PLA生物降解聚酯材料的制备及降解性能的研究

doi:10.3969/j.issn.2097-2806.2026.01.011

摘要/Abstract

摘要：

以纳米纤维素（CNC）为原料，对其进行了羧基化处理后引入聚乳酸（PLA）基体中，研究了羧基化处理的纳米纤维素（CNC-C）、CNC-C掺杂量对CNC-PLA复合聚酯材料力学性能、物相结构、结晶度及降解性能的影响。研究结果表明：羧基化处理后提高了CNC的亲水性能，水接触角从73.5°降低至46.4°，红外光谱测试表明了CNC-C与PLA是通过物理共混制备的复合薄膜，CNC-C的掺入使得复合薄膜的断裂方式从脆性断裂向韧性断裂转变。3% CNC-C/PLA复合薄膜的拉伸强度和断裂延伸率均达到了最大值40.8 MPa、5.5%，该复合薄膜的冷结晶温度（T_c）为最低值114.5 ℃，结晶度达到最大值50.6%。CNC-C的掺入提高了复合薄膜的降解性能，3% CNC-C/PLA复合薄膜在25 ℃下降解一周后失重为1.71%，100 ℃下降解一周后失重为53.5%，具有优异的生物可降解性和力学性能。

关键词: 聚乳酸, 纳米纤维素, 羧基化, 复合薄膜, 生物降解, 结晶度

Abstract:

Nanocellulose (CNC) was carboxylated and then introduced into polylactic acid (PLA) matrix. The effects of carboxylated nanocellulose (CNC-C) and CNC-C doping amount on the mechanical properties, phase structure, crystallinity and degradation properties of CNC-PLA composite polyester were studied. The results showed that, the hydrophilicity of CNC was improved after carboxylation, whose water contact angle was decreased from 73.5° to 46.4°. The infrared spectrum showed that CNC-C and PLA formed composite films by physical blending. The addition of CNC-C made the fracture mode of the composite films change from brittle fracture to ductile fracture. The tensile strength and fracture elongation of 3% CNC-C/PLA composite film both reached the maximum values of 40.8 MPa and 5.5%, and the cold crystallization temperature (T_c) of this composite film was of the minimum value (114.5 ℃), and its crystallinity reached the maximum value of 50.6%. The CNC-C introduced improved the degradability of the composite film. The weight loss of 3% CNC-C/PLA composite film was 1.71% after degradation at 25 ℃ for one week, and it was 53.5% after degradation at 100 ℃ for one week, indicative of excellent biodegradability and mechanical properties.

Key words: polylactic acid, nanocellulose, carboxylation, composite film, biodegradation, crystallinity

中图分类号:

TB332

毛淑佳. PLA生物降解聚酯材料的制备及降解性能的研究[J]. 日用化学工业（中英文）, 2026, 56(1): 88-97.

Shujia Mao. Study on the preparation and degradability of PLA biodegradable polyester material[J]. China Surfactant Detergent & Cosmetics, 2026, 56(1): 88-97.

图/表 13

表1

图1

图2

图3

图4

图5

图6

图7

图8

图9

表2

图10

图11

参考文献 26

[1]	阳思思, 吴红枚, 刘玉媛, 等. 聚乳酸/纳米纤维素复合材料的制备与性能研究进展[J]. 塑料科技, 2022, 50(7): 124-128.
[2]	黄春艳, 李仁焕, 梁家能, 等. 偶联改性棉花纳米纤维素/聚乳酸复合材料的非等温结晶性能和疏水性能研究[J]. 塑料科技, 2020, 48(6): 85-91.
[3]	张静, 丁长坤, 段镜月, 等. 聚乳酸/纤维素纳米晶复合材料的制备与性能研究[J]. 中国塑料, 2018, 32(3): 22-26.
[4]	Parvathy S U, Hema S, Sajith M, et al. A review on barrier properties of nanocellulose and polylactic acid composites[C]// IOP Conference Series: Materials Science and Engineering. IOP Publishing, 2022, 1258(1): 012017.
[5]	刘星, 王文俊, 邵自强, 等. 纳米纤维素/聚乳酸全绿色纳米复合材料的制备及性能[J]. 高等学校化学学报, 2018, 39(2): 373-381. doi: 10.7503/cjcu20170513
[6]	Szymańska-Chargot M, Chylińska M, Pieczywek P M, et al. Evaluation of nanocomposite made of polylactic acid and nanocellulose from carrot pomace modified with silver nanoparticles[J]. Polymers, 2020, 12(4): 812. doi: 10.3390/polym12040812
[7]	袁彩霞, 罗卫华, 袁光明, 等. 增容纳米纤维素/聚乳酸复合材料的制备与性能[J]. 复合材料学报, 2016, 33(12): 2718-2724.
[8]	罗卫华, 王正良, 袁彩霞, 等. 纤维素纳米晶/聚乳酸复合材料的制备与性能[J]. 高分子材料科学与工程, 2014, 30(9): 154-158.
[9]	王骏鹏, 陈维清, 韩欢热, 等. 纤维素纳米纤丝/聚乳酸复合材料的制备及力学性能表征[J]. 塑料科技, 2013, 41(5): 83-86.
[10]	Trifol J, Plackett D, Sillard C, et al. Hybrid poly (lactic acid)/nanocellulose/nanoclay composites with synergistically enhanced barrier properties and improved thermomechanical resistance[J]. Polymer International, 2016, 65(8): 988-995. doi: 10.1002/pi.2016.65.issue-8
[11]	谢沛颖, 谢慧红, 李帅, 等. Pickering乳液凝胶法构筑高疏水型纤维素纳米纤/聚乳酸复合气凝胶[J]. 高分子材料科学与工程, 2022, 38(6): 125-131.
[12]	刘瑞来, 丁晓红, 赵瑨云, 等. 相分离法制备聚乳酸/醋酸纤维素三维微-纳米纤维多孔支架及其生物矿化活性[J]. 高分子材料科学与工程, 2021, 37(12): 137-146.
[13]	朱艳, 曹乐, 贾仕奎, 等. 表面改性CNF对PLA/TPU共混物的结晶与力学性能的影响[J]. 塑料, 2021, 50(2): 23-28.
[14]	Jacob J, Linson N, Mavelil-Sam R, et al. Poly (lactic acid)/nanocellulose biocomposites for sustainable food packaging[J]. Cellulose, 2024, 31(10): 5997-6042. doi: 10.1007/s10570-024-05975-w
[15]	李向力, 章少华, 何世文, 等. 基于纤维素纳米晶的成核效应制备高性能立构复合聚乳酸低温烧结制品[J]. 塑料工业, 2020, 48(8): 136-140.
[16]	俞秋燕, 严灵芝, 刘翔, 等. 聚乳酸/改性纳米纤维素复合材料制备及性能[J]. 包装工程, 2016, 37(7): 28-32.
[17]	史军华, 姚进, 李知函, 等. 改性纳米纤维素/聚乳酸复合材料的制备及性能[J]. 精细化工, 2020, 37(1): 45-50, 79.
[18]	陈倩, 曾威, 石伊康, 等. 接枝细菌纤维素改性聚乳酸复合材料的制备与性能[J]. 复合材料学报, 2023, 40(3): 1430-1437.
[19]	翟天亮, 唐莲, 宋萍, 等. 聚乳酸/纤维素纳米晶纳米复合物的结晶性能[J]. 塑料, 2021, 50(1): 123-126, 139.
[20]	Park S, Kim H, Kim T, et al. Effect of different morphology of nucleating agents on the crystallization behavior of poly lactic acid/nanocellulose composites[J]. Textile Science and Engineering, 2021, 58(6): 322-327.
[21]	张春梅, 宋玉, 刘双会, 等. 聚乳酸/改性纤维素纳米晶的热稳定性和结晶性能[J]. 工程塑料应用, 2020, 48(6): 103-107.
[22]	张奇锋, 王忠, 贾仕奎, 等. 纳米纤维素/聚丁二酸丁二醇酯母粒改性聚乳酸的结晶与力学性能研究[J]. 化工新型材料, 2020, 48(3): 147-151, 156.
[23]	吕勇, 候百权, 宋词, 等. 氧化纳米纤维素纤丝/聚乳酸复合膜制备及其性能研究[J]. 数字印刷, 2019(6): 66-71.
[24]	张博, 王小峰, 郭萌, 等. 聚乳酸表面羧基化改性及细胞相容性研究[J]. 中国塑料, 2021, 35(5): 17-23. doi: 10.19491/j.issn.1001-9278.2021.05.004
[25]	张海蕾, 董奎勇, 马博谋, 等. 端基对聚乳酸热降解的影响[J]. 塑料, 2023, 52(4): 54-59.
[26]	卓梦柯, 邓通, 唐华东, 等. 纤维素纳米晶增强生物可降解复合纤维研究进展[J]. 化工新型材料, 2023, 51(12): 298-302. doi: 10.19817/j.cnki.issn1006-3536.2023.12.004

试样	T_g /℃	T_c /℃	T_m/℃	ΔH_C/（J/g）	ΔH_m /（J/g）	结晶度/%
PLA	62.4	139.6	167.9	0.1	1.5	1.6
1% CNC/PLA	62.2	139.5	167.4	0.5	3.1	2.9
1% CNC-C/PLA	59.6	117.8	167.7	2.6	28.3	27.7
3% CNC-C/PLA	58.8	114.5	167.9	3.6	47.9	50.6
5% CNC-C/PLA	59.2	117.5	167.6	3.2	30.9	30.4