棉用新型含磷氮阻燃剂的合成及其应用

doi:10.13475/j.fzxb.20180903207

摘要/Abstract

摘要：

为实现棉织物的无甲醛阻燃整理,以甲基膦酸二甲酯(DMMP)和二乙醇胺(DEA)为原料,二月桂酸二丁基锡为催化剂,通过酯交换聚合反应,合成了一种含磷氮聚醚二元醇的阻燃剂(PNFR)用于棉织物整理。借助红外光谱仪、热分析仪、扫描电子显微镜、极限氧指数仪和垂直燃烧仪对PNFR的结构及其整理织物性能进行表征。结果表明:当DMMP和DEA的量比为 1.0∶1.3,催化剂用量为反应物总质量的0.5%,反应温度为150 ℃,反应时间为5 h,合成的PNFR质量浓度为200 g/L时,整理后棉织物的续燃和阴燃时间均为0 s,损毁长度为12.1 cm,极限氧指数为28.4%,织物阻燃等级可达国家标准B1级;经10次水洗后,整理棉织物的极限氧指数下降至25.9%,其垂直燃烧性能仍可达B2级。

关键词: 阻燃剂, 磷氮二元醇, 酯交换, 棉织物, 协同阻燃

Abstract:

In order to achieve formaldehyde-free flame retardant finishing on cotton fabrics, a novel phosphorus and nitrogen-containing flame retardant polyether diol(PNFR) was synthesized from dimethyl methylphosphonate(DMMP) and diethanolamine(DEA) by transesterification polymerization using dibutyltin dilaurate as the catalyst, and it is also used for finishing cotton fabric. The structure and application performance of PNFR and the modified cotton were investigated by Fourier infrared spectrometer, thermal analyzer, scanning electron microscope, limited oxygen index tester and vertical burning instrument. The experimental results show that when the molar ratio of DMMP and DEA is 1.0∶1.3, the dosage of catalyst is 0.5% of total mass of reactants, the reaction temperature is 150 ℃, reaction time is 5 h and the dosage of PNFR is 200 g/L, the afterflame time, afterglow time, damaged length and limiting oxygen index(LOI) of the treated cotton fabric are 0 s, 12.1 cm and 28.4% respectively, reaching class B1 of national standard of flame retardant fabrics. Even after 10 washing cycles, class B2 of the treated cotton fabric is achieved while its LOI drops to 25.9%.

Key words: flame retardant, phosphorus and nitrogen-containing polyether diol, transesterification, cotton fabric, synergistic flame retardancy

中图分类号:

TS195.5

孙玉发, 周向东. 棉用新型含磷氮阻燃剂的合成及其应用[J]. 纺织学报, 2019, 40(12): 79-85.

SUN Yufa, ZHOU Xiangdong. Synthesis and characterization of novel phosphorous and nitrogen-containing flame retardant for cotton fabrics[J]. Journal of Textile Research, 2019, 40(12): 79-85.

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参考文献 15

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温度/ ℃	阻燃剂颜色状态	阻燃剂数均分子质量	整理棉的阻燃效果
温度/ ℃	阻燃剂颜色状态	阻燃剂数均分子质量	续燃时间/s	阴燃时间/s	损毁长度/cm
105	黄色黏稠液体	703	13.13	0.00	30.0
120	黄褐色黏稠液体	784	11.07	0.00	30.0
135	黄褐色黏稠液体	825	2.95	0.00	22.3
150	棕色黏稠液体	1 062	0.00	0.00	14.0
165	深棕色黏稠液体	1 034	1.64	0.00	16.1

反应时间/h	阻燃剂颜色状态	阻燃剂数均分子质量	整理棉织物的阻燃效果
反应时间/h	阻燃剂颜色状态	阻燃剂数均分子质量	续燃时间/s	阴燃时间/s	损毁长度/cm
3	淡黄色黏稠液体	680	11.94	0.00	30.0
4	黄色黏稠液体	787	10.36	0.00	30.0
5	黄色黏稠液体	1 062	0.00	0.00	14.0
6	黄褐色黏稠液体	1 049	1.56	0.00	15.8
7	黄褐色黏稠液体	1 035	2.37	0.00	16.2

催化剂质量分数/%	阻燃剂颜色状态	阻燃剂数均分子质量		整理棉织物的阻燃效果
催化剂质量分数/%	阻燃剂颜色状态	阻燃剂数均分子质量		续燃时间/s	阴燃时间/s	损毁长度/cm
0.00	淡黄色黏稠液体		651	12.81	0.00	30.0
0.25	黄色黏稠液体		783	9.79	0.00	28.9
0.50	黄色黏稠液体		1 062	0.00	0.00	14.0
0.75	黄褐色黏稠液体		824	2.76	0.00	21.1
1.00	棕色黏稠液体		815	3.65	0.00	23.2

DMMP 和DEA 的量比	阻燃剂颜色状态	阻燃剂数均分子质量	整理棉织物的阻燃效果
DMMP 和DEA 的量比	阻燃剂颜色状态	阻燃剂数均分子质量	续燃时间/s	阴燃时间/s	损毁长度/cm
1.0∶1.1	淡黄色黏稠液体	827	3.80	0.00	26.3
1.0∶1.2	淡黄色黏稠液体	915	1.04	0.00	18.5
1.0∶1.3	淡黄色黏稠液体	1 062	0.00	0.00	14.0
1.0∶1.4	黄色黏稠液体	834	2.96	0.00	21.3
1.0∶1.5	棕色黏稠液体	751	8.81	0.00	30.0

PNFR质量浓度/(g·L^-1)	白度/ %	质量增加率/%	LOI值/ %	续燃时间/s	损毁长度/cm
100	78.2	8.3	24.9	3.44	26.3
150	75.9	9.1	26.3	2.13	22.7
200	73.1	12.7	28.4	0.00	12.1
250	65.4	13.5	28.7	0.00	10.8