PEN계 공중합체의 합성과 미세구조

박상순; 강승구; 조현철; 윤인선; 권영택; 임승순

Polymer(Korea), Vol.21, No.1, 16-25, January, 1997

Export Citation

PEN계 공중합체의 합성과 미세구조

Synthesis and Sequence Distribution of PEN Copolymers

박상순, 강승구, 조현철, 윤인선, 권영택, 임승순

초록

Poly(ethylene 2,6-naphthalate-co ethylene phthalate) (PEN/PEP) 및 poly(ethylene 2,6-naphthalate-co ethylene isophthalate) (PEN/PEI) 랜덤공중합체를 합성하였고 ¹H-NMR을 이용하여 미세구조분포를 살펴보았다. PEN 공중합체의 융점은 프탈산(또는 이소프탈산) 디메틸에스테르 mol% 함량이 증가갈수록 점차로 감소하는 경향을 나타냈다. 이들 공중합체의 융점강하경향은 몰분율(X_a) 보다는 dyad 방식으로 계산된 sequence 성장확률(P)값에 잘 일치함을 나타냈다. 열처리시킨 PEN 공중합체의 naphthalate 블록길이 (L_nN)는 급냉시킨 PEN 공중합체의 블록길이보다 길어졌다. 이러한 결과로부터 급냉/열처리시킨 PEN 공중합체들간에 있어서 열적성질 및 결정화거동의 변화는 미세구조길이 분포와 중요한 관계가 있음을 알았다.

Poly(ethylene 2,6-naphthalate-co ethylene phthalate) (PEN/PEP) and poly(ethylene 2,6-naphthalate-co ethylene isophthalate) (PEN/PEI) random copolymers were synthesized and their sequence distributions were investigated by ¹H-NMR spectroscopy. In PEN copolymers, point was depressed gradually with the increase of dimethyl phthalate(or dimethyl isophthalate) mol% in composition. The melting depression of PEN copolymers were not derectly depended on molar fraction, X, but rather on the sequence propagation probability, P, which is calculated by dyad method. The block length, L_nN, of naphthalate unit in the annealed copolymers was larger than that of the quenched copolymers. It can be found from the result that the variation of the thermal property and the crystallization behavior have a significant relation to the sequence length distribution of quenched/annealed PEN copolymers.

Keywords:poly(ethylene 2,6-naphthalate) copolymers;sequence distribution;degree of randomness

[References]

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[1] Kamiya N, Yamamoto Y, Inoue Y, Chujo R, Macromolecules, 22, 1676 (1989)

[2] Park SS, Im SS, Kim DK, J. Polym. Sci. A: Polym. Chem., 32(15), 2873 (1994)

[3] Tijsma EJ, Vanderdoes L, Bantjes A, Vulic I, Buning GH, Macromolecules, 27(1), 179 (1994)

[4] Park SS, Im SS, Polym.(Korea), 18(5), 708 (1994)

[5] Yamadera R, Murano M, J. Polym. Sci., 5, 2259 (1967)

[6] Lenz RW, Martin E, Schuler AN, J. Polym. Sci. A: Polym. Chem., 11, 2265 (1973)

[7] Lenz RW, Ohata K, Funt J, J. Polym. Sci. A: Polym. Chem., 11, 2273 (1973)

[8] Lenz RW, Go S, J. Polym. Sci. A: Polym. Chem., 11, 2927 (1973)

[9] Lenz RW, Go S, J. Polym. Sci. A: Polym. Chem., 12, 1 (1974)

[10] Lenz RW, Schuler AN, J. Polym. Sci. Polym. Symp., 63, 343 (1978)

[11] Backson SC, Kenwright AM, Richards RW, Polymer, 36(10), 1991 (1995)

[12] Buchner S, Wiswe D, Zachmann HG, Polymer, 30, 480 (1989)

[13] Flory PJ, Trans. Faraday Soc., 51, 848 (1955)