PP-g-(MAH/St)和PP-g-MAH对聚丙烯/木粉复合材料性能的影响

doi:10.3724/SP.J.1095.2014.30629

摘要/Abstract

摘要： 在转矩流变仪中用熔融接枝法制备马来酸酐(MAH)和苯乙烯(St)接枝聚丙烯（PP）—PP-g-(MAH/St)和PP-g-MAH，将其作为聚丙烯/木粉复合材料的相容剂。 FTIR证实MAH和St单体与PP发生接枝反应。用SEM和DSC等手段考察两种相容剂对PP/木粉复合材料微观形貌和结晶性能的影响，探索了各种PP/木粉复合材料加工和力学性能不同的内在原因。 SEM显示，PP-g-(MAH/St)改性木粉比PP-g-MAH改性木粉在PP基体中分散性更佳，木粉与PP的界面更加模糊，相容性进一步改善。 DSC结果表明，PP-g-(MAH/St)改性体系可增强木粉对PP的异相成核作用，提高结晶温度和结晶度。复合材料的加工和力学性能测试结果表明，PP-g-(MAH/St)改性效果明显优于PP-g-MAH。复合材料的熔体质量流动速率随相容剂用量的增加而逐步下降，PP-g-(MAH/St)改性体系拉伸强度和弯曲强度却逐步上升，并在相容剂用量为4.8 g/100 g PP时达到极值。此时其拉伸强度达40.62 MPa，分别是未改性体系和PP-g-MAH改性体系的1.29和1.17倍；其弯曲强度达45.72 MPa，分别是未改性体系和PP-g-MAH改性体系的1.23和1.59倍；而无缺口冲击强度却在相容剂用量为3.6 g/100 g PP时达到极值13.35 kJ/m2，分别是未改性体系和PP-g-MAH改性体系的1.62倍和1.42倍。

关键词: 聚丙烯, 木粉, 马来酸酐/苯乙烯双单体熔融接枝聚丙烯, 相容性, 性能

Abstract: PPg(MAH/St) and PPgMAH were prepared by melt grafting polypropylene(PP) resin with maleic anhydride(MAH) and styrene(St) in a torque rheometer, and were used as compatiblizers in polypropylene/wood flour composites. The structures of PPg(MAH/St) and PPgMAH were confirmed by FTIR analysis. The effect of these two compatiblizers on the microstructure and crystal properties of PP/wood flour composites was examined by SEM and DSC to interpret and explain the difference of processing and mechanical properties of PP/wood flour composites. SEM analysis indicates that wood flour modified by PPg(MAH/St) has better dispersion in the PP matrix with a blurrier interface and better compatibility than that modified by PPgMAH. DSC results show that the heterogeneous nucleation of wood flour to PP in PPg(MAH/St) modified system is stronger and their crystallization temperature and crystallinity increase. The processing and mechanical properties of PP/wood flour composites reveal that PPg(MAH/St) has better performance than PPgMAH. The meltmess flow rate of the two kinds of composites shows a steady downward trend with the increase of compatiblizer contents, while the tensile and flexural strength of PPg(MAH/St) modified system show a steady upward trend, and reach a maximum at 4.8 g PPg(MAH/St)/100 g PP. The tensile strength reachs to 40.62 MPa which is 1.29 and 1.17 times of the unmodified system and PPgMAH system, respectively, and at the meantime the flexural strength rises to 45.72 MPa which is 1.23 and 1.59 times as high as those of the unmodified system and PPgMAH system. At 3.6 g PPg(MAH/St)/100 g PP, the unnotched impact strength of PPg(MAH/St) system is 13.35 kJ/m2 which is 1.62 and 1.42 times as high as that of unmodified and PPgMAH system, respectively.

Key words: polypropylene, wood flour, polypropylene melt grafted with maleic anhydride/styrene monomer, compatibility, properties

中图分类号:

O632

朱德钦, 生瑜, 童庆松, 王真. PP-g-(MAH/St)和PP-g-MAH对聚丙烯/木粉复合材料性能的影响[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30629.

ZHU Deqin1, SHENG Yu1*, TONG Qinsong2, WANG Zhen1. Effects of PP-g-(MAH/St) and PP-g-MAH on the Properties of Polypropylene/Wood Flour Composites[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30629.

参考文献

[1] Matuana L M,Jin S,Stark N M. Ultraviolet weathering of HDPE/wood-flour Composites Coextruded with a Clear HDPE Cap Layer[J]. Ploym Degrad Stab,2011,96(1):97-106.

[2] Kuang X,Kuang R,Zheng X,et al. Mechanical Properties and Size Stability of Wheat Straw and Recycled LDPE Composites Coupled by Waterborne Coupling Agents[J]. Carbohydr Polym,2010,80(3):927-933.

[3] Zhu D Q,Sheng Y,Liu X R,et al. Effects of a Novel Acrylic-based Compatibilizer on the Mechanical Properties, Contact angle, Water absorption, Density and Processibility of PVC/wood Flour Composite[J]. J Reinf Plast Compos,2012,31(15):1025-1036.

[4] SHENG Yu,ZHU Deqin,SU Xiaofen,et al. Effects of Different Treatment Agent on the Mechanical Properties of PP/wood Flour Composites[J]. Polym Mater Sci Eng,2012,28(10):51-54(in Chinese).

生瑜,朱德钦,苏晓芬,等. 不同改性剂对PP/木粉复合材料性能的影响[J]. 高分子材料科学与工程,2012,28(10):51-54.

[5] Sobczak L,Lang R W,Reif M,et al. Polypropylene-based Wood Polymer Composites—Effect of a Maleated Polypropylene Coupling Agent under Dry and Wet Conditions[J]. J Appl Polym Sci,2013,129(6):3687-3695.

[6] Yang H S,Wolcott M P,Kim H S,et al. Effect of Different Compatibilizing Agents on the Mechanical Properties of Lignocellulosic Material Filled Polyethylene bi-composites[J]. Compos Struct,2007,79(3):369-375.

[7] Keener T J,Stuart R K,Brown T K. Maleated Coupling Agents for Natural Fibre Composites[J]. Compos,Part A,2004,(35):357-362.

[8] XIE Xuming,LI Ying,ZHANG Jingchun. Study of Melt Free Radical Grafting of Maleic Anhydride and Styrene onto Polypropylene and Its Properties[J]. Acta Polym Sin,2002,(4):7-12(in Chinese).

谢续明,李颖,张景春. 马来酸酐-苯乙烯熔融接枝聚丙烯的影响因素及其性能研究[J]. 高分子学报,2002,(4):7-12.

[9] LI Ying,XIE Xuming. Studies on Mechanism of Free Radical Melt-grafting of Multi-monomer System for Maleic Anhydride/ styrene onto Polypropylene[J]. Chem J Chinese Univ，2000,21(4):637-6424(in Chinese).

李颖,谢续明. 马来酸酐-苯乙烯多组分单体熔融接枝聚丙烯的机理研究[J]. 高等学校化学学报,2000,21(4):637-642.

[10] Xie X M,Chen N H,Guo B H,et al. Study of Multi-monomer Melt-grafting onto Polypropylene in an Extruder[J]. Polym Int,2000,49(12):1677-1683.

[11] WANG Lu,GUO Baohua,XIE Xuming. The Preparation of MAH/St Multi-monomer Melt Grafting on ABS and Its Compatibilizer Effect on PA6/ABS Blends[J]. Acta Polym Sin,2005,(2):213-218(in Chinese).

王璐，郭宝华，谢续明. ABS的MAH/St多单体熔融接枝及其对PA6/ABS共混体系相形态和力学性能的影响[J]. 高分子学报,2005,(2):213-218.

[12] ZHANG Guiyun，SHAO Muyan，LI Qizhuang，et al. Effect of Difunctional PP-g-(MAH-St) on Properties of PP and PP Composite[J]. Plastics,2011,40(4):37-39(in Chinese).

张桂云，邵慕妍，李祈庄，等. 双功能PP-g-(MAH-St)对PP及复合材料性能的影响[J]. 塑料,2011,40(4):37-39.

[13] FANG Zhiqi,TANG Longxiang,LIU Chunhua. Studies and Applications of the Solidphase Grafting of MAH and St onto PP[J]. Polym Mater Sci Eng,2003,19(2):83-85(in Chinese).

方治齐,唐龙祥,刘春华. 马来酸酐、苯乙烯双单体固相接枝聚丙烯及其应用[J]. 高分子材料科学与工程,2003,19(2):83-85.

[14] ZHANG Jiamin,LIAN Zhaoxun. Influence of a Compatibilizer and Processing Conditions on Morphology and Mechanical Properties of PA1010/PP Blends[J]. China Plast,2010,24(11):68-71(in Chinese).

张甲敏,连照勋. 相容剂和加工工艺对PA1010/PP共混体系形态和力学性能的影响[J]. 中国塑料,2010,24(11):68-71.

[15] LV Xilin ,YU Chengbing ,ZHAO Xiulan ,et al. Effects of PP-g-(MAH-St) on Mechanical Properties of PP/Wood Powder Composites[J]. China Plast,2009,23(1):64-67(in Chinese).

吕希林,俞成丙,赵秀兰,等. PP-g-(MAH-St)对PP/木粉复合材料力学性能的影响[J]. 中国塑料,2009,23(1):64-67.

[16] GB/T3682-2000. Determination of the Melt Mass-flow Rate(MFR) and the Melt Volume-flow Rate(MVR) of Thermoplastics[S]. Beijing:China Standards Press,2000(in Chinese).

GB/T3682-2000. 热塑性塑料熔体质量流动速率和熔体体积流动速率的测定[S]. 北京:中国标准出版社,2000.

[17] GB/T 1040-2006. Plastics-Determination of Tensile Properties[S]. Beijing:China Standards Press,2006(in Chinese).

GB/T 1040-2006. 塑料拉伸性能的测定[S]. 北京:中国标准出版社,2006.

[18] GB/T9341-2000. Plastics-Determination of Flexural Properties[S]. Beijing:China Standards Press,2000(in Chinese).

GB/T9341-2000. 塑料弯曲性能实验方法[S]. 北京:中国标准出版社,2000.

[19] GB/T1043-2008. Plastics-Determination of Charpy Impact Properties[S]. Beijing:China Standards Press,2008(in Chinese).

GB/T1043-2008. 塑料简支梁冲击性能的测定[S]. 北京:中国标准出版社,2008.

[20] DEND Qinying,LIU Lan,DENG Huimin. Spectral Analysis Tutorial[M]. Beijing:Science Press,2003,59-69(in Chinese).

邓芹英,刘岚,邓慧敏. 波谱分析教程[M]. 北京:科学出版社,2003,59-69.

[21] WANG Guiheng. Polymer Materials Processing Principles[M]. Beijing:Chemical Industry Press,1991(in Chinese).

王贵恒. 高分子材料成型加工原理[M]. 北京:化学工业出版社,1991.

[22] Wolcott M P,Yin S Z,Rials T G. Using Dynamic Mechanical Spectroscopy to Monitor the Crystallization of PP/MAPP Blends in the Presence of Wood[J]. Compos Interfaces,2000,7(1):3-12.

[23] Harper D,Wolcott M. Interaction Between Coupling Agent and Lubricants in Wood-polypropylene Composites[J]. Compos Part A:Appl S,2004,35(3):385-394.

[24] Lai S M,Feng C,Wang Y Y,et al. Comparative Study of Maleated Polyolefins as Compatibilizers for Polyethylene Wood Flour Composites[J]. J Appl Polym Sci,2003,87(3):487-496.

[25] Oksman K,Lindberg H. Influence of Thermoplastic Elastomers on Adhesion in Polyetylene-wood Flour Composite[J]. J Appl Polym Sci,1998,68(11):1845-1855.