主链含酰亚胺环和炔基的聚酰亚胺型聚氨酯弹性体的合成及阻燃性能

doi:10.7503/cjcu20130586

摘要/Abstract

摘要：

以均苯四甲酸酐、 D,L-苯丙氨酸和1,4-丁炔二醇为原料合成了一种含有酰亚胺环和炔基的二醇, 并以其为扩链剂, 采用预聚体法, 与4,4-二苯基甲烷二异氰酸酯(MDI)和聚四氢呋喃醚二醇(PTMG)反应, 合成了不同硬段含量的主链含有酰亚胺环和炔基的热塑性聚酰亚胺型聚氨酯弹性体. 用红外光谱(FTIR)、电子拉力机、热失重分析(TG)、广角X射线衍射(XRD)、 UL-94垂直燃烧和极限氧指数对聚酰亚胺型聚氨酯弹性体进行了表征. 结果表明, 这种聚氨酯呈现出无定形结构; 其拉伸强度随着硬段含量的增加而增大; 与传统的热塑性聚氨酯相比, 酰亚胺环和炔基改性的聚酰亚胺型聚氨酯弹性体的热分解过程非常缓慢, 呈现出较好的热稳定性; 不同硬段含量的聚酰亚胺型聚氨酯弹性体的UL-94垂直燃烧均达到V-2级别; 其极限氧指数随着硬段含量的增加而增大.

关键词: 聚酰亚胺型聚氨酯弹性体, 酰亚胺, 炔基, 热稳定性, 阻燃性能

Abstract:

A kind of glycol containing imide and alkynyl function was synthesized from pyromellitic dianhydride(PMAD), butynediol(2-butyne-1,4-diol) and D,L-phenylalanine(DLP). Linear imide and alkynyl modified thermoplastic poly(imide-urethane)s were prepared by the obtained glycol, 4,4'-diphenylmethane diisocyanate(MDI) and poly(tetrahydrofuran)(PTMG) via prepolymerization. The poly(imide-urethane)s structures were characterized with Fourier transform infrared spectroscopy(FTIR), universal testing machine tension, thermalgravimetric analysis(TGA), wide-angle X-ray diffraction(XRD). The results showed that the novel thermoplastic poly(imide-urethane)s elastomer with amorphous structure were successfully synthesized. The tensile strength increases with the hard segment contents. Comparing with the conventional thermoplastic polyurethanes extended by 1,4-butanediol, the poly(imide-urethane)s show slower thermal degradation rate during the degradation process. The polymers with different hard segments contents all reach a UL-94 V-2 rating, and the limiting oxygen index(LOI) value increases with different hard segments contents.

Key words: Thermoplastic polyurethane, Imide, Alkynyl, Thermal stability, Flame retardancy

中图分类号:

O631.1

TrendMD:

唐启恒, 艾青松, 杨荣杰, 何吉宇. 主链含酰亚胺环和炔基的聚酰亚胺型聚氨酯弹性体的合成及阻燃性能. 高等学校化学学报, 2014, 35(1): 199.

TANG Qiheng, AI Qingsong, YANG Rongjie, HE Jiyu. Synthesis and Flame Retardancy of Novel Thermally Stable Poly(imideurethane)s Containing Imide and Alkynyl Groups in Main Chain. Chem. J. Chinese Universities, 2014, 35(1): 199.

图/表 5

参考文献 28

[1]	Liu X. H., Zhao Y., Liu Z., Wang D. J., Wu J. G., Xu D. F., Chem. J. Chinese Universities, 2008, 29(10), 2096—2100
	(刘新海, 赵莹, 刘智, 王笃金, 吴瑾光, 徐端夫.高等学校化学学报, 2008,29(10), 2096—2100)
[2]	Zhang A.S., Wang D., Yang X. L., Wu J. J., Zhu C. Z., Yang S. G., Acta Polymerica Sinica, 2013, (7), 943—948
	(张安苏, 汪东, 杨晓丽, 吴俊杰, 朱才镇, 杨曙光. 高分子学报, 2013, (7), 943—948)
[3]	Wiggins M. J., MacEwan M., Anderson J. M., Hiltner A., J. Biomed. Mater. Res. Part A, 2004, 68A(4), 668—683
[4]	You C. J., Xu J. G., Zeng Y. Z., Li Y., Jia D. M., Nishi T., Chinese Journal of Polymer Science, 2010, 28(6), 913—922
[5]	Gao C. H., Chen M. Y., Ni J. N., Hua J. J., Xu X. M., Lin W. W., Zheng Q., Chinese Journal of Polymer Science, 2010, 28(2), 219—229
[6]	Luo J. B., Ma C., Liao R., Wan J., Zhang P., Zhang J., Chem. J. Chinese Universities, 2010, 31(6), 1268—1273
	(罗建斌, 马晨, 廖戎, 万静, 张鹏, 张杰.高等学校化学学报, 2010,31(6), 1268—1273)
[7]	Hu X. Y., Zhang Y. X., Zhang T., Yu Q., Chen H., Chem. J. Chinese Universities, 2009, 30(3), 613—617
	(胡小洋, 张燕霞, 张弢, 于谦, 陈红.高等学校化学学报, 2009,30(3), 613—617)
[8]	Wang L.L., Dong X., Liu X. G., Xing Q., Huang M. M., Hu H. Q., Wang D. J., Acta Polymerica Sinica, 2013, (3), 367—376
	(王莉莉, 董侠, 刘祥贵, 邢倩, 黄淼铭, 胡海青, 王笃金. 高分子学报, 2013, (3), 367—376)
[9]	Liu C. C., Zhang A. Y., Ye L., Feng Z. G., Chinese Journal of Polymer Science, 2013, 31(2), 251—262
[10]	Chen J. H., Liu W. Q., Xuan Y. N., Zhang B., Guangzhou Chemistry, 2003, 28(4), 6—11
	(陈精华, 刘伟区, 宣宜宁, 张斌.广州化学, 2003,28(4), 6—11)
[11]	Chen J. H., Liu W. Q., Xuan Y. N., Zhang B., Polyurethane Industry, 2004, 19(1), 12—14
	(陈精华, 刘伟区, 宣宜宁, 张斌.聚氨酯工业, 2004,19(1), 12—14)
[12]	Takeichi T., Suefuji K., Inoue K., J. Polym. Sci. Part A: Polym. Chem., 2002, 40(20), 3497—3503
[13]	Cervantes-Uc J. M., Espinosa J. I. M., Cauich-Rodriguez J. V., Avila-Ortega A., Vazquez-Torres H., Marcos-Fernandez A., Polym. Degrad. Stab., 2009, 94(10), 1666—1677
[14]	Petrovi Z. S., Zavargo Z., Flyn J. H., Macknight W. J., J. Appl. Polym. Sci., 1994, 51(6), 1087—1095
[15]	Sendijarevic A., Sendijarevic V., Frisch K.C., Vlajic M., J. Elastom. Plast., 1991, 23(3), 192—217
[16]	Roth W., Hanella K., Stainbach V., Frosch P., Internationales Wissenschaftliches Kolloquium-Technische HochschuleIlmenau, 1983, 28(2), 167—170
[17]	Sankaran S., Chanda M., J. Appl. Polym. Sci., 1990, 39(7), 1459—1466
[18]	Qin X., Yang X., Wang X., Wang M., J. Polym. Sci. Part A: Polym. Chem., 2005, 43(19), 4469—4477
[19]	Takeichi T., Ujiie K., Inoue K., Polymer, 2005, 46(25), 11225—11231
[20]	Li X.M., Luo Z. H., Kuang S. L., Zhao T., Aerospace Materials and Technology, 2009, (2), 46—49
	(李学梅, 罗振华, 匡松连, 赵彤. 航空材料与科技, 2009, (2), 46—49)
[21]	Bian X.S., Polymeric Materials Science and Engineering, 1987, (4), 1—6
	(卞新声. 高分子材料科学与工程, 1987, (4), 1—6)
[22]	Wei J. F., Li H. T., Meng X. S., Fan W. F., Liu Z. Z., Wang Z., Thermosetting Resin, 2011, 26(3), 1—5
	(魏建峰, 李宏涛, 孟祥胜, 范卫锋, 刘志真, 王震.热固性树脂, 2011,26(3), 1—5)
[23]	Zeng H. M., Mai K. C., Ye L. X., Chem. J. Chinese Universities, 1985, 6(5), 461—466
	(曾汉民, 麦堪成, 叶兰欣.高等学校化学学报, 1985,6(5), 461—466)
[24]	Wang M.C.,Wei L. H., Zhao T., Yu R. L., Feng Z. H., Acta Polymerica Sinica, 2006, (2), 241—247
	(王明存, 魏柳荷, 赵彤, 余瑞莲, 冯志海. 高分子学报, 2006, (2), 241—247)
[25]	Tang Q.H., Ai Q. S., He J. Y., Li X. D., Yang R. J., High Perform. Polym., 2013, DOI: 10.1177/0954008313486280
[26]	Xu Y. J., Petrovic Z., Das S., Wilkes G. L., Polymer, 2008, 49(19), 4248—4258
[27]	Ojha U., Kulkarni P., Faust R., Polymer, 2009, 50(15), 3448—3457
[28]	Hood M. A., Wang B. B., Sands J. M., Scala J. J. L., Beyer F. L., Li C. Y., Polymer, 2010, 51(10), 2191—2198

Sample	m(MDI)∶m(PTMG)∶m(CE)^*	T_5%/℃	LOI(%)	Dripping	UL-94(3.2 mm)
TPU20	17.35∶80.00∶2.65	308.5	19.5	Yes, burns until clamping	No class
TPIU20	12.71∶80.00∶7.29	323.5	22.5	Yes, immediate extinguishing after removing the fiame	V-2
TPIU30	14.52∶70.00∶15.48	312.0	27.0	Yes, immediate extinguishing after removing the fiame	V-2
TPIU40	16.32∶60.00∶23.68	293.0	29.5	Yes, immediate extinguishing after removing the fiame	V-2

Sample	m(MDI)∶m(PTMG)∶m(CE)^*	T_5%/℃	LOI(%)	Dripping	UL-94(3.2 mm)
TPU20	17.35∶80.00∶2.65	308.5	19.5	Yes, burns until clamping	No class
TPIU20	12.71∶80.00∶7.29	323.5	22.5	Yes, immediate extinguishing after removing the fiame	V-2
TPIU30	14.52∶70.00∶15.48	312.0	27.0	Yes, immediate extinguishing after removing the fiame	V-2
TPIU40	16.32∶60.00∶23.68	293.0	29.5	Yes, immediate extinguishing after removing the fiame	V-2