聚磷腈改性沸石咪唑酯骨架材料的制备及其在聚酯阻燃中的应用

doi:10.13475/j.fzxb.20211106809

纺织学报 ›› 2022, Vol. 43 ›› Issue (11): 104-112.doi: 10.13475/j.fzxb.20211106809

聚磷腈改性沸石咪唑酯骨架材料的制备及其在聚酯阻燃中的应用

李宝洁¹^,², 朱元昭¹^,², 钟毅¹^,²^,³, 徐红¹^,²^,³, 毛志平¹^,²^,³()

1.东华大学生态纺织教育部重点实验室, 上海 201620
2.东华大学化学与化工学院, 上海 201620
3.东华大学纺织科技创新中心, 上海 201620

收稿日期:2021-11-12 修回日期:2022-07-22 出版日期:2022-11-15 发布日期:2022-12-26
通讯作者: 毛志平
作者简介:李宝洁(1997—),男,硕士生。主要研究方向为聚合物材料阻燃改性。
基金资助:
国家重点研发计划项目(2018YFC1801502)

Preparation and application of polyphosphazene modified zeolite imidazolate framework materials for flame retardancy of poly(ethylene terephthalate)

LI Baojie¹^,², ZHU Yuanzhao¹^,², ZHONG Yi¹^,²^,³, XU Hong¹^,²^,³, MAO Zhiping¹^,²^,³()

1. Key Laboratory of Science and Technology of Eco-Textile, Ministry of Education, Donghua University, Shanghai 201620, China
2. College of Chemistry and Chemical Engineering, Donghua University, Shanghai 201620, China
3. Innovation Center for Textile Science and Technology, Donghua University, Shanghai 201620, China

Received:2021-11-12 Revised:2022-07-22 Published:2022-11-15 Online:2022-12-26
Contact: MAO Zhiping

摘要/Abstract

摘要：

为提高聚对苯二甲酸乙二醇酯(PET)的阻燃性能,以六水合硝酸锌和2-甲基咪唑制备沸石咪唑酯骨架材料(ZIF-8),之后用六氯环三磷腈和4,4 -二羟基二苯砜对ZIF-8进行表面修饰合成一种ZIF-8聚环三磷睛-共磺酰基双酰/(PZS)亚微米颗粒,并与PET通过熔融共混制备PET阻燃复合材料。借助热重分析仪、极限氧指数仪、垂直燃烧仪、万能材料试验机以及扫描电镜等对复合材料的热稳定性、阻燃抗熔滴性、力学性能以及阻燃机制进行分析。结果表明:添加6%的ZIF-8/PZS亚微米颗粒使PET的极限氧指数(LOI值)提高到29.2%,并通过UL-94 V-0等级,而复合材料的力学性能没有受到严重影响;ZIF-8/PZS可以在气相和凝聚相中同时发挥效用,从而赋予PET复合材料优异的阻燃性能。

关键词: 亚微米颗粒, 阻燃纤维, 抗熔滴, 熔融共混, 聚对苯二甲酸乙二醇酯, 沸石咪唑酯骨架材料

Abstract:

In order to improve the flame retardancy of poly (ethylene terephthalate) (PET), a zeolite imidazolate framework material (ZIF-8) was fabricated from zinc nitrate hexahydrate and 2-methylimidazole. The surface of ZIF-8 were modified with hexachlorocyclotriphosphazene and 4,4-dihydroxydiphenylsulfone to synthesize a ZIF-8/PZS submicron particle. PET flame-retardant composites were prepared by melt blending with PET and their flame-retardant properties were investigated. Thermogravimetric analyzer, limiting oxygen index meter, vertical combustion meter, material testing machine and scanning electron microscope were used to analyze the thermal stability, flame retardancy, melt-dripping resistance, mechanical properties and flame-retardant mechanism of composite materials. The results show that the addition of 6% ZIF-8/PZS submicron particles increases the LOI value of PET to 29.2% and passes UL-94 V-0 level. The mechanical properties of the composite materials are not severely affected. ZIF-8/PZS can be effective in both the gas phase and the condensed phase, thereby giving PET composites excellent flame-retardant properties.

Key words: submicron particles, flame retardant fiber, anti-dripping, melt blending, poly (ethylene terephthalate), zeolite imidazolate framework materials

中图分类号:

TS195.2

李宝洁, 朱元昭, 钟毅, 徐红, 毛志平. 聚磷腈改性沸石咪唑酯骨架材料的制备及其在聚酯阻燃中的应用[J]. 纺织学报, 2022, 43(11): 104-112.

LI Baojie, ZHU Yuanzhao, ZHONG Yi, XU Hong, MAO Zhiping. Preparation and application of polyphosphazene modified zeolite imidazolate framework materials for flame retardancy of poly(ethylene terephthalate)[J]. Journal of Textile Research, 2022, 43(11): 104-112.

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样品编号	T_-5%/ ℃	T_max/ ℃	800 ℃残炭率/ %	最大分解速率/ (%·min^-1)
1^#	391	437	9.4	19.8
2^#	343	418	14.2	17.9
3^#	331	405	12.1	15.8
4^#	339	421	15.3	15.3
5^#	336	403	16.1	13.4
6^#	335	416	16.4	13.9

样品编号	LOI值/%	垂直燃烧实验
样品编号	LOI值/%	UL94等级	熔滴	点燃脱脂棉
1^#	23.1±0.1	V-2	严重	是
2^#	26.0±0.1	V-1	缓慢	否
3^#	25.5±0.1	V-1	严重	否
4^#	27.3±0.1	V-0	很少	否
5^#	29.2±0.1	V-0	很少	否
6^#	30.6±0.1	V-0	很少	否

样品	元素含量/(mg·g^-1)
样品	C	N	P	Zn
5^#	61.56	3.18	2.42	12.05
5^#残炭	86.52	1.20	13.36	79.75

聚磷腈改性沸石咪唑酯骨架材料的制备及其在聚酯阻燃中的应用

Preparation and application of polyphosphazene modified zeolite imidazolate framework materials for flame retardancy of poly(ethylene terephthalate)

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参考文献 22

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样品编号	ZIF-8 质量/g	PZS 质量/g	ZIF-8/PZS 质量/g	PET 质量/g	总质量/ g
1^#	—	—	—	100	100
2^#	3	—	—	97	100
3^#	—	3	—	97	100
4^#	—	—	3	97	100
5^#	—	—	6	94	100
6^#	—	—	9	91	100

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样品编号	ZIF-8 质量/g	PZS 质量/g	ZIF-8/PZS 质量/g	PET 质量/g	总质量/ g
1^#	—	—	—	100	100
2^#	3	—	—	97	100
3^#	—	3	—	97	100
4^#	—	—	3	97	100
5^#	—	—	6	94	100
6^#	—	—	9	91	100

样品编号	ZIF-8 质量/g	PZS 质量/g	ZIF-8/PZS 质量/g	PET 质量/g	总质量/ g
1^#	—	—	—	100	100
2^#	3	—	—	97	100
3^#	—	3	—	97	100
4^#	—	—	3	97	100
5^#	—	—	6	94	100
6^#	—	—	9	91	100