生物降解聚酯弹性体粒子改性聚乳酸复合材料的制备及性能

黎永轩; 朱韵来; 彭博; 焦贵宾; 王庆国

doi:10.13801/j.cnki.fhclxb.20201116.002

生物降解聚酯弹性体粒子改性聚乳酸复合材料的制备及性能

doi: 10.13801/j.cnki.fhclxb.20201116.002

黎永轩^1,,
朱韵来^1,,
彭博^1,,
焦贵宾^1,,
王庆国^{1, 2, ,}

1.
青岛科技大学　高分子科学与工程学院，青岛 266042
2.
橡塑材料与工程教育部重点实验室，青岛 266042

基金项目: 国家自然科学基金(51773104；51373085)；山东省重点研发项目(2017GGX20138)

详细信息

通讯作者:
王庆国，博士，教授，博士生导师，研究方向为生态环境高分子材料的合成及性能优化　 E-mail：qwang@qust.edu.cn

中图分类号: TB324；TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2020-08-31
- 录用日期: 2020-11-08
- 网络出版日期: 2020-11-16
- 刊出日期: 2021-08-15

Preparation and properties of biodegradable polyester elastomer particle modified poly(lactic acid) composites

LI Yongxuan^1
,,
ZHU Yunlai^1
,,
PENG Bo^1
,,
JIAO Guibin^1
,,
WANG Qingguo^{1, 2
, ,}

1.
School of Polymer Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
2.
Key Laboratory of Rubber-plastics, Ministry of Education, Qingdao 266042, China

摘要

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。
- 聚乳酸 /
- 聚酯弹性体粒子 /
- 复合材料 /
- 韧性 /
- 结晶 /
- 生物降解
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.
- polylactic acid /
- polyester elastomer particles /
- composites /
- toughness /
- crystallization /
- biodegradation

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图 1 CBEP的粒径分布曲线

Figure 1. Particle size distribution curves of CBEP

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图 2 PLA及CBEP/PLA复合材料的力学性能

Figure 2. Mechanical properties of PLA and CBEP/PLA composites

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图 3 CBEP/PLA复合材料颈缩样条的照片 (a) 及应力-应变曲线 (b)

Figure 3. Photo (a) and stress-strain curves (b) of CBEP/PLA composites necking specimen

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图 4 PLA及CBEP/PLA复合材料颈缩样条的DSC曲线

Figure 4. DSC curves of PLA and CBEP/PLA composites necking specimen

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图 5 PLA及CBEP/PLA复合材料的结晶曲线

Figure 5. Crystallization data of PLA and CBEP/PLA composites ((a) Nonisothermal crystallization DSC curves; (b) Isothermal crystallization DSC curves; (c) X_t-t curves; (d) Avrami plots; (e) Subsequent melting DSC curves)

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图 6 PLA及CBEP/PLA复合材料的POM图像

Figure 6. POM images of PLA and CBEP/PLA composites

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图 7 CBEP在脂肪酶环境下的降解性能

Figure 7. Degradability of CBEP under lipase solution

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图 8 PLA及CBEP/PLA复合材料在脂肪酶环境下的质量损失率

Figure 8. Mass loss rate of PLA and CBEP/PLA composites under lipase solution

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图 9 CBEP添加量不同的CBEP/PLA复合材料在土壤环境下的质量损失率

Figure 9. Mass loss rate of CBEP/PLA composites with different ratios of CBEP after soil burial

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图 10 PLA及CBEP/PLA复合材料在土壤掩埋4个月后的体视显微镜图像

Figure 10. Stereo microscope images of PLA and CBEP/PLA composites after soil burial for 4 months ((a) PLA; (b) PLA-Ca₁₀; (c) PLA-Cb₁₀; (d) PLA-Cc₁₀)

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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/%
Kind of CBEP	Particle size/mm	Mass ratio of PLA/%	0	2.5	5	7.5	10
CBEP-a	200	100	PLA	PLA-Ca_2.5	PLA-Ca₅	PLA-Ca_7.5	PLA-Ca₁₀
CBEP-b	500	100		PLA-Cb_2.5	PLA-Cb₅	PLA-Cb_7.5	PLA-Cb₁₀
CBEP-c	1 000	100		PLA-Cc_2.5	PLA-Cc₅	PLA-Cc_7.5	PLA-Cc₁₀

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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	T_m/℃	ΔH_m/(J∙g⁻¹)	ΔH_c/(J∙g⁻¹)	X_c/%	t_1/2/min	n	K/10⁻³min⁻ⁿ
PLA	167.7	34.23	30.87	36.81	9.8	2.70	1.47
PLA-Ca_7.5	165.3	36.38	27.93	42.05	7.7	2.49	4.27
PLA-Cb_7.5	165.5	34.38	29.23	39.74	8.2	2.49	3.70
PLA-Cc_7.5	166.3	33.62	30.85	38.86	8.9	2.55	2.65
Notes: T_m—Melting temperature; ΔH_m—Melting enthalpy; ΔH_c—Crystalline enthalpy; X_c—Crystallinity; t_1/2—Crystallization half-time; n—Avrami index; K—Crystallization rate constants.

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