공기분위기 하에서 열처리된 고입체 규칙성 폴리아크릴로니트릴의 XRD에 의한 환화반응 속도 연구

Zhi-xianXu; JingXu; Liang-huaXu; Yong-qiangDai; Li-weiXue; Ri-guangJin; Zhi-xian Xu; Jing Xu; Liang-hua Xu; Yong-qiang Dai; Li-wei Xue; Ri-guang Jin

Polymer(Korea), Vol.32, No.2, 150-156, March, 2008

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공기분위기 하에서 열처리된 고입체 규칙성 폴리아크릴로니트릴의 XRD에 의한 환화반응 속도 연구

Kinetic Study of Cyclization of High-Tacticity Polyacrylonitrile Heat-Treated under Air Atmosphere via XRD

Zhi-xianXu, JingXu¹, Liang-huaXu¹, Yong-qiangDai¹, Li-weiXue¹, Ri-guangJin^{1, †}

Anyang Normal College, Anyang 455000, Henan
¹Beijing University of Chemical Technology State Key Laboratory of Chemical Resource Engineering, Beijing 100029

Zhi-xian Xu, Jing Xu¹, Liang-hua Xu¹, Yong-qiang Dai¹, Li-wei Xue¹, and Ri-guang Jin^{1, †}

Anyang Normal College, Anyang 455000, Henan, China
¹State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China

E-mail:

Two different polyacrylonitrile samples (PANs, triad tacticity fraction is 0.25 and 0.64) were synthesized and used to study the kinetics of cyclization. Polymers were treated at different temperatures between 250 to 300 ℃ under air atmosphere, and analyzed by X-ray diffractometer. The sharp and strong peak at 2θ＝16.5o corresponds to a lateral repeat distance that is the (100) diffraction in hexagonal lattice, while the peak at 2θ＝25.5o reflects the (101) diffraction. In comparing their areas of different heat treated samples, the cyclization of both PANs was identified as a first-order reaction. The rate constants of cyclization reaction at different temperatures and the active energy parameter were obtained. This results might provide an important effect on pre-oxidation of polyacrylonitrile fiber.

Keywords:high-tacticity polyacrylonitrile;cyclization;kinetics

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[1] Bahl OP, Mathur RB, Kundra KD, Fibre Sci. Technol., 15, 147 (1981)

[2] Edie DD, Carbon, 36, 345 (1998)

[3] Bhanu VA, Rangarajan P, Wiles K, Bortner M, Sankarpandian M, Godshall D, Glass TE, Banthia AK, Yang J, Wilkes G, Baird D, McGrath JE, Polymer, 43(18), 4841 (2002)

[4] Tsai TS, Lin CH, J. Appl. Polym. Sci., 42, 3045 (1991)

[5] Thomas WM, Pelon JJ, J. Polym. Sci., 13, 329 (1954)

[6] Maslowski E, Urbanska A, Am. Text Intern., FW6-8, 5 (1989)

[7] Rangarajan P, Bhanu VA, Godshall D, Wilkes GL, McGrath JE, Baird DG, Polymer, 43(9), 2699 (2002)

[8] Tsai JS, J. Mater. Sci. Lett., 12(24), 1911 (1993)

[9] Bahl OP, Manocha LM, Carbon, 12, 417 (1974)

[10] Watt W, Carbon, 10, 121 (1972)

[11] Zhixian X, Riguang J, Journal of Beijing University of Chemical Technology, 34, 608 (2007)

[12] Zhixian X, Riguang J, J. Appl. Polym. Sci., (waiting publish)

[13] Dunham MG, Edie DD, Carbon, 30, 435 (1992)

[14] Noh I, Yu H, J. Polym. Sci. B: Polym. Lett., 4, 721 (1966)

[15] Morita K, Miyachi H, Hiramatsu T, Carbon, 19, 11 (1981)

[16] Hay JN, J. Polym. Sci. A-1, 6, 2127 (1968)

[17] Fitzer E, Muller DJ, Carbon, 13, 63 (1975)

[18] Kamide K, Ono H, Hisatani K, Polym. J., 24, 917 (1992)

[19] Nakano Y, Hisatani K, Polym. Int., 35, 207 (1994)

[20] Nakano Y, Hisatani K, Kamide K, Polym. Int., 35, 249 (1994)

[21] Nakano Y, Hisatani K, Kamide K, Polym. Int., 35, 397 (1994)

[22] Nakano Y, Hisatani K, Kamide K, Polym. Int., 36, 87 (1995)

[23] Perepelkin KE, Fibre Chem., 35, 409 (2003)

[24] Hu H, X-ray diffraction technology, Textile Industrial Company, China, p 43 (1988)

[25] Bohn CR, Schaefgen JR, Slatton WO, J. Polym. Sci., 55, 531 (1961)

[26] Renjith D, Nair CPR, Sivadasan P, Ninan KN, Polym. Int., 54, 1110 (2005)

[27] Zhao G, Chen B, J. Appl. Sci., 6, 278 (1988)