离子液体增塑改性玉米淀粉/聚丁二酸丁二醇酯共混材料的结构与性能

doi:10.7503/cjcu20160385

摘要/Abstract

摘要：

为考察离子液体对淀粉/聚丁二酸丁二醇酯(PBS)的作用效果, 降低淀粉/PBS的脆性, 以离子液体(1-丁基-3-甲基咪唑氯盐[BMIM]Cl)作为增塑改性剂通过熔融共混法制备了玉米淀粉/聚丁二酸丁二醇酯(PBS) 共混材料, 采用红外光谱(FTIR)、扫描电镜(SEM)、热重分析(TGA)、 X射线衍射分析(XRD)及力学性能测试方法研究了[BMIM]Cl对淀粉/PBS共混材料结构和性能的影响. 结果表明, [BMIM]Cl能与淀粉/PBS分子发生强相互作用, 破坏淀粉/PBS共混物中原有的氢键与结晶结构, 增强界面相互作用, 改善相容性, 进而改变淀粉/PBS共混材料的结构与性能; [BMIM]Cl的加入不影响淀粉/PBS的热稳定性, 可使材料玻璃化转变温度(T_g)、结晶温度(T_c)、冷结晶温度(T_cc)及结晶度(X_c)降低. [BMIM]Cl具有显著降低淀粉/PBS脆性的作用, 使其断裂伸长率大幅度增加, 拉伸强度和弹性模量降低.

关键词: 聚丁二酸丁二醇酯, 淀粉, 共混材料, 离子液体, 相容性

Abstract:

In order to study the effect of the ionic liquid on starch/poly(butylene succinate)(PBS) blends and reduce the brittleness of the blends, starch/PBS blends plasticized with ionic liquid([BMIM]Cl) were prepared by melt blending. Infrared absorption spectroscopy(IR), scanning electron microscopy(SEM), thermal gravimetric analysis(TGA), X-ray diffraction(XRD) and mechanical test were adopted to study the effects of [BMIM]Cl on the structure and performance of starch/PBS blends. The results showed that [BMIM]Cl can form strong interactions between starch and PBS molecules, thus disrupting the inter and intra hydrogen bonding of starch and PBS chains and also destroying the crystal structure, which improved the interfacial bonding strength and compatibility between starch and PBS. The glass transition temperature(T_g), crystallization point(T_c), cold crystallization temperatures(T_cc) and crystallinity(X_c) of starch/PBS blends declined with addition of [BMIM]Cl, that means the intermolecular forces in PBS were weakened by the incorporation of [BMIM]Cl and the activity of chain segments were enhanced; furthermore, the ordered arrangement of PBS main chain in crystalline region could be disturbed, owing to the specific interactions between PBS and [BMIM]Cl. However, the thermal stability of the blends could not be affected of [BMIM]Cl. Meanwhile, with addition of [BMIM]Cl, the tensile strength and elastic modulus decreased, while the elongation at break increased and the brittleness of starch/PBS blends reduced significantly, which indicated that strong interaction and good compatility occured in starch/PBS blends.

Key words: Poly(butylene succinate), Starch, Blend, Ionic liquid, Compatibility

中图分类号:

O636
TQ321.2

TrendMD:

雷蓓, 罗辉, 石孟可, 张熙. 离子液体增塑改性玉米淀粉/聚丁二酸丁二醇酯共混材料的结构与性能. 高等学校化学学报, 2016, 37(9): 1722.

LEI Bei, LUO Hui, SHI Mengke, ZHANG Xi. Structure and Properties of Starch/Poly(butylene succinate) Blends Plasticized by [BMIM]Cl^†. Chem. J. Chinese Universities, 2016, 37(9): 1722.

图/表 7

Fig.1 FTIR spectra of starch/PBS blends with various contents of [BMIM]Cl Mass fraction of [BMIM]Cl: a. 0; b. 5%; c. 10%;d. 15%; e. 20%.

Fig.2 SEM images of starch/PBS blends with various contents of [BMIM]Cl Mass fraction of [BMIM]Cl: (A) 0; (B) 5%; (C) 20%.

Fig.3 DTG curves of starch/PBS blends with various contents of [BMIM]Cl Mass fraction of [BMIM]Cl: a. 0; b. 5%; c. 10%; d. 15%; e. 20%.

Fig.4 DSC melting(A) and crystallization (B) curves of starch/PBS blends with various contents of [BMIM]Cl Mass fraction of [BMIM]Cl: a. 0; b. 5%; c. 10%; d. 15%; e. 20%.

Table 1 DSC data of starch/PBS blends

Sample	ΔH_m/(J·g^-1)	X_c(%)	T_c/℃	T_cc/℃	T_g/℃
SP	33.17	50.12	65.76	89.62	-33.88
SPL5	30.65	48.63	65.70	89.28	-34.61
SPL10	28.63	47.59	64.22	88.33	-35.05
SPL15	26.86	46.67	62.48	88.26	-36.77
SPL20	25.19	45.68	62.02	88.04	-38.82

Fig.5 XRD diffractograms of starch/PBS blends with various contents of [BMIM]Cl Mass fraction of [BMIM]Cl: a. 0; b. 5%; c. 20%.

Table 2 Mechanical properties of starch/PBS blends plasticized with [BMIM]Cl

Sample	Tensile strength/MPa	Elongation at break(%)	Young’s modulus/MPa
SP	15.38	7.27	1143
SPL5	13.56	12.50	860
SPL10	10.79	14.06	687
SPL15	9.53	23.98	303
SPL20	7.26	36.20	162

参考文献 28

[1]	Zhang C. H., Zhao X., Huang J. T., Plastics,2008, 37(3), 8—10
	(张昌辉, 赵霞, 黄继涛. 塑料,2008, 37(3), 8—10)
[2]	Wang G. L., Xu J., Guo B. H., Polymer Bulletin, 2011, (4), 99—109
	(王国利, 徐军, 郭宝华. 分子通报, 2011, (4), 99—109)
[3]	Liu X. Y., Tu Z. G., Zhao S. F., Plastics Science and Technology,2014, 42(4), 92—13
	(刘晓燕, 涂志刚, 赵素芳. 塑料科技,2014, 42(4), 92—13)
[4]	Liu J., Ji J. H., Zhang W., Wang X. W., Zhao J., New Chemical Materials,2013, 41(8), 1—3
	(刘军, 季君晖, 张维, 王小威, 赵剑. 化工新型材料,2013, 41(8), 1—3)
[5]	Wang X. L., Zhang Y. R., Wang Y. Z., Acta Polymerica Sinica, 2011, (1), 24—37
	(汪秀丽, 张玉荣, 王玉忠. 高分子学报, 2011, (1), 24—37)
[6]	Cui Y. S., Wang X. D., Ning Z. Y., China Plastics,2014, 28(8), 1—13
	(崔永生, 王训道, 宁桌远. 中国塑料,2014, 28(8), 1—13)
[7]	Li J.W., Luo X. G., Lin X. Y., Zhou Y., Starch-Starke,2013, 65, 831—839
[8]	Zeng J. B., Jiao L., Li Y. D., Srinivasan M., Carbohydrate Polymers,2011, 83, 762—768
[9]	Dean K., Yu L., Bateman S., Wu D. Y., Journal of Applied Polymer Science,2007, 103, 802—811
[10]	Boonprasith P., Wootthikanokkhan J., Nimitsiriwat N., Journal of Applied Polymer Science,2013, 130(2), 1114—1123
[11]	Lai S. M., Huang C. K., Shen H. F., Journal of Applied Polymer Science,2005, 97(1), 257—264
[12]	Smits A. L. M., Kruiskamp P. H., Van Soet J. J. G., Vliegenthart J. F. G., Carbohydrate Polymers,2003, 53(4), 409—416
[13]	Wang W., Journal of Polymers and the Environment, 2013, 21(1), 46—53
[14]	Li H. B., Huneault M. A., Journal of Applied Polymer Science,2011, 119(4), 2439—2448
[15]	Liu B., Lü Q., Fang R., Cheng X., Advanced Materials Research,2011, 306/307, 1717—1721
[16]	Huang M., Yu J., Ma X., Polymer Degradation and Stability,2005, 90(3), 501—507
[17]	Xing X., Zhang X. Z., Zhang Y., China Plastics,2013, 27(7), 1—7
	(邢潇, 张须臻, 张勇. 中国塑料,2013, 27(7), 1—7)
[18]	Xie F., Halley P. J., Avérous L., Progress in Polymer Science,2012, 37(4), 595—623
[19]	Zhang H., Wu J., Zhang J., He J., Macromolecules,2005, 38, 8272—8277
[20]	Cheng L. Y., Liu W. W., Zhang Y. M., Wang P. H., Journal of Textile Research,2008, 29(2), 129—132
	(程凌燕, 刘崴崴, 张玉梅, 王华平. 纺织学报,2008, 29(2), 129—132)
[21]	Zdanowicz M., Spychaj T., Polimery,2011, 56(11/12), 861—864
[22]	Wilpiszewska K., Spychaj T., Carbohydrate Polymers,2011, 86, 424—428
[23]	Standardizotion Administration of the People’s Republic of China, GB13022-91, Plastics-Determination of Tensile Properies of Films, Standards Press of China, Beijing, 1991
	(中国国家标准化管理委员会, GB13022-91, 塑料薄膜拉伸性能的测定, 北京, 中国标准出版社, 1991)
[24]	Bodirlau R., Spiridon I., Teaca C. A., Materiale Plastice,2010, 47(2), 126—129
[25]	Yasuniwa M., Satou T., Journal of Polymer Science: Part B: Polymer Physics,2002, 40(21), 2411—2420
[26]	Miao W. H., Chen S. J., Zhang J., Plastics Science and Technology,2011, 4, 86—90
	(缪文虎, 陈双俊, 张军. 塑料科技, 2011, 4, 86—90)
[27]	Liu G. M., Zheng L. C., Zhang X. Q., Li C. C., Macromolecules,2012, 45, 5487—5493
[28]	Zeng J. B., Li Y. D., Zhu Q. Y., Yang K. K., Wang X. L., Wang Y. Z., Polymer,2009, 50, 1178—1186