폴리부틸렌테레프탈레이트와 파라아세톡시벤조산의 용융공중합 속도론에 대한 고찰

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

Polymer(Korea), Vol.24, No.1, 16-22, January, 2000

Export Citation

폴리부틸렌테레프탈레이트와 파라아세톡시벤조산의 용융공중합 속도론에 대한 고찰

Kinetic Consideration of Melt-copolymerization of Poly(butylene terephthalate) (PBT) and p-Acetoxybenzoic Acid (ABA)

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-acetoxylbenzoic acid, ABA)을 용융 에스테르 교환반응시킴으로써 주쇄 고분자에 강직한 벤젠고리가 도입된 poly(butylene terephthalate-co-oxybenzoate) (PBOT)를 합성하였다. PBT와 ABA를 다양한 조성비에서 중합하는 과정의 속도론적 고찰을 통해 ABA의 단독중합 속도상수와 PBT에의 공중합 속도상수 및 그 비를 구하였으며 각각의 활성화에너지를 구하였다. PBT와 ABA의 조성비를 4/6, 5/5, 6/4로 하고 온도를 각각 250, 260, 270°C로하여 실험한 결과 공중합반응은 ABA함량이 낮고 또 그 전환율이 크지 않을 경우 의사 2차반응으로 볼수 있었다. 이때의 공중합 속도에 대한 단독중합 속도의 비는 1.08에서 3.17사이의 값을 가졌으며, ABA함량과 온도가 높을수록 큰 값을 가졌다. 이로써 PBT/ABA계의 공중합은 반응온도가 높고 ABA조성비가 클수록 ABA의 블록성이 강해지는 경향을 나타냈다.

Poly(butylene terephthalate-co-oxybenzoate)(PBOT) containing mesogenic oxybenzoate units in the main chain was synthesized through ester exchange reaction by melt mixing of poly(butylene terephthalate)(PBT) and p-acetoxybenzoic acid(ABA). From the kinetics of the copolymerization reaction, the activation energies and the rate constants of homopolymerization and copolymerization, k_b and k_c, could be determined. From the reaction conditions of different compositions, 4/6, 5/5, and 6/4 of PBT/ABA, at 250, 260, and 270 ℃, it was revealed that copolymerization between PBT and ABA proceeds on a pseudo-second order reaction if the ABA content and its conversion are low. In this case, the ratio of rate constants of homopolumerization to copolymerixation was in the range from 1.08 to 3.17, indicating that the copolymer with more notable block character was obtained at the higher mole fraction of ABA and at higher temperature.

[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, Westdahl 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] Mathew J, Ghadage RS, Ponrathnam S, Prasad SD, Macromolecules, 27(15), 4021 (1994)

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

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

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

[17] Mathew J, Bahulekar RV, Macromolecules, 25, 7338 (1992)

[18] Han X, Hall HK, Macromolecules, 29, 1874 (1992)

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