磷酸酯化聚乙烯亚胺阻燃粘胶织物的制备与性能

doi:10.13475/j.fzxb.20220201401

纺织学报 ›› 2023, Vol. 44 ›› Issue (06): 161-167.doi: 10.13475/j.fzxb.20220201401

磷酸酯化聚乙烯亚胺阻燃粘胶织物的制备与性能

蒋之铭¹^,²^,³^,⁴, 张超¹^,²^,³^,⁴, 张晨曦¹^,²^,³^,⁴, 朱平¹^,²^,³^,⁴()

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
3.青岛大学新型防火阻燃材料开发与应用国家地方联合工程研究中心, 山东青岛 266071
4.省部共建生物多糖纤维成形与生态纺织国家重点实验室, 山东青岛 266071

收稿日期:2022-02-11 修回日期:2022-12-02 出版日期:2023-06-15 发布日期:2023-07-20
通讯作者: 朱平
作者简介:蒋之铭(1989—),男,副教授,博士。主要研究方向为纤维改性及功能纺织品。
基金资助:
国家重点研发计划项目(2017YFB0309001)

Preparation and properties of flame-retardant viscose fabrics modified with phosphated polyethyleneimine

JIANG Zhiming¹^,²^,³^,⁴, ZHANG Chao¹^,²^,³^,⁴, ZHANG Chenxi¹^,²^,³^,⁴, ZHU Ping¹^,²^,³^,⁴()

1. Institute of Functional Textiles and Advanced Materials, Qingdao University, Qingdao, Shandong 266071, China
2. College of Textile & Clothing, Qingdao University, Qingdao, Shandong 266071, China
3. National Engineering Research Center for Advanced Fire-Safety Materials D & A (Shandong), Qingdao University, Qingdao, Shandong 266071, China
4. State Key Laboratory of Bio-Fibers and Eco-Textiles, Qingdao, Shandong 266071, China

Received:2022-02-11 Revised:2022-12-02 Published:2023-06-15 Online:2023-07-20
Contact: ZHU Ping

摘要/Abstract

摘要：

为降低多元羧酸交联剂的强酸性对阻燃粘胶织物的强力损伤,以多氨基磷酸酯化聚乙烯亚胺(BPEI-DP)为阻燃剂, 在1,2,3,4-丁烷四羧酸(BTCA)的交联作用下得到阻燃粘胶织物,研究了其表面化学组成、阻燃性能、热降解稳定性能和热释放行为,分析了BPEI-DP/BTCA体系对粘胶织物力学性能的影响。结果表明:阻燃粘胶织物的极限氧指数(LOI)提升至28.9%,垂直燃烧测试中阻燃织物离火自熄,无续燃和阴燃现象,损毁长度为9.9 cm; 相比于纯粘胶织物,阻燃粘胶织物的成炭性显著提升,热释放明显降低,最大热释放速率下降了34%;其耐水洗性能与N-羟甲基-3-(二甲氧基膦酰基)丙酰胺阻燃粘胶织物相当,20次标准水洗后LOI值从28.9%下降至24.9%;该阻燃体系有效保留了粘胶织物的断裂强力,保留率可达70%左右,为高品质阻燃纺织品的设计制备提供了思路。

关键词: 粘胶织物, 磷酸酯化聚乙烯亚胺, 1,2,3,4-丁烷四羧酸, 阻燃整理, 力学性能

Abstract:

Objective As one of the most important regenerated cellulose materials, viscose fibers are easily flammable and it has potential threat to human lives and properties. Researches show that viscose textiles can obtain flame retardancy by flame-retardant additives and finishing. Compared with flame-retardant additives, textile finishing is easy to operate. 1,2,3,4-Butane tetracarboxylic acid (BTCA), as a common cross-linker, has been widely applied to prepare functional cellulose textiles. However, its highly acidic condition may cause big strength loss of viscose fabrics. It is necessary to find an efficient way to reduce strength loss of flame-retardant viscose fabrics cross-linked with BTCA.
Method A multi-amino phosphated polyethyleneimine (BPEI-DP) was synthesized through simple Atherton-Todd reaction and applied to prepare flame-retardant viscose fabric crosslinking with BTCA. The design of BPEI-DP can decrease the acidic condition of BTCA and flame-retardant viscose fabric with low strength loss was achieved. Also, the BTCA crosslinking can improved the washing durability of flame-retardant viscose fabric. The flame retardancy, heat release, thermal stability, washing durability and mechanical properties were investigated.
Results The limiting oxygen index (LOI) value of the viscose fabric was found to increase to 28.9% after finishing with BPEI-DP and BTCA, and the treated fabric presented self-extinguishing behavior with no afterflame/aftergrow appearance and damage length of 9.9 cm in the vertical burning test (Fig. 2 and Tab. 1). The viscose fiber becomes rougher after flame-retardant finishing and some additional characteristic absorption peaks were appeared on the treated viscose fabric (Fig. 3 and Fig. 4), which indicates that flame retardancy was successfully deposited onto the viscose fibers. BPEI-DP/BTCA flame-retardant system showed significantly improvement in the carbon-forming ability of viscose fabric. The appearance of flame-retardant fiber was well maintained after combustion (Fig. 6). 40.0% and 14.8% of char residues were maintained at 800 ^oC under N₂and air atmosphere, respectively(Fig. 7 and Tab. 2). From cone calorimetry test (CCT), it is found that the with maximum heat release rate(pHRR) was reduced by 34% from 284 kW/m² to 189 kW/m² (Fig. 8 and Tab. 3). The washing resistance of BPEI-DP/BTCA treated viscose fabric was comparable to that of Pyrovatex CP. LOI value has slight reduction along with the increase of washing cycles. After 20 standard washing cycles, LOI value decreased from 28.9% to 24.9%, which is much higher than control viscose fabric (Fig. 9). This flame-retardant finishing system effectively maintained the strength of flame retardant viscose fabric. The breaking forces in the warp and weft direction reduced from (406±18) N to (284±13) N and (254±6) N to (168±11) N, respectively. Compared with control viscose fabric, the strength retention rate could reach about 70% and the whiteness has a significant reduction from (77.6±0.3)% to (30.1±0.5)% after flame-retardant finishing (Tab. 4).
Conclusion This study provides ideas for the design and preparation of flame-retardant cellulose fabric with low strength loss. BPEI-DP can not only render viscose fabric with good flame retardancy through improving the char-forming capacity, but also reduce the strength loss of viscose fabric crosslinking with BTCA by decreasing its acidic condition. However, the washing durability of BPEI-DP/BTCA treated viscose fabric is unsatisfactory and this finishing system has bad effect on the whiteness of viscose fabric. Therefore, more efficient and friendly flame-retardant system need to be developed to improve the washing durability and inherent properties of flame-retardant fabric.

Key words: viscose fabric, phosphated polyethyleneimine, 1,2,3,4-butane tetracarboxylic acid, flame-retardant finishing, mechanical property

中图分类号:

TS195.5

蒋之铭, 张超, 张晨曦, 朱平. 磷酸酯化聚乙烯亚胺阻燃粘胶织物的制备与性能[J]. 纺织学报, 2023, 44(06): 161-167.

JIANG Zhiming, ZHANG Chao, ZHANG Chenxi, ZHU Ping. Preparation and properties of flame-retardant viscose fabrics modified with phosphated polyethyleneimine[J]. Journal of Textile Research, 2023, 44(06): 161-167.

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BPEI-DP 质量浓度/ (g·L^-1)	负载量/ %	LOI值/ %	续燃时间/s	阴燃时间/s	损毁长度/cm
0	0	21.0	18.1	50.0	≥30.0
100	4.3	23.2	3.6	0	≥30.0
200	9.1	24.1	1.5	0	≥30.0
300	15.0	25.9	0	0	24.7
400	19.7	27.2	0	0	23.1
500	23.6	28.9	0	0	9.9

样品名称	T_5%/℃		T_max/℃		残炭量/%
	T_5%/℃		T_max/℃		T_max时		800 ℃时
	氮气	空气	氮气	空气	氮气	空气	氮气	空气
	原粘胶织物	262	259	340	326	45.0	47.5	18.8	—
阻燃粘胶织物	167	214	270	269	74.5	76.7	40.0	14.8

样品名称	pHRR/ (kW·m^-2)	THR/ (MJ·m^-2)	Av-EHC/ (MJ·kg^-1)	CO₂与CO 质量比/ (kg·kg^-1)
原粘胶织物	284	5.9	13.2	14.8
阻燃粘胶织物	189	5.7	11.2	9.9

样品名称	断裂强力/N		白度/%
样品名称	经向	纬向	白度/%
原粘胶织物	406±18	254±6		77.6±0.3
阻燃粘胶织物	284±13	168±11		30.1±0.5

磷酸酯化聚乙烯亚胺阻燃粘胶织物的制备与性能

Preparation and properties of flame-retardant viscose fabrics modified with phosphated polyethyleneimine

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