新型聚酯增塑剂的合成及增塑聚氯乙烯性能

doi:10.7503/cjcu20150223

摘要/Abstract

摘要：

以生物质化工产品衣康酸加氢产物2-甲基丁二酸为原料, 采用熔融缩聚法制备了一种新型聚酯增塑剂聚2-甲基丁二酸1,3-丙二醇酯, 采用红外光谱(FTIR)和核磁共振(¹H NMR)对聚酯的结构进行了表征. 通过扫描电镜(SEM)、动态力学分析(DMA)、拉伸测试对该聚酯增塑聚氯乙烯(PVC)的增塑效果进行的表征结果表明, 该聚酯与PVC相容性良好, 可大大改善PVC材料的硬度, 增加其断裂伸长率, 降低PVC的玻璃化转变温度、拉伸强度及拉伸模量. 与小分子增塑剂邻苯二甲酸二辛酯(DOP)相比, 合成的新型聚酯增塑剂具有优异的耐抽出性、耐挥发性和耐迁移性, 可提高PVC材料的使用寿命.

关键词: 聚2-甲基丁二酸1, 3-丙二醇酯, 聚氯乙烯, 增塑剂, 耐久性

Abstract:

A novel plasticizer based on the hydrogenation of itaconic acid, poly(1,3-propylene 2-methyl-succinate)(1,3-PPM) was synthesized by 1,3-propanediol and 2-methylsuccinate acid through melt polycondensation. The plasticizing effect in poly(vinyl chloride)(PVC) was characterized. The results showed that 1,3-PPM displayed excellent compatibility with PVC. The glass transition temperature, tensile strength, tensile modulus and hardness of PVC films plasticized by 1,3-PPM decreased and elongation at break increased significantly with the increasing of plasticizer. Furthermore, compared to the traditional plasticizer dioctyl phthalate(DOP), 1,3-PPM had superior durability(volatility resistance, extractability and migration stability).

Key words: Poly(1, 3-propylene 2-methylsuccinate), Poly(vinyl chloride), Plasticizer, Durability

中图分类号:

TrendMD:

高传慧, 郭方荣, 王晓红, 张欣华, 王传兴, 武玉民. 新型聚酯增塑剂的合成及增塑聚氯乙烯性能. 高等学校化学学报, 2015, 36(8): 1634.

GAO Chuanhui, GUO Fangrong, WANG Xiaohong, ZHANG Xinhua, WANG Chuanxing, WU Yumin. Synthesis of a Novel Polyester Plasticizer and Its Plasticizing Effect in Poly(vinylchloride)^†. Chem. J. Chinese Universities, 2015, 36(8): 1634.

图/表 9

Scheme 1 Structural formula of 1,3-PPM

Fig.1 FTIR spectrum of 1,3-PPM

Fig.2 1H NMR spectrum of 1,3-PPM

Fig.3 GPC spectrum of 1,3-PPM

Fig.4 SEM images of PVC plasticized by 1,3-PPM with different concentrations(A) 40 phr; (B) 50 phr; (C) 60 phr; (D) 70 phr; (E) 80 phr. phr: parts per hundred of resin.

Fig.5 DMA of PVC plasticized by 1,3-PPM with different concentrationsa. 40 phr; b. 50 phr; c. 60 phr; d. 70 phr;e. 80 phr.

Fig.6 Mechanical properties of PVC/1,3-PPM(a) and PVC/DOP(b)(A) Elongation at break; (B) tensile modulus; (C) tensile strength.

Table 1 Surface hardness of PVC films*

Compound	Concentration(phr)	Shore hardness
1,3-PPM	40	33(HD)
	50	30(HD)
	60	82(HA)
	70	78(HA)
	80	72(HA)
DOP	40	85(HA)
	50	81(HA)
	60	78(HA)
	70	75(HA)
	80	67(HA)
PVC		82(HD)

Table 2 Mass loss of 1,3-PPM and DOP in different mediums

Medium	Mass loss rate(%)		Measurement condition
Medium	DOP		1,3-PPM
Ethanol	9.60	1.89	20 ℃, 48 h
Cyclohexane	16.52	5.45	20 ℃, 48 h
Xylene	20.36	4.35	20 ℃, 48 h
Activated carbon	1.69	0.52	40 ℃, 48 h
Natural rubber	4.12	1.54	70 ℃, 0.5 MPa, 7 d

参考文献 25

[1]	Tao Y., Zuo L., Contemporary Chemical Industry, 2008, 37(6), 647—650
	(陶宇, 左玲. 当代化工, 2008, 37(6), 647—650)
[2]	Lv R. H., Zhou C. L., Lei J. X., Li Q. M., Chem. J. Chinese Universities, 2008, 29(5), 1050—1055
	(吕瑞华, 周昌林, 雷景新, 李启满. 高等学校化学学报, 2008, 29(5), 1050—1055)
[3]	Bao Y.Z., Weng Z. X., Huang Z. M., Pan Z. R.,Acta Polymerica Sinica, 1999, (6), 680—686
	(包永忠, 翁志学, 黄志明, 潘祖仁. 高分子学报, 1999, (6), 680—686)
[4]	Chen Z. Q., Yan P., Li M. Q., Wei M., Chen W. Z., Journal of Chengdu Medical College, 2007, 2(1), 63—66
	(陈朝琼, 严平, 李茂全, 魏敏, 陈卫中. 成都医学院学报, 2007, 2(1), 63—66 )
[5]	Lindstrom A., Hakkarainen M., Journal of Applied Polymer Science, 2007, 104(4), 2458—2467
[6]	Liu C. H., Sun Y. M., Yang Y. C., Liang T., Modern Food Science and Technology, 2012, 28(3), 339—341
	(柳春红, 孙远明, 杨艺超, 梁添. 现代食品科技, 2012, 28(3), 339—341)
[7]	Wang D.R.,China Rubber Science and Technology Market, 2004, (4), 8—10
	(汪多仁. 橡胶科技市场, 2004, (4), 8—10)
[8]	Li M., Yuan J. F., Pan M. W., Song H., Tang L. D., Polymer Materials Science ﹠ Engineering, 2012, 28(1), 37—40
	(李明, 袁金凤, 潘明旺, 宋辉, 汤丽丹. 高分子材料科学与工程, 2012, 28(1), 37—40)
[9]	Ren W.W., Synthesis and Application Research of Straight Chain Polyester Plasticizers, Xi’an University of Science and Technology, Xi’an, 2010
	(任文文. 直链型聚酯增塑剂的合成与应用研究, 西安: 西安科技大学, 2010)
[10]	Heinze D., Mang T., Peter K., Moller M., Weichold O., Journal of Applied Polymer Science, 2013, 131(9), 40226
[11]	Lindstrom A., Hakkarainen M., Journal of Applied Polymer Science, 2006, 100(3), 2180—2188
[12]	Yin B., Hakkarainen M., Journal of Applied Polymer Science, 2011, 119(4), 2400—2407
[13]	Willke T., Vorlop K. D., Applied Microbiology Biotechnology, 2001, 56, 289—295
[14]	Yahiro K., Shibata S., Jia S., Park Y., Okabe M., Journal of Fermentation and Bioengineering, 1997, 84(4), 375—377
[15]	Okabe M., Lies D., Kanamasa S., Park E.Y., Applied Microbiology and Biotechnology, 2009, 84(4), 597—606
[16]	Wang Y. Y., Gao C. H., Wang C. X., Wu Y. M., Journal of Qingdao University of Science and Technology(Natural Science Edition), 2014, 35(1), 9—12
	(汪盈盈, 高传慧, 王传兴, 武玉民. 青岛科技大学学报(自然科学版), 2014, 35(1), 9—12)
[17]	GB/T1040.1-2006, Plastics-Determination of Tensile Properties, Part 1: General Principles, Standards Press of China, Beijing, 2007
	(中华人民共和国国家质量监督检验检疫总局和中国国家标准化管理委员会, GB/T 1040 GB/T 1040.1-2006, 塑料-拉伸性能的测定, 第1部分: 总则, 北京: 中国标准出版社, 2007)
[18]	GB/T1690-2010, Rubber, Vulcanized or Thermoplastic-Determination of the Effect of Liquids, Standards Press of China, Beijing, 2011
	(中华人民共和国国家质量监督检验检疫总局和中国国家标准化管理委员会, GB/T 1690-2010, 硫化橡胶或热塑性橡胶-耐液体试验方法, 北京: 中国标准出版社, 2011)
[19]	ISO 176-2005, Plastics-Determination of Loss of Plasticizers-Activated Carbon Method, International Organization for Standardization, 2005
[20]	ISO 177-1988, Plastics-Determination of Migration of Plasticizers, International Organization for Standardization, 1988
[21]	Wang Y., Zhang Q. W., Ren Y. M., Jing L. J., Wei T. X., Chem. Res. Chinese Universities, 2014, 30(1), 42—48
[22]	Rahman M., Brazel C. S., Progress in Polymer Science, 2004, 29(1), 1223—1248
[23]	Luan Y. H., Wu J., Zhan M. S., Zhang J. M., Zhang J., He J. S., Chem. J. Chinese Universities, 2012, 33(10), 2135—2137
	(栾贻浩, 武进, 詹茂盛, 张金明, 张军, 何嘉松. 高等学校化学学报, 2012, 33(10), 2135—2137)
[24]	Cheng Z. H., Yu X. D., Chen P. P., Wang C. P., Chu F. X., Paint ﹠ Coatings Industry, 2011, 41(2), 76—79
	(程增会, 于向东, 陈鹏鹏, 王春鹏, 储富祥. 涂料工业, 2011, 41(2), 76—79)
[25]	Yang T., Yu T.L.,Plastics Additives, 2009, (5), 13—14
	(杨涛, 于同利. 塑料助剂, 2009, (5), 13—14)