纺织学报 ›› 2026, Vol. 47 ›› Issue (05): 18-27.doi: 10.13475/j.fzxb.20250904601

• 纤维材料 • 上一篇    下一篇

聚乳酸/聚己内酯共混纤维的制备及其性能

冯笑琳1,2, 魏静雯1,2, 李旭明1,2()   

  1. 1 绍兴大学 纺织科学与工程学院, 浙江 绍兴 312000
    2 浙江省清洁染整技术研究重点实验室, 浙江 绍兴 312000
  • 收稿日期:2025-09-11 修回日期:2026-03-17 出版日期:2026-05-15 发布日期:2026-07-10
  • 通讯作者: 李旭明(1977—),男,教授,博士。主要研究方向为纺织新材料及复合材料。E-mail: lixm@usx.edu.cn
  • 作者简介:冯笑琳(2000—),女,硕士生。主要研究方向为纺织新材料及复合材料。

Preparation and properties of polylactic acid/poly (ε-caprolactone) blended fibers

FENG Xiaolin1,2, WEI Jingwen1,2, LI Xuming1,2()   

  1. 1 College of Textile Science and Engineering, Shaoxing University, Shaoxing, Zhejiang 312000, China
    2 Zhejiang Provincial Key Laboratory of Clean Dyeing and Finishing Technology, Shaoxing, Zhejiang 312000, China
  • Received:2025-09-11 Revised:2026-03-17 Published:2026-05-15 Online:2026-07-10

摘要:

为解决聚乳酸(PLA)纤维脆性大、韧性差的问题,以PLA为基体,聚己内酯(PCL)为增韧相,多功能环氧扩链剂(ADR)为增容剂,通过熔融纺丝及热牵伸工艺制备出PLA/PCL共混纤维以及PLA/PCL/ADR共混纤维。系统分析了共混物的截面形貌、结晶及热学性能,着重研究了PCL质量分数为10%、15%、20%、25%、30%时对PLA的增韧效果,以及在PLA与PCL质量比为80∶20的基础上添加ADR质量分数分别为0.25%、0.5%、0.75%、1%、2%、5%时对PLA/PCL的增容效果以及对纤维力学性能的影响。结果表明:共混纤维随着PCL质量分数的增加,PLA/PCL结晶度和热稳定性都呈现略微提高后下降的趋势;当PCL质量分数为20%、牵伸倍数为3时,相比于纯PLA纤维其断裂强度下降24.46%,而断裂伸长率上升36.73%;当在PLA与PCL质量比为80∶20时加入0.75% ADR,所制备的PLA/PCL20/ADR0.75共混纤维,在牵伸倍数为3时,相较于纯PLA纤维其断裂强度和断裂伸长率分别提高5.98%和72.92%;PLA/PCL20/ADR0.75共混纤维热稳定性得到提升,最大质量损失速率下的分解温度达到367.83 ℃,较纯PLA提高4 ℃左右。通过调整PCL和ADR的质量分数,可以达到PLA纤维增韧的目标。

关键词: 聚乳酸纤维, 聚己内酯, 多功能环氧扩链剂, 熔融纺丝, 增韧改性, 界面相容性, 力学性能

Abstract:

Objective Polylactic acid (PLA) is an environmentally friendly polymer material, but it has problems such as high brittleness and poor toughness, which to some extent limit its application. Therefore, toughening modification of PLA is of great significance for improving its mechanical properties and expanding its applications in fields such as packaging and biomedicine.

Method PLA/PCL and PLA/PCL/ADR composite fibers were prepared via melt spinning and hot drawing processes, using poly(lactic acid) (PLA) as the matrix, poly(ε-caprolactone) (PCL) as the toughening agent, and a multifunctional epoxy oligomer (ADR) as the compatibilizer. The cross-sectional morphology, crystallization behavior, and thermal properties of the blends were characterized. The study focused on the influence of adding PCL at mass concentrations of 10%, 15%, 20%, 25%, and 30% on the toughening of PLA; and on adding ADR at mass concentrations of 0.25%, 0.5%, 0.75%, 1%, 2%, and 5% on the compatibilization between PLA and PCL and its influence on the mechanical properties of the fibers.

Results As the PCL content increases, the PLA/PCL system gradually shows obvious phase separation. Since the decomposition temperature at the maximam mass loss rate (Tmax) of PCL (401.02 ℃) is higher than that of PLA (363.79 ℃), the addition of low content PCL to some extent worked to improve the thermal stability of the blend, but when the PCL content exceeded 20%, the decomposition temperature began to decrease. when the PCL content was 30%, Tmaxdropped to 357.57 ℃, which is related to the intensification of phase separation and the increase of interface defects. A small amount of PCL would cause a heterogeneous nucleation effect. When the PCL content was 10%, the crystallinity of PLA increased from 30.39% to 31.72%, but as the PCL content further increased, the crystallinity of PLA decreased due to poor compatibility and the interference of flexible chain segments. When the PCL content was 20% and the draw ratio was 3, the elongation at break of the blended fibers was increased by 36.73% compared to the pure PLA, but the break strength decreased by 24.46%. After introducing ADR to 0.75% for reactive reinforcement, the compatibility of the system was significantly improved, Tmax increases to 367. 83 ℃, and the break strength and elongation at break of the blended fibers were increased by 5.98% and 72.92%, respectively, compared to pure PLA.

Conclusion Introducing PCL into the PLA system can effectively improve the toughness of the fibers. When the PCL content is 20% and the draw ratio is 3, the elongation at break of the blended fibers is approximately 36.73% higher than that of pure PLA, but the breaking strength decreases by about 24.46%. This indicates that there are still certain compatibility issues between PLA and PCL. After introducing ADR as a reactive compatibilizer, the interfacial compatibility of the system is significantly improved. When the ADR content is 0.75%, the PLA/PCL20/ADR0.75 blended fibers exhibit superior comprehensive performance, with their breaking strength and elongation at break increasing by 5.98% and 72.92%, respectively, compared to pure PLA. At the same time, the thermal stability of the blended system is enhanced, with the Tmax reaching 367. 83 ℃, which is approximately 4 ℃ higher than that of pure PLA. The results indicate that by reasonably regulating the PCL content and introducing an appropriate amount of ADR for reactive reinforcement, the toughness of PLA can be improved while maintaining its degradability.

Key words: polylactic acid fiber, polycaprolactone, multifunctional epoxy chain extender, melt spinning, toughening modification, interfacial compatibility, mechanical property

中图分类号: 

  • TS102.6

图1

纤维制备过程流程图"

表1

PLA/PCL/ADR共混比例"

样品编号 质量分数/%
PLA PCL ADR
PLA/PCL20/ADR0.25 80 20 0.25
PLA/PCL20/ADR0.5 80 20 0.50
PLA/PCL20/ADR0.75 80 20 0.75
PLA/PCL20/ADR1 80 20 1
PLA/PCL20/ADR2 80 20 2
PLA/PCL20/ADR5 80 20 5

表2

PLA/PCL/ADR共混纤维牵伸工艺"

样品编号 牵伸温度/℃ 牵伸速度/(cm·min-1) 牵伸倍数
A-70-150 70 150 3
A-80-150 80 150 3
A-90-150 90 150 3
A-100-150 100 150 3
A-110-150 110 150 3
A-90-100 90 100 3
A-90-130 90 130 3
A-90-170 90 170 3

图2

不同质量比的PLA/PCL共混物截面微观形貌照片"

图3

不同质量比的PLA/PCL/ADR共混物截面微观形貌图"

图4

PLA/PCL和PLA/PCL/ADR共混物的红外光谱图"

图5

PLA与PCL分子间作用力示意图"

图6

ADR-4370S的分子结构式以及PLA和PCL与ADR反应过程"

表3

不同质量比的PLA/PCL共混物样品的热解温度参数"

样品编号 T5/℃ T10/℃ T50/℃ Tmax/℃
PLA 307.23 325.89 356.21 363.79
PLA/PCL10 316.71 327.10 356.78 364.63
PLA/PCL15 320.94 329.96 357.03 365.28
PLA/PCL20 322.69 331.62 358.05 365.05
PLA/PCL25 325.98 333.63 359.45 364.51
PLA/PCL30 316.54 326.07 353.70 357.57
PCL 358.38 375.11 394.58 401.02

图7

不同质量比的PLA/PCL共混物样品的质量保留率"

图8

不同质量比PLA/PCL/ADR共混物样品的质量保留率曲线"

表4

不同质量比的PLA/PCL/ADR共混物样品的热解温度参数"

样品编号 T5/℃ T10/℃ T50/℃ Tmax/℃
PLA/PCL20 322.69 331.62 358.05 365.05
PLA/PCL20/ADR0.5 317.32 326.76 352.37 356.54
PLA/PCL20/ADR0.75 327.10 336.14 360.78 367.83
PLA/PCL20/ADR1 319.80 330.56 357.72 362.01
PLA/PCL20/ADR2 319.72 332.14 357.63 359.59
PLA/PCL20/ADR5 319.02 330.60 358.22 358.43

图9

DSC升温曲线"

表5

不同质量比的PLA/PCL、PLA/PCL/ADR共混物相关特征参数"

样品编号 玻璃化转变温度/℃ 结晶温度/℃ 结晶焓/(J·g-1) 熔融温度/℃ 热融焓/(J·g-1) 结晶度/%
PLA 60.18 102.46 23.46 173.26 51.73 30.39
PLA/PCL10 60.09 92.84 19.42 172.63 45.97 31.72
PLA/PCL15 60.01 91.91 18.79 172.48 43.10 30.75
PLA/PCL20 60.35 91.75 16.07 172.85 38.28 29.85
PLA/PCL25 60.06 92.28 12.98 172.65 32.35 27.77
PLA/PCL30 59.57 92.12 14.11 172.33 31.75 27.09
PLA/PCL20/ADR0.5 60.05 92.60 13.49 172.60 35.52 29.61
PLA/PCL20/ADR0.75 58.91 92.78 13.79 172.64 35.55 29.25
PLA/PCL20/ADR1 59.2 92.42 14.83 172.37 36.38 28.97
PLA/PCL20/ADR2 59.54 93.26 15.16 172.40 35.36 27.15
PLA/PCL20/ADR5 59.38 93.76 14.78 172.27 33.61 25.31

图10

不同牵伸温度和不同牵伸速度下PLA/PCL/ADR共混纤维的XRD曲线"

表6

PLA/PCL/ADR共混纤维的结晶参数"

样品编号 结晶度/% 晶粒尺寸/nm
A-70-150 17.00 9.34
A-80-150 18.52 15.55
A-90-150 20.39 17.42
A-100-150 19.27 16.79
A-110-150 18.19 14.98
A-90-100 14.27 15.62
A-90-130 13.69 13.32
A-90-170 16.09 15.47

图11

不同质量比的PLA/PCL共混纤维力学性能"

图12

牵伸倍数为3时的PLA/PCL共混纤维比应力-应变曲线"

图13

不同质量比的PLA/PCL/ADR共混纤维力学性能"

图14

牵伸倍数为3时的PLA/PCL/ADR共混纤维比应力-应变曲线"

[1] 乔思杰, 邢桐贺, 童爱心, 等. 不同聚乳酸材料的性能对比[J]. 纺织学报, 2025, 46(3): 27-33.
QIAO Sijie, XING Tonghe, TONG Aixin, et al. Comparison of properties of different polylactic acid materials[J]. Journal of Textile Research, 2025, 46(3): 27-33.
[2] MARTÍNEZ W E C, ACOSTA Y K R, REYES ACOSTA A V, et al. Advances in polylactic acid-based composites as a promising biomaterial for food packaging and biomedical applications: reinforcement strategies, functional enhancements, and future research directions[J]. Sustainable Materials and Technologies, 2025, 45: e01560.
[3] LI Y C, WANG S, QIAN S, et al. Depolymerization and Re/upcycling of biodegradable PLA plastics[J]. ACS-Omega, 2024, 9(12): 13509-13521.
doi: 10.1021/acsomega.3c08674
[4] PLAMADIALA I, CROITORU C, POP M A, et al. Enhancing polylactic acid (PLA) performance: a review of additives in fused deposition modelling (FDM) filaments[J]. Polymers, 2025, 17(2): 34.
doi: 10.3390/polym17010034
[5] 刘彦麟, 顾伟文, 魏建斐, 等. 耐热聚乳酸材料的研究进展[J]. 纺织学报, 2022, 43(6): 180-186.
LIU Yanlin, GU Weiwen, WEI Jianfei, et al. Research progress and status quo of heat-resistant polylactic acid materials[J]. Journal of Textile Research, 2022, 43(6): 180-186.
[6] NTRIVALA M A, PITSAVAS A C, LAZARIDOU K, et al. Polycaprolactone (PCL): the biodegradable polyester shaping the future of materials: a review on synthesis, properties, biodegradation, applications and future perspectives[J]. European Polymer Journal, 2025, 234: 114033.
doi: 10.1016/j.eurpolymj.2025.114033
[7] VAN DE VOORDE K M, POKORSKI J K, KORLEY L T J. Exploring morphological effects on the mechanics of blended poly(lactic acid)/poly(ε-caprolactone) extruded fibers fabricated using multilayer coextrusion[J]. Macromolecules, 2020, 53(13): 5047-5055.
doi: 10.1021/acs.macromol.0c00289
[8] 杨皓然, 黄柯柯, 刘钢, 等. 高韧、耐热PLA/PCL共混材料的制备与性能研究[J]. 塑料科技, 2022, 50(5): 1-6.
YANG Haoran, HUANG Keke, LIU Gang, et al. Preparation and properties of PLA/PCL blends with high toughness and heat resistant[J]. Plastics Science and Technology, 2022, 50(5): 1-6.
[9] MATUMBA K I, MOKHENA T C, OJIJO V, et al. Morphological characteristics, properties, and applications of polylactide/poly(ε-caprolactone) blends and their composites: a review[J]. Macromolecular Materials and Engineering, 2024, 309(8): 2400056.
doi: 10.1002/mame.v309.8
[10] 刘霖, 寿韬, 廖飞扬, 等. 高韧性生物基聚乳酸/聚氨酯共混物的制备及性能研究[J]. 中国塑料, 2025, 39(7): 1-5.
doi: 10.19491/j.issn.1001-9278.2025.07.001
LIU Lin, SHOU Tao, LIAO Feiyang, et al. Study on preparation and properties of highly tough bio-based polylactic acid/polyurethane blends[J]. China Plastics, 2025, 39(7): 1-5.
doi: 10.19491/j.issn.1001-9278.2025.07.001
[11] 丁庆谊. 不同类型增容剂对PLLA/PCL共混物的性能和老化的影响[D]. 南昌: 南昌大学, 2024: 5-13.
DING Qingyi. Effects of different types of compatibilizers on the properties and aging of PLLA/PCL blends[D]. Nanchang: Nanchang University, 2024: 5-13.
[12] LEE J S, HWANG G H, KWON Y S, et al. Influences of carbon nanotube on structures and properties of compatibilized polylactide/polypropylene blend-based ternary nanocomposites[J]. Journal of Thermoplastic Composite Materials, 2023, 36(7): 2815-2835.
doi: 10.1177/08927057221086835
[13] WANG B, YE X, WANG B W, et al. Reactive graphene as highly efficient compatibilizer for cocontinuous poly(lactic acid)/poly(ε-caprolactone) blends toward robust biodegradable nanocomposites[J]. Composites Science and Technology, 2022, 221: 109326.
doi: 10.1016/j.compscitech.2022.109326
[14] DING W J, ZHOU Y F, WANG W Q, et al. The reactive compatibilization of montmorillonite for immiscible anionic polyamide 6/polystyrene blends via in situ polymerization[J]. Polymer-Plastics Technology and Materials, 2020, 59(8): 884-894.
doi: 10.1080/25740881.2019.1708101
[15] SUN C, REN L, QIN Y X, et al. In-situ reaction compatibilization modification ofbiodegradable poly (lactic acid)/poly (3-hydroxybutyrate-co-4-hydroxy-butyrate) blends by multifunctional epoxy compound[J]. Journal of Polymer Research, 2025, 32(2): 46.
doi: 10.1007/s10965-025-04270-x
[16] YAN T Q, WANG X D, QIAO Y J. Strategy to antibacterial, high-mechanical, and degradable polylactic acid/chitosan composite film through reactive compatibilization via epoxy chain extender[J]. ACS Omega, 2024, 9(25): 27312-27320.
doi: 10.1021/acsomega.4c01849
[17] KOUTSOMITOPOULOU A F, BÉNÉZET J C, BERGERET A, et al. Preparation and characterization of olive pit powder as a filler to PLA-matrix bio-composites[J]. Powder Technology, 2014, 255: 10-16.
doi: 10.1016/j.powtec.2013.10.047
[18] 李晓川, 瞿芊芊, 李旭明. 熔融纺聚乳酸/聚丙烯纤维的制备及其性能[J]. 纺织学报, 2019, 40(3): 8-12.
LI Xiaochuan, QU Qianqian, LI Xuming. Preparation and properties of polylactic acid/polypropylene blend fiber by melt spinning[J]. Journal of Textile Research, 2019, 40(3): 8-12.
doi: 10.1177/004051757004000102
[19] 许义喆. PLA/PCL纤维膜复合载药PVA/SA水凝胶双层皮肤支架的制备及其性能研究[D]. 昆明: 昆明理工大学, 2024: 29.
XU Yizhe. Preparation and properties of PLA/PCL fiber membrane composite drug-loaded PVA/SA hydrogel double-layer skin scaffold[D]. Kunming: Kunming University of Science and Technology, 2024: 29.
[20] 夏学莲, 史向阳, 赵海鹏, 等. 环氧/异氰酸酯扩链增容PBAT/PLA复合材料的机理研究进展[J]. 化工新型材料, 2023, 51(3): 266-274.
doi: 10.19817/j.cnki.issn1006-3536.2023.03.047
XIA Xuelian, SHI Xiangyang, ZHAO Haipeng, et al. Progress on mechanism of epoxy/isocyanate chain-enlarging compatibilization of PBAT/PLA composites[J]. New Chemical Materials, 2023, 51(3): 266-274.
doi: 10.19817/j.cnki.issn1006-3536.2023.03.047
[21] 欧宗权, 于金超, 潘志娟. 光致变色聚乳酸/聚3-羟基丁酸酯共混纤维的纺制及其结构与性能[J]. 纺织学报, 2024, 45(12): 9-17.
doi: 10.13475/j.fzxb.20230905101
OU Zongquan, YU Jinchao, PAN Zhijuan. Spinning of photochromic polylactic acid/polyhydroxybutyrate blend fiber and its structure and properties[J]. Journal of Textile Research, 2024, 45(12): 9-17.
doi: 10.13475/j.fzxb.20230905101
[1] 吕丽华, 潘佳欣, 张多多. 废弃大麻纤维吸声复合材料的制备及其性能[J]. 纺织学报, 2026, 47(05): 133-140.
[2] 林启松, 戴钧明, 查全亮, 徐涛, 吕汪洋. 聚丁二酸丁二醇酯预取向丝与牵伸丝的制备及性能[J]. 纺织学报, 2026, 47(04): 9-16.
[3] 赵立环, 闫子妍, 张蓉, 袁明珠, 聂秀雯, 刘新蕊. 海岛长丝合成革基布的碱减量工艺及其力学性能[J]. 纺织学报, 2026, 47(04): 154-162.
[4] 林晓静, 毛迎, 陈文兴, 吕汪洋. 载姜黄素静电纺丝纤维膜的制备及其抗菌与抗氧化性能[J]. 纺织学报, 2026, 47(03): 217-224.
[5] 李好义, 田鑫哲, 张毅, 牟文英, 张超, 赵千龙, 杨卫民. 导电各向异性复合心脏补片的熔体静电纺丝/直写构建及体外评价[J]. 纺织学报, 2026, 47(03): 70-76.
[6] 刘金枝, 赵回汇, 吴焕友, 张建明, 高晶. 壳聚糖/聚己内酯取向纳米纤维膜的结构调控与物理引导作用[J]. 纺织学报, 2026, 47(03): 9-17.
[7] 张纪超, 刘昱辰, 张豪, 耿嘉骏, 蔡硕, 杨茹梦, 刘莹, 魏朋. 单体组分对萘基液晶聚芳酯纤维结构与性能的调控[J]. 纺织学报, 2026, 47(02): 65-72.
[8] 赵泽文, 吕宽, 苏旭中, 孙丰鑫. 短纤纱力学性能的宏细观耦合分析与数值模拟[J]. 纺织学报, 2026, 47(01): 106-114.
[9] 王瀚文, 李万鑫, 李晨, 喻麟洁, 王文庆, 董振峰, 魏建斐, 朱志国, 王锐. 金属氯化物对聚酰胺66氢键调控及力学性能的影响[J]. 纺织学报, 2025, 46(11): 9-18.
[10] 孙燕燕, 张世韬, 刘衡, 李明远, 蔡正国, 孙俊芬, 陈龙. 聚丙烯/聚对苯二甲酸丁二醇酯共混纤维的制备及其流变与热性能[J]. 纺织学报, 2025, 46(10): 11-18.
[11] 顾戚惠, 阳知乾, 王海楼, 魏发云, 张伟. 机织间隔织物增强水泥基复合材料的制备及其力学性能[J]. 纺织学报, 2025, 46(10): 120-128.
[12] 高敏, 程春祖, 徐中凯, 赵庆波, 张东, 代欣欣. 含硅改性磷氮阻燃Lyocell纤维的制备及其性能[J]. 纺织学报, 2025, 46(10): 19-29.
[13] 侯颖慧, 刘肖燕, 柳东辰, 郝矿荣, 邹婷. 基于体外降解的输尿管支架管的多目标优化[J]. 纺织学报, 2025, 46(09): 154-162.
[14] 高闻语, 陈诚, 奚晓玮, 邓林红, 刘杨. 改性丝素蛋白纤维增强胶原基角膜修复材料的制备及其性能[J]. 纺织学报, 2025, 46(08): 1-9.
[15] 梁锋, 方沿, 张伟华, 唐余玲, 李双洋, 周建飞, 石碧. 基于金属-多酚网络的胶原蛋白基纤维制备及其力学性能[J]. 纺织学报, 2025, 46(08): 10-17.
Viewed
Full text


Abstract

Cited

  Shared   
  Discussed   
No Suggested Reading articles found!