无卤无磷阻燃聚酰胺超细纤维合成革的制备及其性能

doi:10.13475/j.fzxb.20240100901

纺织学报 ›› 2024, Vol. 45 ›› Issue (11): 162-169.doi: 10.13475/j.fzxb.20240100901

无卤无磷阻燃聚酰胺超细纤维合成革的制备及其性能

杜蕾¹^,², 王士杰¹^,², 蒋之铭¹^,²(), 朱平¹^,²

1.青岛大学功能纺织品与先进材料研究院, 山东青岛 266071
2.青岛大学纺织服装学院, 山东青岛 266071

收稿日期:2024-01-08 修回日期:2024-06-03 出版日期:2024-11-15 发布日期:2024-12-30
通讯作者: 蒋之铭(1989—),男,副教授,博士。主要研究方向为功能纺织材料。E-mail:jzm070315@163.com。
作者简介:杜蕾(1999—),女,硕士生。主要研究方向为阻燃纤维纺织品。
基金资助:
国家自然科学基金项目(51991354);国家自然科学基金项目(51991350)

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. 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 Published:2024-11-15 Online:2024-12-30

摘要/Abstract

摘要： 超细纤维合成革(MSL)凭借其优异的透气、耐磨、耐用等特性,广泛应用于家居内饰、高铁、汽车及航空航天等领域,但其易燃和熔滴问题严重威胁人身财产安全,极大限制了其在特定领域中的应用。为解决此问题,采用层层自组装技术,以生物多糖卡拉胶(KC)为阴离子电解质,分别与阳离子电解质聚乙烯亚胺(PEI)、3-氨丙基三乙氧基硅烷(APTES)及其混合物相结合,通过构建无卤无磷体系制备了阻燃聚酰胺超细纤维合成革(PA/MSL)。结果表明:APTES的引入可显著提升超细纤维合成革的成炭能力,有效解决了超细纤维合成革的融滴问题,与PA/MSL原样和KC/PEI体系相比,由KC/APTES体系制备的超细纤维合成革的极限氧指数为26.0%,无熔滴产生,在800 ℃氮气和空气气氛下的残炭量分别为14.2%和10.3%;此外,KC/APTES/PEI三元体系能赋予超细纤维合成革优异的阻燃性能,当KC/APTES/PEI涂层负载量为34.1%时,超细纤维合成革的极限氧指数提升至37%,且可在垂直燃烧测试中实现自熄,无熔滴产生。

关键词: 超细纤维合成革, 阻燃, 抗熔滴, 生物多糖卡拉胶, 层层自组装, 聚酰胺

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

中图分类号:

TS195.5

杜蕾, 王士杰, 蒋之铭, 朱平. 无卤无磷阻燃聚酰胺超细纤维合成革的制备及其性能[J]. 纺织学报, 2024, 45(11): 162-169.

DU Lei, WANG Shijie, JIANG Zhiming, ZHU Ping. Preparation and properties of halogen-free and phosphorus-free environment-friendly flame-retardant system for polyamide microfiber synthetic leather[J]. Journal of Textile Research, 2024, 45(11): 162-169.

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链接本文: http://www.fzxb.org.cn/CN/10.13475/j.fzxb.20240100901

http://www.fzxb.org.cn/CN/Y2024/V45/I11/162

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

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/%
样品	气氛	质量损失5%时的温度/℃	第1个	第2个	第3个	第4个	第5个	800 ℃时的残炭量/%
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

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

无卤无磷阻燃聚酰胺超细纤维合成革的制备及其性能

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

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