Preparation and properties of biodegradable polyester elastomer particle modified poly(lactic acid) composites
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摘要: 以不同粒径的羧基封端生物降解聚酯弹性体粒子(CBEP)改性聚乳酸(PLA)制备了CBEP/PLA复合材料,对复合材料的力学、结晶与降解等性能进行了测试,并研究了CBEP对PLA性能的影响及作用机理。结果表明,CBEP可显著提高PLA的韧性,复合材料样条在拉伸时出现了颈缩现象,尤其是添加了7.5% (与PLA的质量比)粒径在200 nm的CBEP-a的复合材料的断裂伸长率由纯PLA的4.6%提高至155%,而复合材料的缺口冲击强度最高达到了纯PLA的2倍。同时CBEP可提高PLA的结晶性能,其中添加7.5%粒径在200 nm的CBEP-a的复合材料的等温结晶半结晶时间较纯PLA缩短了21.4%。而降解实验结果表明,添加了10%粒径在200 nm的CBEP-a的复合材料在脂肪酶环境下与土壤掩埋环境下的降解质量损失率分别由纯PLA的0.34%与0.25%,提高至2.52%与1.20%。CBEP/PLA复合材料在生物医药与环保材料等领域具有广阔的发展与应用前景。Abstract: The carboxyl-terminated biodegradable polyester elastomer particles (CBEP)/poly (lactic acid) (PLA) composites were prepared by different particle sizes of CBEP blended with PLA. The mechanical, crystallization and degradation properties of the composites were tested, and the effect and mechanism of CBEP on the properties of PLA were studied.The results show that CBEP can significantly improve the toughness of PLA, and the composite specimens appear necking during stretching, especially the elongation at break of the composites with 7.5% (mass ratio to PLA) CBEP-a (particle size of 200 nm) increases from 4.6% of neat PLA to 155%. And the notched impact strength of CBEP/PLA composites is up to 2 times of neat PLA. CBEP can also improve the crystallization properties of PLA, in which the isothermal crystallization half-crystallization time of the composites with 7.5% CBEP-a (particle size of 200 nm) is shortened by 21.4% compared with the neat PLA.The results of the degradation experiments show that the mass loss of the composites with 10% CBEP-a (particle size of 200 nm) in lipase and soil environment is increased from 0.34% and 0.25% of neat PLA to 2.52% and 1.20%, respectively. The CBEP/PLA composites have broad development and application in the fields of biomedicine and environmentally friendly materials.
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Key words:
- polylactic acid /
- polyester elastomer particles /
- composites /
- toughness /
- crystallization /
- biodegradation
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表 1 羧基封端生物降解聚酯弹性体粒子(CBEP)/聚乳酸(PLA)复合材料的原料质量比及样品名称
Table 1. Mass ratios and sample name of carboxyl-terminated biodegradable polyester elastomer particles (CBEP)/poly (lactic acid) (PLA) composites
Kind of CBEP Particle size/mm Mass ratio of PLA/% Mass ratio of CBEP/% 0 2.5 5 7.5 10 CBEP-a 200 100 PLA PLA-Ca2.5 PLA-Ca5 PLA-Ca7.5 PLA-Ca10 CBEP-b 500 100 PLA-Cb2.5 PLA-Cb5 PLA-Cb7.5 PLA-Cb10 CBEP-c 1 000 100 PLA-Cc2.5 PLA-Cc5 PLA-Cc7.5 PLA-Cc10 表 2 PLA及CBEP/PLA复合材料的等温熔融结晶动力学参数
Table 2. Kinetic parameters for isothermal melt crystallization of PLA and CBEP/PLA composites
Sample Tm/℃ ΔHm/(J∙g−1) ΔHc/(J∙g−1) Xc/% t1/2/min n K/10−3 min−n PLA 167.7 34.23 30.87 36.81 9.8 2.70 1.47 PLA-Ca7.5 165.3 36.38 27.93 42.05 7.7 2.49 4.27 PLA-Cb7.5 165.5 34.38 29.23 39.74 8.2 2.49 3.70 PLA-Cc7.5 166.3 33.62 30.85 38.86 8.9 2.55 2.65 Notes: Tm—Melting temperature; ΔHm—Melting enthalpy; ΔHc—Crystalline enthalpy; Xc—Crystallinity; t1/2—Crystallization half-time; n—Avrami index; K—Crystallization rate constants. -
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