)

[15] Goranov K, Fakirov S, Zachmann HG, Macromol. Chem., 194, 1791 (1993)

[16] Li VG, Huang MR, Guam GH, Sun T, Angew. Makromol. Chem., 227, 69 (1995)

[17] Economy J, Siemens R, Karis T, Geiss R, Viney C, Volksen W, Macromolecules, 21, 2777 (1988)

[18] Cao J, Su WC, Wu ZW, Kitayama T, Hatada K, Polymer, 35(16), 3549 (1994)