Journal of Textile Research ›› 2025, Vol. 46 ›› Issue (08): 154-163.doi: 10.13475/j.fzxb.20241201901

• Dyeing and Finishing Engineering • Previous Articles     Next Articles

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. 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 Online:2025-08-15 Published:2025-08-15
  • Contact: YU Senlong E-mail:ysl@dhu.edu.cn

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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 (Rmax) 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 Rmax 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

CLC Number: 

  • TS195.2

Fig.1

Schematic illustration of flame-retardant modification for PLA fabric"

Fig.2

Microscopic morphologies(a) and elemental compositions(b) of flame-retardant PLA fabrics"

Tab.1

P content and mass change of flame-retardant PLA fabrics"

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

Fig.3

FT-IR spectra of flame-retardant PLA fabrics"

Tab.2

Thermal stability data of flame-retardant PLA fabrics"

织物 T5%/
℃		 Tmax/
℃		 Rmax/
(%·℃-1)		 600 ℃时的
残炭量/%
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

Fig.4

TG and DTG curves of flame-retardant PLA fabrics under nitrogen and air atmospheres. (a) TG curves under nitrogen; (b) DTG curves under nitrogen; (c) TG curves in air; (d) DTG curves in air"

Fig.5

Flame retardancy of PLA fabrics. (a) LOI and UL-94; (b) Damaged length; (c) Digital photographs of UL-94 test"

Fig.6

CCT-PHRR curves(a), CCT-THR curves(b) and MCC-PHRR curves (c) of PLA and FR-PLA-4C fabrics"

Fig.7

FR-IR spectra at different temperature of PLA and FR-PLA-4C during thermal degradation process"

Fig.8

Three-dimensional TG-IR spectra of PLA and FR-PLA-4C fabrics"

Fig.9

SEM images of flame-retardant PLA fabrics residues"

Fig.10

Raman spectrum of flame-retardant PLA fabrics residues"

Fig.11

Service performance of flame-retardant PLA fabrics. (a) Breaking strength and bending length; (b) Flexibility and permeability; (c) Washing durability"

Tab.3

Visual appearance of flame-retardant PLA fabrics"

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
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