PLA/TPEE共混物的制备及性能
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摘要
采用熔融共混法制备聚乳酸/热塑性聚醚酯弹性体(PLA/TPEE)共混物,探究共混物配比、急冷和等温热处理温度对材料冲击性能及耐热性能的影响。差示扫描量热法测试结果表明,急冷定型所得样品的结晶度小于7%,接近非晶态。而等温热处理所得样品的结晶度均达到30%以上。相对于急冷样品,90℃等温热处理20min所得样品的冲击性能和耐热性能均得到增强。当TPEE含量为20%时,90℃等温结晶处理20min所得样品的无缺口冲击强度和维卡软化点温度分别由急冷样条的50.89kJ/m~2和66.2℃提升至53.47kJ/m~2和160.8℃,达到无缺口冲击强度和耐热性能最佳平衡点。90℃热处理20min时,PLA基体生成大量细小晶体,一方面大大提升材料的耐热性能;另一方面,能够有效分散应力,并与TPEE分散相一起诱导材料屈服,从而提升冲击韧性。
Polylactide/thermoplastic poly(ether-ester) elastomer(PLA/TPEE) blends were prepared by melt blending method. Influences of mass ratio,quenching and isothermal heat treatment temperature on impact toughness and heat resistance of the PLA/TPEE blends were researched. According to DSC results,it is confirmed that the quenched specimens show low crystallinites(less than 7%),roughly being amorphous. In contrast,the crystallinities of crystallized specimens through isothermal heat treatment increase up to more than 30%. Moreover,compared with the quenched specimens with poor heat resistance,the crystallized specimens through isothermal heat treatment at 90℃ for 20 min present significantly enhanced heat resistance and improved impact toughness. The PLA/TPEE blend containing 20% TPEE isothermally heat treated at 90℃ for 20 min shows the optimum comprehensive performance,which unnotched impact strength and vicat softening temperature increase from 50.89 kJ/m~2 and 66.2℃ for the quenched PLA/TPEE blend to 53.47 kJ/m~2 and 160.8℃,respectively. It is found that there are a large amount of fine crystals formed in PLA matrix as the PLA/TPEE blends have been heat treated at 90℃ for 20 min. The aggregation structure filled with fine crystals not only can largely increase the heat resistance,but also show a synergistic toughening effect with TPEE through dispersing stress and inducing matrix yielding.
Polylactide/thermoplastic poly(ether-ester) elastomer(PLA/TPEE) blends were prepared by melt blending method. Influences of mass ratio,quenching and isothermal heat treatment temperature on impact toughness and heat resistance of the PLA/TPEE blends were researched. According to DSC results,it is confirmed that the quenched specimens show low crystallinites(less than 7%),roughly being amorphous. In contrast,the crystallinities of crystallized specimens through isothermal heat treatment increase up to more than 30%. Moreover,compared with the quenched specimens with poor heat resistance,the crystallized specimens through isothermal heat treatment at 90℃ for 20 min present significantly enhanced heat resistance and improved impact toughness. The PLA/TPEE blend containing 20% TPEE isothermally heat treated at 90℃ for 20 min shows the optimum comprehensive performance,which unnotched impact strength and vicat softening temperature increase from 50.89 kJ/m~2 and 66.2℃ for the quenched PLA/TPEE blend to 53.47 kJ/m~2 and 160.8℃,respectively. It is found that there are a large amount of fine crystals formed in PLA matrix as the PLA/TPEE blends have been heat treated at 90℃ for 20 min. The aggregation structure filled with fine crystals not only can largely increase the heat resistance,but also show a synergistic toughening effect with TPEE through dispersing stress and inducing matrix yielding.
引文
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[2]Lu Xueli,Lyu Qiaoqiang,Huang Xiulong,et al.Isothermal melt crystallization and performance evaluation of polylactide/thermoplastic polyester blends with multi-functional epoxy[J].Journal of Applied Polymer Science,2018,135(23):doi:10.1002/app.46343.
[3]Han Zhizhong,Zhang Youcheng,Yang Weimin,et al.Advances in Microcellular foam processing of PLA[J].Key Engineering Materials,2016,717:68-72.
[4]Yang Yong,Zhang Lisheng,Xiong Zhu,et al.Research progress in the heat resistance,toughening and filling modification of PLA[J].Science China Chemistry,2016,59(11):1 355-1 368.
[5]朱大勇,徐俊鹏,曹礼彬,等.PLA热稳定性和降解性能研究及其应用[J].工程塑料应用,2018,46(1):119-122.Zhu Dayong,Xu Junpeng,Cao Libin,et al.Thermal stability and the degradation performance of poly(lactic acid)and its application[J].Engineering Plastics Application,2018,46(1):119-122.
[6]Liu Zhenwei,Luo Yuanlin,Bai Hongwei,et al.Remarkably enhanced impact toughness and heat resistance of poly(L-lactide)/thermoplastic polyurethane blends by constructing stereocomplex crystallites in the matrix[J].ACS Sustainable Chemistry&Engineering,2016,4(1):111-120.
[7]Zhou Yinghui,Lei Liang,Yang Bo,et al.Preparation of PLA-based nanocomposites modified by nano-attapulgite with good toughnessstrength balance[J].Polymer Testing,2017,60:78-83.
[8]阳范文,林永亮,田秀梅,等.PLA/PCL共混物的制备及其在医用材料中的应用[J].工程塑料应用,2014,42(2):1-5.Yang Fanwen,Lin Yongliang,Tian Xiumei,et al.Preparation of PLA/PCL blend and its application on medical materials[J].Engineering Plastics Application,2014,42(2):1-5.
[9]Nagarajan V,Zhang Kunyu,Misra M,et al.Overcoming the fundamental challenges in improving the impact strength and crystallinity of PLA biocomposites:Influence of nucleating agent and mold temperature[J].ACS Applied Materials&Interfaces,2015,7(21):11 203-11 214.
[10]陈烜,石慧,陈文凯,等.癸二酸二苯甲酰肼对PLA等温结晶行为及拉伸性影响[J].工程塑料应用,2017,45(7):101-106.Chen Xuan,Shi Hui,Chen Wenkai,et al.Influence of SBH on isothermal crystallization behavior and tensile performance of PLA[J].Engineering Plastics Application,2017,45(7):101-106.
[11]Lai Sun-Mou,Wu Wan-Ling,Wang Yu-Jhen.Annealing effect on the shape memory properties of polylactic acid(PLA)/thermoplastic polyurethane(TPU)bio-based blends[J].Journal of Polymer Research,2016,23(5):99-111.
[12]王思思,庞素娟,徐鼐,等.聚乳酸/聚己二酸-对苯二甲酸丁二醇酯共混物等温结晶行为及等温热处理对力学性能的影响[J].高分子材料科学与工程,2016,32(8):38-44.Wang Sisi,Pang Sujuan,Xu Nai,et al.Isothermal crystallization behavior of PLA/PBAT blend and effects of isothermal heating treatment on mechanical performance of PLA/PBAT blend[J].Polymer Materials Science&Engineering,2016,32(8):38-44.
[13]Nassar S F,Guinault A,Delpouve N,et al.Multi-scale analysis of the impact of polylactide morphology on gas barrier properties[J].Polymer,2017,108:163-172.
[14]Zhang Jianming,Tashiro K,Tsuji H,et al.Disorder-to-order phase transition and multiple melting behavior of poly(L-lactide)investigated by simultaneous measurements of WAXD and DSC[J].Macromolecules,2008,41(4):1 352-1 357.
[15]Liu Guoming,Zhang Xiuqin,Wang Dujin.Tailoring crystallization:towards high-performance poly(lactic acid)[J].Advanced Materials,2014,26(40):6 905-6 911.
[16]Suksut B,Deeprasertkul C.Effect of nucleating agents on physical properties of poly(lactic acid)and its blend with natural rubber[J].Journal of Polymers and the Environment,2011,19(1):288-296.
[17]Wang Sisi,Pang Sujuan,Pan Lisha,et al.Compatibilization of poly(lactic acid)/ethylene-propylene-diene rubber blends by using organic montmorillonite as a compatibilizer[J].Journal of Applied Polymer Science,2016,133(46):doi:10.1002/app.44192.
[18]Nagarajan V,Mohanty A K,Misra M.Perspective on polylactic acid(PLA)based sustainable materials for durable applications:Focus on toughness and heat resistance[J].ACS Sustainable Chemistry&Engineering,2016,4(6):2 899-2 916.