Journal of Textile Research ›› 2024, Vol. 45 ›› Issue (11): 162-169.doi: 10.13475/j.fzxb.20240100901

• Original article • Previous Articles     Next Articles

Preparation and properties of halogen-free and phosphorus-free environment-friendly flame-retardant system for polyamide microfiber synthetic leather

DU Lei1,2, WANG Shijie1,2, JIANG Zhiming1,2(), ZHU Ping1,2   

  1. 1. Institute of Functional Textiles and Advanced Materials, Qingdao University, Qingdao, Shandong 266071, China
    2. College of Textile and Clothing, Qingdao University, Qingdao, Shandong 266071, China
  • Received:2024-01-08 Revised:2024-06-03 Online:2024-11-15 Published:2024-12-30
  • Contact: JIANG Zhiming E-mail:jzm070315@163.com

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Abstract:

Objective As an excellent substitute for natural leather, microfiber synthetic leather (MSL) is widely used in aerospace, high-speed rail, domestic decoration and other fields because of its excellent performance such as air permeability and wear resistance. However, MSL is composed of flammable polymers like polyamide, polyester, and polyurethane. When it burns, serious droplet melting occurs, endangering personal safety. As a result, it is critical to endow MSL with flame-retardant properties.

Method In order to solve the flammability of polyamide microfiber synthetic leather (PA/MSL), layer by layer self-assembly technique was applied using biological polysaccharide carrageenan (KC) as anion component, and polyethylenimine (PEI), (3-aminopropyl)triethoxysilane polymer (APTES) and their mixtures as cationic components. The influence of different components on the flame retardation of PA/MSL was investigated.

Results Compared with the control sample, the modified MSL presented some additional characteristic peaks responding to KC, PEI and APTES in the infrared spectra. In addition, the surface of the modified MSL was covered by the flame-retardant coating. Meanwhile, S and Si elements with uniform distribution were detected in the modified MSL, which were from the KC and APTES, respectively. The results indicated that the flame-retardant coating was successfully assembled on the surface of MSL. The flame-retardant performance of the modified MSL were analyzed by vertical flammability test (VFT) and limited oxygen index (LOI). KC/PEI and KC/APTES were found to improve the flame retardant performance of MSL with LOI values of 24% and 26%. Furthermore, the modified MSL by ternary self-assembly systems (KC/APTES/PEI) presented perfect flame retardancy with LOI value of 37%, and self-extinguishing behavior could be achieved without melt-dropping in VFT. The thermal stability of the modified MSL was analyzed through thermal degradation. Compared with control sample, the carbon residue of the modified MSL was increased to 14.2% at 800 ℃ in nitrogen gas atmosphere. The carbon residue of modified MSL by KC/APTES and KC/APTES/PEI showed characteristic peaks belonging to Si-O-Si bonds, indicating the formation of silicon-carbon chemical compounds. Meanwhile, silicon or sulfur elements were maintained in the char residues. The combustion behavior of control sample and modified MSL were studied by cone calorimetry test. The total heat release and total smoke release of modified MSL did not decrease as compared to the control sample. Still, the increased TTI demonstrated that the assembled coating had some effect on increasing the flame-retardant performance of the MSL.

Conclusion The influences of different cationic and anionic components on the flame retardant and anti-dripping properties of PA/MSL were investigated using layer by layer self-assembly technology. The flame-retardant performance and thermal stability properties of modified MSL were analyzed. The results showed that all flame-retardant coatings significantly improve its carbon formation capacity. Meanwhile, the ternary self-assembly systems (KC/APTES/PEI) greatly improved the flame-retardant performance of PA/MSL and the LOI values increased to 37% with self-extinguishing behavior and anti-drip phenomenon. This study presented a facile method to prepare flame-retardant MSL with non-phosphorous flame-retardant coating, which promotes the green development of flame-retardant materials.

Key words: microfiber synthetic leather, flame retardant, anti-dripping, bio-polysaccharide carrageenan, layer by layer self-assembly, polyamide

CLC Number: 

  • TS195.5

Fig.1

FT-IR spectra of different samples"

Fig.2

SEM images (×200) and EDS mapping of different microfiber synthetic leather. (a)PA/MSL microfiber synthetic leather;(b) KC/PEI flame-retardant microfiber synthetic leather; (c) KC/APTES flame-retardant microfiber synthetic leather;(d) KC/APTES/PEI flame-retardant microfiber synthetic leather"

Fig.3

Digital images of different microfiber synthetic leather after VFT. (a)PA/MSL microfiber synthetic leather;(b) KC/PEI flame-retardant microfiber synthetic leather;(c) KC/APTES flame-retardant microfiber synthetic leather;(d) KC/APTES/PEI flame-retardant microfiber synthetic leather"

Tab.1

LOI and VFT data of different microfiber synthetic leather"

样品 负载量/
%		 损毁
长度/
cm		 续燃
时间/
s		 阴燃
时间/
s		 是否
熔滴		 LOI值/
%
PA/MSL超
纤革原样		 0 30.0 48 0 是 18.1
KC/PEI阻燃
超纤革		 31.0 11.0 38 0 是 24.0
KC/APTES
阻燃超纤革		 24.9 30.0 80 0 否 26.0
KC/APTES/PEI
阻燃超纤革		 34.1 11.0 87 0 否 37.0

Fig.4

TG and DTG curves of different microfiber synthetic leather in N2 and air atmosphere. (a) TG curves in N 2 ;(b) DTG curves in N2;(c) TG curves in air;(d) DTG curves in air"

Tab.2

TG and DTG data of different microfiber synthetic leather in N2 and air atmosphere"

样品 气氛 质量损失5%时
的温度/℃		 最大质量损失温度/℃ 800 ℃时的
残炭量/%
第1个 第2个 第3个 第4个 第5个
PA/MSL超纤革原样 氮气 280 246 316 430 — — 2.5
KC/PEI阻燃超纤革 210 233 254 410 — — 10.4
KC/APTES阻燃超纤革 200 203 262 396 — — 14.2
KC/APTES/PEI阻燃超纤革 241 232 254 395 420 — 10.9
PA/MSL超纤革原样 空气 284 242 — 340 432 586 0.4
KC/PEI阻燃超纤革 202 229 261 361 426 614 1.2
KC/APTES阻燃超纤革 209 197 256 363 424 617 10.3
KC/APTES/PEI阻燃超纤革 232 227 259 379 423 638 2.9

Fig.5

FT-IR spectra of char residues from flame-retardant microfiber synthetic leather after combustion"

Fig.6

SEM images (×2 000) and EDS mapping of char residues for flame-retardant microfiber synthetic leather after combustion"

Fig.7

HRR (a), THR (b) and TSP (c) curves of different microfiber synthetic leather"

Tab.3

Data obtained from CCT for different microfiber synthetic leather"

样品名称 点火
时间/s		 最大热释
放速率/
(kW·m-2)		 平均热
释放速率/
(kW·m-2)		 总热
释放量/
(MJ·m-2)		 总烟
释放量/
(m2·m-2)
PA/MSL
超纤革原样		 15 154.9 24.2 7.0 0.05
KC/PEI
阻燃超纤革		 41 184.7 27.5 7.0 1.70
KC/APTES
阻燃超纤革		 20 180.9 23.8 6.7 1.27
KC/APTES/PEI
阻燃超纤革		 27 183.8 24.6 6.8 0.90
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