DOPO-BPS/OSEP/EP-CE阻燃复合材料的制备及性能

doi:10.16265/j.cnki.issn1003-3033.2025.02.0976

中国安全科学学报 ›› 2025, Vol. 35 ›› Issue (2): 111-117.doi: 10.16265/j.cnki.issn1003-3033.2025.02.0976

DOPO-BPS/OSEP/EP-CE阻燃复合材料的制备及性能

刘勇¹^,²^,³(), 姜一帆¹, 耿鑫玺¹, 张焘⁴

¹ 湖南科技大学资源环境与安全工程学院,湖南湘潭 411201
² 地下空间防火防爆材料与装备湖南省工程研究中心,湖南湘潭 411201
³ 火灾爆炸防控与应急技术湖南省普通高等学校重点实验室,湖南湘潭 411201
⁴ 南京工业大学安全科学与工程学院,江苏南京 211816

收稿日期:2024-09-02 修回日期:2024-11-11 出版日期:2025-02-28
作者简介:
刘勇 (1984—),男,湖南宁乡人,博士,副教授,主要从事危险化学品道路运输安全、海泡石防火阻燃等方面的研究。E-mail:yliu1@hnust.edu.cn。
基金资助:
湖南省自然科学基金资助(2024JJ8338)

Preparation and properties of DOPO-BPS/OSEP/EP-CE flame retardant composite materials

LIU Yong¹^,²^,³(), JIANG Yifan¹, GENG Xinxi¹, ZHANG Tao⁴

¹ College of Resources, Environment and Safety Engineering, Hunan University of Science and Technology, Xiangtan Hunan 411201, China
² Hunan Engineering Research Center for Fire and Explosion Prevention Materials and Equipment in Underground Spaces, Xiangtan Hunan 411201, China
³ Key Laboratory of Fire and Explosion Prevention and Emergency Technology in Hunan Province, Xiangtan Hunan 411201, China
⁴ College of Safety Science and Engineering, Nanjing Technology University, Nanjing Jiangsu 211816, China

Received:2024-09-02 Revised:2024-11-11 Published:2025-02-28

摘要/Abstract

摘要：

为提高环氧树脂(EP)-氰酸酯树脂(CE)复合材料的阻燃与抑烟性能,首先以9,10-二氢-9-氧杂-10-磷杂菲10-氧化物(DOPO)与4,4'-二羟基二苯砜(BPS)为原料,合成一种新型阻燃剂DOPO-BPS,通过溶液浇筑法,将DOPO-BPS与有机海泡石(OSEP)共同引入EP-CE基体中,制备阻燃DOPO-BPS/OSEP/EP-CE复合材料;然后在傅里叶红外光谱仪(FTIR)分析、核磁共振(NMR)分析、热重分析(TGA)、极限氧指数(LOI)测试、UL-94垂直燃烧测试和锥形量热仪分析的基础上,研究不同比例的DOPO-BPS与OSEP对EP-CE复合材料阻燃性能和抑烟性能的影响。研究表明:DOPO-BPS的磷杂菲环结构能形成稳定炭层,阻断热氧传递,与OSEP的协同作用显著提升了阻燃效果和抑烟性能。当阻燃剂DOPO-BPS与OSEP以9∶1的质量比添加至EP-CE时,阻燃性能和抑烟性能最佳,阻燃性能达V-0级,LOI增至31.4%,且热释放速率峰值、总热释放量和产烟总量相比于EP-CE,分别降低了29.7%、32.2%和32.7%。

关键词: 环氧树脂(EP), 氰酸酯树脂(CE), 9,10-二氢-9-氧杂-10-磷杂菲10-氧化物(DOPO), 4,4'-二羟基二苯砜(BPS), 有机海泡石(OSEP), 阻燃, 复合材料

Abstract:

To enhance the flame retardancy and smoke suppression performance of EP-CE composites, a novel flame retardant was synthesized using DOPO and BPS as raw materials. The flame-retardant DOPO-BPS/OSEP/EP-CE composites were fabricated by the solution casting method, where DOPO-BPS and OSEP were jointly introduced into EP-CE matrix. Based on Fourier transform infrared spectroscopy (FTIR) analysis, nuclear magnetic resonance (NMR) analysis, thermogravimetric analysis (TGA), limiting oxygen index (LOI) test, UL-94 vertical burning test, and cone calorimeter analysis, the effects of different ratios of DOPO-BPS and OSEP on the flame retardancy and smoke suppression properties of EP-CE composite materials were studied. The results show that the phosphaphenanthrene ring structure of DOPO-BPS could form a stable carbon layer and block the transfer of heat and oxygen. The synergistic effect with OSEP significantly improves the flame retardant effect and smoke suppression performance. When the flame retardant DOPO-BPS and OSEP are added to EP-CE at a mass fraction of 9∶1, the flame retardant performance and smoke suppression performance are the best, the flame retardant performance reaches V-0 level, and the LOI increases to 31.4%. Compared with EP-CE, the peak heat release rate, total heat release and total smoke production decrease by 29.7%, 32.2% and 32.7%, respectively.

Key words: epoxy resin (EP), cyanate ester resin (CE), 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO), bisphenol sulfone (BPS), organic sepiolite (OSEP), flame retardancy, composite materials

中图分类号:

X932爆炸安全与防火、防爆

刘勇, 姜一帆, 耿鑫玺, 张焘. DOPO-BPS/OSEP/EP-CE阻燃复合材料的制备及性能[J]. 中国安全科学学报, 2025, 35(2): 111-117.

LIU Yong, JIANG Yifan, GENG Xinxi, ZHANG Tao. Preparation and properties of DOPO-BPS/OSEP/EP-CE flame retardant composite materials[J]. China Safety Science Journal, 2025, 35(2): 111-117.

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参考文献 12

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样品	EP	CE	DOPO- BPS	OSEP
EP-CE	60.0	40.0	0.0	0.0
7DOPO-BPS/3OSEP/EP-CE	54.0	36.0	7.0	3.0
8DOPO-BPS/2OSEP/EP-CE	54.0	36.0	8.0	2.0
9DOPO-BPS/1OSEP/EP-CE	54.0	36.0	9.0	1.0
3OSEP/EP-CE	58.2	38.8	0.0	3.0
10DOPO-BPS/EP-CE	54.0	36.0	10.0	0.0

样品	初始失重温度 t_5%/℃	最大失重速率温度 t_max/℃	残余物质量分数/%
EP-CE	356.7	385.7	15.2
9DOPO-BPS/1OSEP/EP-CE	323.6	395.1	18.0
8DOPO-BPS/2OSEP/EP-CE	329.6	395.1	16.5
7DOPO-BPS/3OSEP/EP-CE	345.6	396.6	16.3
10DOPO-BPS/EP-CE	353.8	394.8	18.9
3OSEP/EP-CE	363.4	401.4	16.0

样品	LOI /%	等级	滴落	总燃烧时间/s
EP-CE	24.4	NR	是	>250
7DOPO-BPS/3OSEP/EP-CE	29.8	V-1	否	134.5
8DOPO-BPS/2OSEP/EP-CE	30.6	V-1	否	98.5
9DOPO-BPS/1OSEP/EP-CE	31.4	V-0	否	47.5
10DOPO-BPS/EP-CE	30.9	V-0	否	46.5
3%OSEP/EP-CE	24.6	NR	是	>250

样品	PHRR/ (kW·m^-2)	THR/ (MJ·m^-2)
EP-CE	581.1	100.8
10DOPO-BPS/EP-CE	458.1	73.3
3OSEP/EP-CE	557.7	86.7
9DOPO-BPS/1OSEP/EP-CE	408.5	68.3

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DOPO-BPS/OSEP/EP-CE阻燃复合材料的制备及性能

Preparation and properties of DOPO-BPS/OSEP/EP-CE flame retardant composite materials

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