Journal of Textile Research ›› 2025, Vol. 46 ›› Issue (08): 127-135.doi: 10.13475/j.fzxb.20240805901

• Textile Engineering • Previous Articles     Next Articles

Improvement of thermal dimensional stability properties of polylactic acid meltblown nonwovens

ZHANG Xinyu1,2, JIN Xiaopei2, ZHU Jintang2, CUI Huashuai2, WU Pengfei2, CUI Ning2, SHI Xianning2()   

  1. 1. School of Materials Science and Engineering, Tiangong University, Tianjin 300387, China
    2. State Key Laboratory of Bio-based Fiber Materials, China Textile Academy, Beijing 100025, China
  • Received:2024-08-29 Revised:2025-01-02 Online:2025-08-15 Published:2025-08-15
  • Contact: SHI Xianning E-mail:shixianning@cta.gt.cn

Abstract:

Objective Polylactic acid (PLA) meltblown nonwoven fabric has poor heat resistance and a large shrinkage rate after heating, which seriously restricts its application in the field of filter materials. PLA meltblown nonwoven fabric cannot meet the disinfection requirements under 50-60 ℃ during mask production. Research has found that increasing the crystallinity of PLA meltblown nonwoven fabric can improve its heat resistance, thereby enhancing its dimensional stability.

Method This article solves this problem by increasing crystallinity and the number of grains, thereby increasing physical cross-linking points and limiting polymer relaxation. Non isothermal crystallization kinetics of PLA and diphenylhydrazide sebacic acid(PLA/TMC-300) were studied using DSC. The cooling crystallization process of PLA and PLA/TMC-300 was observed using a polarizing microscope. The effect of nucleating agent on the crystallinity of PLA meltblown nonwoven fabric was studied by XRD, and the effect of nucleating agent on the dimensional stability of PLA meltblown nonwoven fabric was studied by hot water shrinkage rate.

Results A comparative study on the non isothermal crystallization kinetics of PLA and PLA/benzoylhydrazine sebacate (TMC-300) showed that TMC-300 can significantly improve the crystallization ability of PLA. Polarized microscopy observation of the cooling crystallization process of PLA and PLA/TMC-300 also revealed that the addition of TMC-300 increased the crystallization temperature, crystallization rate, crystallinity, and grain number of PLA. XRD studies have found that compared to PLA meltblown nonwoven fabric, PLA/TMC-300 meltblown nonwoven fabric has increased crystallinity and more complete crystals. The study on the thermal dimensional stability of two types of meltblown nonwoven fabrics found that TMC-300 can effectively improve the dimensional stability of PLA meltblown nonwoven fabrics, whether by extending the heat treatment time or increasing the heat treatment temperature. After heat treatment at 50 ℃ for 1 h, the area shrinkage rate of PLA meltblown nonwoven fabric was 19%, while the area shrinkage rate of PLA/TMC-300 meltblown nonwoven fabric was 4.9%, and the length shrinkage rate was only 0.98%.

Conclusion Whether by extending the heat treatment time or increasing the heat treatment temperature, TMC-300 can effectively improve the dimensional stability of PLA meltblown nonwoven fabrics. After heat treatment at 50 ℃ for 1 hour, the area shrinkage rate of PLA/TMC-300 meltblown non-woven fabric is 4.9%, and the length shrinkage rate is only 0.98%, which fully meets the production requirements of masks. TMC-300 heterogeneous nucleation can improve the crystallization ability of PLA, increase the crystallinity and the number of grains, and act as physical cross-linking points in the aggregated three-phase structure of grains, limiting the thermal relaxation ability of amorphous polymer segments. Therefore, PLA meltblown nonwoven fabric can maintain better dimensional stability at high temperatures macroscopically.

Key words: polylactic acid meltblown nonwoven fabric, nucleating agent, non-isothermal crystallization kinetics, size shrinkage rate, mask

CLC Number: 

  • TQ316.63

Tab.1

Process parameters of PLA melt blown nonwoven fabric"

主要工艺指标 设定参数
螺杆温度 215 ℃
计量泵温度 220 ℃
模头温度 240 ℃
热空气温度 260 ℃
计量泵挤出量 2.4 mL/min
热空气速度 60 m/s
收布距离 15 cm
收布速度 10 cm/min

Fig.1

SEM surface morphology of PLA meltblown nonwoven fabric before and after thermal treatment(×100)"

Fig.2

Non-isothermal crystallization DSC curves of PLA(a) and PLA/TMC-300(b) at meltblown fabrics different cooling rates"

Tab.2

Non-isothermal crystallization DSC parameters of PLA and PLA/TMC-300 at different cooling rates"

试样名称 Φ/
(℃·min-1)
Tp/
Tonset/
ΔH/
(J·g-1)
2 111.15 116.60 43.4947
4 105.65 112.26 41.4167
PLA 6 102.38 110.43 34.7827
8 99.48 109.33 23.0319
10 98.93 108.14 13.4829
2 137.60 140.79 57.3163
4 133.11 137.23 54.1355
PLA/TMC-300 6 130.35 134.19 52.3443
8 128.47 132.23 51.6665
10 126.89 130.71 50.8657

Fig.3

X (T)-T and X(t)-t curves of non-isothermal crystallization of PLA (a) and PLA/TMC-300 (b) under different cooling rates"

Fig.4

Relationship curves between lgΦ and lgt of PLA and PLA/TMC-300 under different X(t)"

Tab.3

Non-isothermal crystallization kinetics parameters of PLA and PLA/TMC-300 under Mo equation"

试样名称 X(t)/% α F(T)
20 1.24 14.56
40 1.24 19.28
PLA 60 1.27 24.26
80 1.33 32.05
100 1.51 80.23
20 1.07 9.80
40 1.08 11.30
PLA/TMC-300 60 1.08 12.45
80 1.08 13.81
100 1.28 44.44

Fig.5

Relationship curve between ln(Φ/ T P 2)and 1 000/TP of PLA and PLA/TMC-300 meltblown nonwoven fabrics"

Fig.6

PLA and PLA/TMC-300 cooling crystallization process"

Fig.7

XRD curves of PLA and PLA/TMC-300 meltblown nonwoven fabrics"

Fig.8

Size shrinkage of PLA and PLA/TMC-300 meltblown nonwoven fabric under different heating temperature(a) and time(b)"

Fig.9

Schematic diagram of TMC-300 improving PLA size stability"

[1] XU J, XIAO X, ZHANG W, et al. Air-filtering masks for respiratory protection from PM2.5 and pandemic pathogens[J]. One Earth, 2020, 3(5): 574-589.
[2] ZHANG H, LIU J, ZHANG X, et al. Design of electret polypropylene melt blown air filtration material containing nucleating agent for effective PM2.5 cap-ture[J]. Royal Society of Chemistry, 2018, 8(15): 7932-7941.
[3] CORREA H L, CORREA D G. Polymer applications for medical care in the COVID-19 pandemic crisis: will we still speak ill of these materials?[J]. Frontiers in Materials, 2020, 7: 283-284.
[4] 魏聪, 周静, 魏鹏举, 等. 几种常见消毒方式对一次性使用医用口罩细菌过滤效率的影响及消毒效果的验证[J]. 医疗装备, 2020, 33(11): 13-15.
WEI Cong, ZHOU Jing, WEI Pengju, et al. Effects of several common disinfection methods on the bacterial filtration efficiency and disinfection effectiveness of disposable medical masks[J]. Medical Equipment, 2020, 33 (11): 13-15.
[5] ZHAO X, YU J, LIANG X, et al. Crystallization behaviors regulations and mechanical performances enhancement approaches of polylactic acid (PLA) biodegradable materials modified by organic nucleating agents[J]. International Journal of Biological Macromolecules, 2023. DOI: 10.1016/j.ijbiomac.2023.123581.
[6] LUNT J. Large-scale production, properties and commercial applications of polylactic acid polymers[J]. Polymer Degradation and Stability, 1998, 59(1-3): 145-152.
[7] 李昊晨, 张祥, 龙云瑞, 等. 聚乳酸耐热改性的研究进展[J]. 高分子通报, 2024, 37(4): 430-441.
LI Haochen, ZHANG Xiang, LONG Yunrui, et al. Research progress on heat-resistant modification of polylactic acid[J] Polymer Bulletin, 2024, 37 (4): 430-441.
[8] KAWAMOTO N, SAKAI A, HORIKOSHI T, et al. Nucleating agent for poly(L-lactic acid): An optimization of chemical structure of hydrazide compound for advanced nucleation ability[J]. Journal of Applied Polymer Science, 2007, 103(1): 198-203.
[9] FENG Y, MA P, XU P, et al. The crystallization behavior of poly (lactic acid) with different types of nucleating agents[J]. International journal of biological macromolecules, 2018, 106: 955-962.
[10] 薛白, 郭丹, 包建军. 成核剂TMC-300对聚乳酸耐热性能的影响[J]. 高分子材料科学与工程, 2014, 30(3): 59-63.
XUE Bai, GUO Dan, BAO Jianjun. Effect of nucleating agent TMC-300 on the heat resistance of polylactic acid[J]. Polymer Materials Science and Engi-neering, 2014, 30 (3): 59-63.
[11] HU W B. Polymer features in crystallization[J]. Chinese Journal of Polymer Science, 2022, 40(6): 545-555.
[12] ZHANG X, ZHAO S, MOHAMED M G, et al. Crystallization behaviors of poly (ethylene terephthalate)(PET) with monosilane isobutyl-polyhedral oligomeric silsesquioxanes (POSS)[J]. Journal of Materials Science, 2020, 55: 14642-14655.
[13] CHEN L, DOU Q. Influence of the combination of nucleating agent and plasticizer on the non-isothermal crystallization kinetics and activation energies of poly (lactic acid)[J]. Journal of Thermal Analysis and Calorimetry, 2020, 139: 1069-1090.
[14] 储永竞, 邱志成, 李鑫, 等. 连续原位聚合黑色PET的结晶行为研究[J]. 合成纤维工业, 2022, 45(5):1-10.
CHU Yongjing, QIU Zhicheng, LI Xin, et al. Study on the crystallization behavior of continuous in situ polymerization of black PET[J]. Synthetic Fiber Industry, 2022, 45 (5): 1-10.
[15] NAMPOOTHIRI K M, NAIR N R, JOHN R P. An overview of the recent developments in polylactide (PLA) research[J]. Bioresource Technology, 2010, 101(22): 8493-8501.
doi: 10.1016/j.biortech.2010.05.092 pmid: 20630747
[16] 李向阳, 郑文强, 毛晨曦, 等. 成核剂TMC-300对聚乳酸非等温结晶动力学的影响[J]. 塑料科技, 2013, 41 (10): 102-106.
LI Xiangyang, ZHENG Wenqiang, MAO Chenxi, et al. Effect of nucleating agent TMC-300 on the non isothermal crystallization kinetics of polylactic acid[J]. Plastics Technology, 2013, 41 (10): 102-106.
[17] AURAS R, HARTE B, SELKE S. An overview of polylactides as packaging materials[J]. Macromolecular Bioscience, 2004, 4(9): 835-864.
pmid: 15468294
[18] 吕超, 罗书品, 郭文静. 基于力学性能和结晶行为探究不同成核剂对聚乳酸性能影响[J]. 复合材料学报, 2024, 41(6):3168-3181.
LÜ Chao, LUO Shupin, GUO Wenjing. Investigating the influence of different nucleating agents on the properties of polylactic acid based on mechanical properties and crystallization behavior[J]. Journal of Composite Materials, 2024, 41(6):3168-3181.
[19] DE SANTIS P, KOVACS A J. Molecular conformation of poly (S‐lactic acid)[J]. Biopolymers: Original Research on Biomolecules, 1968, 6(3): 299-306.
[20] LIU Y, JIANG S, YAN W, et al. Crystallization 0morphology regulation on enhancing heat resistance of polylactic acid[J]. Polymers, 2020. DOI: 10.3390/polym12071563.
[21] 张剑锋. 熔喷聚乳酸空气净化材料的微观结构与驻极体性能和过滤性能相关性研究[D]. 杭州: 杭州电子科技大学, 2020: 20-21.
ZHANG Jianfeng. Study on the correlation between microstructure, polarizability, and filtration performance of melt blown polylactic acid air purification mate-rials[D]. Hangzhou: Hangzhou University of Electronic Science and Technology, 2020: 20-21.
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