有机膦酸改性聚乳酸织物的制备及其性能

doi:10.13475/j.fzxb.20241201901

纺织学报 ›› 2025, Vol. 46 ›› Issue (08): 154-163.doi: 10.13475/j.fzxb.20241201901

有机膦酸改性聚乳酸织物的制备及其性能

陈展毓¹^,², 俞森龙¹^,²(), 周家良³, 朱丽萍¹^,², 周哲¹^,², 相恒学¹^,², 朱美芳¹^,²

1.东华大学先进纤维材料全国重点实验室, 上海 201620
2.东华大学材料科学与工程学院, 上海 201620
3.江苏集萃先进纤维材料研究所有限公司, 江苏南通 226000

收稿日期:2024-12-10 修回日期:2025-04-14 出版日期:2025-08-15 发布日期:2025-08-15
通讯作者: 俞森龙(1990—),男,高级工程师,博士。主要研究方向为功能纤维。E-mail:ysl@dhu.edu.cn。
作者简介:陈展毓(2000—),女,硕士生。主要研究方向为聚乳酸阻燃改性。
基金资助:
山东省重点研发计划(重大科技创新工程)项目(2023CXGC010611);河南省重大科技专项(231100320200)

Preparation of polylactic acid fabrics modified with phosphonic acid and their properties

CHEN Zhanyu¹^,², YU Senlong¹^,²(), ZHOU Jialiang³, ZHU Liping¹^,², ZHOU Zhe¹^,², XIANG Hengxue¹^,², ZHU Meifang¹^,²

1. State Key Laboratory of Advanced Fiber Materials, Donghu University, Shanghai 201620, China
2. College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
3. Jiangsu Gem Advanced Fiber Materials Research Institute Co., Ltd., Nantong, Jiangsu 226000, China

Received:2024-12-10 Revised:2025-04-14 Published:2025-08-15 Online:2025-08-15

摘要/Abstract

摘要： 针对聚乳酸(PLA)织物易燃烧且熔滴严重的问题,采用绿色环保磷系阻燃剂,通过简单易行的溶液浸渍表面改性技术对其进行阻燃抗熔滴功能改性。借助场发射扫描电镜、傅里叶红外光谱、热失重分析仪、氧指数仪、垂直燃烧、锥形量热仪、万能材料试验机等研究阻燃剂对PLA织物表面形貌、热稳定性、燃烧行为、织物强度等性能的影响规律,并揭示其阻燃机制。结果表明: 当浸渍处理4次时,阻燃PLA织物(FR-PLA-4C)的增重率(16.5%)与磷含量(41.45 mg/g)最高,阻燃性能与热稳定性提升最明显,极限氧指数达到30.8%,垂直燃烧等级达到V-0,样品损毁长度下降至7.7 cm,热释放速率峰值为259.92 kW/m²(下降8.9%),总热释放量为10.40 MJ/m²(下降9.6%),600 ℃时的残炭量可达12.0%,阻燃织物兼具气相与凝聚相阻燃作用;此外,FR-PLA-4C织物具有良好的力学强度、柔软度与透气性,拉伸强力提升至260.8 N,改性后织物外观色泽没有明显变化,具有良好的实际应用前景。

关键词: 聚乳酸织物, 溶液浸渍, 阻燃织物, 阻燃机制, 磷系阻燃剂, 功能纺织品

Abstract:

Objective As a type of promising biodegradable materials, polylactic acid (PLA) has been widely used in making textile fibers, commodity plastics, packaging materials and biological materials due to its excellent biocompatibility and considerable degradability. However, PLA still exists diverse problems such as high brittleness and poor heat resistance. Especially, PLA is easily burned with serious melt droplets at high temperature, limiting the further applications in automotive interior and building decoration. Therefore, development of a simple and eco-friendly flame-retardant PLA modification method is significant and necessary.

Method The efficient flame-retardant modification of PLA fabrics was carried out via a dipping treatment. To start with, PLA fabrics were rinsed with anhydrous ethanol and then impregnated in a 150 g/L solution of methylphosphonic acid/methylphosphonate for 30 s. The fabrics were subsequently dried in a 60 ℃ oven for 15 min to complete the flame retardant treatment. The treated fabrics were denoted as FR-PLA-xC, where x represented the number of dipping. The morphology, chemical composition, thermal stability and flame retardant property were characterized by means of scanning electron microscope, EDS, Fourier transform infrared spectroscopy, thermogravimetric analyzer, cone calorimetry and limiting oxygen index.

Results The SEM of fabric surface morphology showed that methylphosphonic acid/methyl methylphosphonate flame retardancy was evenly distributed on the PLA fabrics after surface flame-retardant modification. The mass fraction and phosphorus content of flame-retardant fabrics were the highest with 4-time dipping treatment. Thus, the FR-PLA-4C fabric showed the most significant improvement in flame retardancy with the limiting oxygen index (LOI) of 30.8% and the vertical burning classification of V-0. Furthermore, the flame retardancy of FR-PLA-4C fabrics was characterized by cone calorimeter test and microcalorimetry test. The peak heat release rate (PHRR) and total heat release (THR) dropped to 259.92 kW/m² and 10.4 MJ/m², representing deceases by 8.9% and 10.4%, respectively. This indicates that FR-PLA-4C fabric generated less flammable volatile substances and produced more carbon-containing residues when it was exposed to high-temperature radiation. Under the nitrogen atmosphere, the initial degradation temperature (T₅_%) of pure PLA fabric was 342.8 ℃, the maximum thermal degradation rate (R_max) was 18.2%/min, and the high-temperature residue was 0%. After flame retardant modification, the T₅_% of FR-PLA-4C was 275.3 ℃, the R_max was 17.2%/min, and the residue was 12.0%. The flame-retardant mechanism was analyzed by TG-IR, SEM and Raman spectroscopy, incorporating both condensed phase and gas phase. Compared with PLA fabric, the graphitization degree of char residues was significantly improved by organic-phosphonic acid coating. Moreover, the FR-PLA-4C exhibited ideal service performance, the tensile strength increased from 135.7 N (PLA) to 260.8 N.

Conclusion The flame-retardant PLA fabric (FR-PLA) was successfully fabricated by dipping surface treatment. The chemical structure, thermal stability, flame retardancy, tensile strength and service performance were studied. Specifically, the FR-PLA-4C fabric exhibited the most excellent flame retardancy (LOI 30.8%, UL-94 V-0). The PHRR and the THR were deceased by 8.9% and 10.4%, respectively as well as the residual carbon at 600 ℃ could reach 12.0%. Additionally, the mechanism of the FR-PLA fabric included both gas phase and condensed phase. Moreover, the tensile strength was significantly improved by flame-retardant modification, while the softness and breathability were slightly affected by coating. Besides, the visual appearance and color of the fabric had no obvious change as well as it expressed certain washing durability with LOI value of 25.0% after 30 min laundry. To sum up, the FR-PLA-4C fabric simultaneously exhibited ideal flame retardancy, mechanical property and service performance, which has a promising prospect in home textiles, indoor decoration, and industrial fabrics, etc.

Key words: polylactic acid fabric, solution impregnation, flame-retardant fabric, flame-retardant mechanism, phosphorous flame retardant, functional textile

中图分类号:

TS195.2

陈展毓, 俞森龙, 周家良, 朱丽萍, 周哲, 相恒学, 朱美芳. 有机膦酸改性聚乳酸织物的制备及其性能[J]. 纺织学报, 2025, 46(08): 154-163.

CHEN Zhanyu, YU Senlong, ZHOU Jialiang, ZHU Liping, ZHOU Zhe, XIANG Hengxue, ZHU Meifang. Preparation of polylactic acid fabrics modified with phosphonic acid and their properties[J]. Journal of Textile Research, 2025, 46(08): 154-163.

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链接本文: http://www.fzxb.org.cn/CN/10.13475/j.fzxb.20241201901

http://www.fzxb.org.cn/CN/Y2025/V46/I08/154

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参考文献 21

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织物编号	P含量/(mg·g^-1)	涂层增重率/%
PLA	0.33	0
FR-PLA-2C	35.23	13.5
FR-PLA-4C	41.45	16.5
FR-PLA-6C	38.90	15.1
FR-PLA-8C	32.22	13.7

织物	T_5%/ ℃		T_max/ ℃		R_max/ (%·℃^-1)		600 ℃时的残炭量/%
织物	氮气	空气	氮气	空气	氮气	空气	氮气	空气
PLA	342.8	312.7	384.3	374.2	52.02	50.74	0	0
FR-PLA-2C	271.3	261.2	386.2	376.4	26.62	46.34	11.5	0.69
FR-PLA-4C	275.3	265.4	383.7	373.7	23.82	42.09	12.0	2.80
FR-PLA-6C	295.5	275.2	384.0	374.5	30.84	46.99	11.4	0.79
FR-PLA-8C	290.4	270.4	382.7	372.4	30.23	46.18	11.2	0.83

织物种类	ΔE值
PLA与FR-PLA-2C	0.96
PLA与FR-PLA-4C	1.09
PLA与FR-PLA-6C	1.14
PLA与FR-PLA-8C	1.47

有机膦酸改性聚乳酸织物的制备及其性能

Preparation of polylactic acid fabrics modified with phosphonic acid and their properties

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