Journal of Textile Research ›› 2026, Vol. 47 ›› Issue (1): 63-71.doi: 10.13475/j.fzxb.20250503201

• Fiber Materials • Previous Articles     Next Articles

Preparation and properties of flame retardant poly(L-lactic acid)/pentaerythritol phosphate fibers and fabrics

DONG Zhenfeng1, ZHANG Anying2, WEI Jianfei3, ZHU Zhiguo1, WANG Rui3()   

  1. 1. School of Materials Design and Engineering, Beijing Institute of Fashion Technology, Beijing 100029, China
    2. Xinxing Cathay International (Beijing) Institute of Materials Technology Co., Ltd., Beijing 100078, China
    3. Beijing Key Laboratory of Clothing Materials R&D and Assessment, Beijing Institute of Fashion Technology, Beijing 100029, China
  • Received:2025-05-20 Revised:2025-11-03 Online:2026-01-15 Published:2026-01-15
  • Contact: WANG Rui E-mail:clywangrui@bift.edu.cn

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Abstract:

Objective Poly (L-lactic acid) (PLLA) is a biodegradable polymer synthesized from renewable biomass resources. Its main raw materials are starch-rich crops. In natural environments, PLLA can be gradually decomposed by microorganisms into carbon dioxide and water, which are non-toxic and harmless to the human body. This aligns with the green development logic of ″coming from nature and returning to nature″. PLLA exhibits good mechanical strength, stiffness, and processing fluidity. It can be processed into products of various forms meeting application needs in different fields. PLA has become a research hotspot and application focus in the field of materials science in recent years.

However, PLLA and its fabrics also has obvious performance shortcomings, among which flammability is the most critical one. Its limiting oxygen index (LOI value) is only 21%, meaning that PLLA is easily flammable when in contact with an open flame. This defect severely restricts its application in fields with explicit fire resistance requirements. In order to improve the flame retardancy of PLA fabrics, a large number of studies have been conducted in the industry. Pentaerythritol phosphate, as a cage-like phosphate flame retardant, not only has extremely low biological toxicity (avoiding the harm of conventional flame retardants to the environment and human body) but also can interact with the terminal hydroxyl groups in the PLA molecular chain to form a stable flame-retardant system. While increasing the LOI value of PLLA and suppressing molten dripping during combustion, it retains the original physical and mechanical properties as well as biodegradability of PLLA to the greatest extent, opening up a new path for the application of PLLA in fields with high fire protection requirements.

Method The PLLA/PEPA masterbatch with 40% PEPA was prepared using a twin-screw extruder, and then the masterbatch was mixed with PLLA followed by injection molding to fabricate a series of PLLA/PEPA composites with different mass percentages of PEPA. The structure and properties of the composites were characterized and tested using differential scanning calorimetry, thermogravimetric analysis, extreme oxygen index analyzer, cone calorimeter, vertical combustion tester, and universal tensile machine. The composite with the best comprehensive performance was optimized for the preparation of fibers and fabrics, and the flame retardant performance of the fabrics was evaluated.

Results When the mass fraction of PEPA added was not greater than 6%, PLLA/PEPA showed good processing performance, and the glass transition temperature, crystallization temperature, melting temperature, and thermal decomposition temperature of the composite were not significantly affected. When the mass percentage of PEPA added was 5%, the LOI value of the composite was 32%, the vertical combustion test reached V-0 level, and the ignition time was prolonged by about 25 s. The composite with 5% PEPA added demonstrated good spinnability. The mechanical testing results showed that the fiber fineness was 185.7 dtex(72 f), and the fiber breaking strength and elongation at break were 2.38 cN/dtex and 21.5%, respectively. Flame retardant performance testing conformed that the LOI value of the fabric was about 33%, the vertical combustion test of the fabric was V-0 level, and the flame retardant performance of the fabric remained unchanged after 30 cycles of water washing. Study on flame retardant mechanism suggested that the improvement of flame retardant performance of PLLA by PEPA was attributed to the combined effect of free radical scavenging mechanism, condensed phase flame retardant mechanism and cross-linking induced melt viscosity increase.

Conclusion After adding PEPA with a mass fraction of 5% to PLLA, the flame retardant performance of the material is significantly improved in effectively increasing the difficulty of ignition, delaying the combustion process, and reducing the flame spread rate. The fabric obtained from the modified PLLA fibers by weaving maintains excellent mechanical properties as well as flame retardant performance, balancing practicality and safety. More importantly, the flame retardant effect of the fabric does not decrease after 30 washing cycles, showing outstanding performance stability. This scheme provides a new method with great application value for preparing safe, harmless, environmentally friendly and biodegradable flame retardant fabrics.

Key words: poly(L-lactic acid), pentaerythritol phosphate, flame retardant performance, spinnability, limiting oxygen index, ignition time

CLC Number: 

  • TQ342.89

Fig.1

DSC results of PLLA, PEPA and PLLA/PEPA"

Fig.2

SEM image of PEPA after removal of PLLA from composite"

Tab.1

Melting enthalpies of PLLA and PLLA/PEPA"

样品名称 热焓/(J·g-1) 样品名称 热焓/(J·g-1)
PLLA 34.47 PLLA/PEPA4 35.40
PLLA/PEPA2 35.89 PLLA/PEPA5 37.52
PLLA/PEPA3 35.73 PLLA/PEPA6 38.70

Fig.3

Thermal behavior analysis of PLLA/PEPA"

Fig.4

Relationship between combustion parameters and time of PLLA and PLLA/PEPA. (a) HRR; (b) THR; (c) TSP; (d) Mass retention rate"

Tab.2

LOI value and vertical combustion results of PLLA/PEPA"

样品
名称		 LOI值/% 垂直燃烧性能测试结果
第1次引燃后
自熄时间/s		 第2次引燃后
自熄时间/s		 是否有熔滴 是否引燃
脱脂棉		 等级 熔滴状态
PLLA 21±1 24.6±4.6 23.0±4.8 是 是 无 液滴
PLLA/PEPA1 26±1 17.0±4.1 2.0±0.5 是 是 V-2 液滴
PLLA/PEPA2 28±1 14.6±2.3 1.7±0.3 是 是 V-2 漫流
PLLA/PEPA3 30±1 8.1±0.9 0 是 否 V-0 漫流
PLLA/PEPA4 31±1 2.9±1.2 0 是 否 V-0 漫流
PLLA/PEPA5 32±1 1.8±0.2 0 是 否 V-0 漫流
PLLA/PEPA6 33±1 1.8±0.3 0 是 否 V-0 漫流
PLLA/PEPA8 33±1 1.6±0.3 0 是 否 V-0 漫流

Fig.5

Vertical combustion states of PLLA (left) and PLLA/PEPA5 (right)"

Fig.6

Rheological test results of PLLA/PEPA5"

Tab.3

Mechanical properties of PLLA and PLLA/PEAP fibers"

样品名称 线密度/
(dtex(96 f))		 断裂强度/
(cN·dtex-1)		 断裂伸长率/
%
PLLA 113.0 3.31 25.21
PLLA/PEPA3 113.2 2.65 27.14
PLLA/PEPA5 112.8 2.51 23.55

Fig.7

SEM images of PLLA/PEPA5 fibers and PEPA with PLLA dissolved. (a) Fiber surface; (b) Fiber cross-section; (c) PEPA dissolved from PLLA in fibers"

Tab.4

PLLA/PEPA5 fabric flame retardant performance test results"

方向 LOI值/% 垂直燃烧性能测试结果
续燃时间/s 阴燃时间/s 损毁长度/mm 滴落物
水洗前 水洗30次后 水洗前 水洗30次后 水洗前 水洗30次后 水洗前 水洗30次后 水洗前 水洗30次后
经向 33.0 32.6 0 0 0 0 156 136 无 无
纬向 32.6 33.1 0 0 0 0 161 132 无 无

Fig.8

Photos and SEM images of PLLA/PEPA combustion residues. (a) PLLA/PEPA2; (b) PLLA/PEPA4; (c) PLLA/PEPA6; (d) Flaky residue (×700); (e) Granular residue (×700); (f) Granular residue (×5 000)"

Fig.9

Reaction of anhydrous decomposition products of PEPA with hydroxyl groups"

Fig.10

Reaction formala of phosphoric acid with terminal hydroxyl groups of PLLA"

Fig.11

Raman spectra of combustion residues"

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