阻燃型环氧树脂/低分子聚苯醚材料固化及热解动力学

doi:10.16265/j.cnki.issn1003-3033.2025.07.1462

摘要/Abstract

摘要： 为提高环氧树脂(EP)在应用领域的安全性,使用苯二甲酸钙(CaT)这一有机金属框架化合物(MOF)材料,协同液体阻燃剂双酚A双(二苯基磷酸酯)(BDP)阻燃改性EP/低分子聚苯醚(PPO)体系,通过极限氧指数、垂直燃烧测试和锥形量热测试表征其阻燃性能,并利用Kissinger、FWO和Crane方程研究改性EP/PPO体系的固化动力学及热解动力学。结果表明:当添加8%BDP和2%CaT至EP中,复合材料表现出良好的阻燃性能,极限氧指数达34.5%,垂直燃烧测试获V-0级别,且其峰值热释放速率和总热释放较纯EP分别降低76.6%及51.5%;CaT有利于固化反应;利用非等温差示扫描量热曲线外推法能够得到最佳固化温度为:初始100 ℃,后120 ℃,最后170 ℃;通过非等温热重分析及热解动力学分析可发现EP/PPO体系表现出更低的活化能。

关键词: 阻燃, 环氧树脂(EP), 低分子聚苯醚(PPO), 固化动力学, 热解动力学

Abstract:

To improve the safety of EP in application fields, Calcium Terephthalate(CaT), a metal-organic framework (MOF) material, was utilized synergistically with the liquid flame retardant bisphenol A bis (diphenyl phosphate) (BDP) to flame-retardant modify the EP/PPO system. The flame retardant properties were characterized using the limiting oxygen index, vertical burning test, and cone calorimeter tests. The curing kinetics and pyrolysis kinetics of the modified EP/PPO system were investigated using the Kissinger, FWO (Flynn-Wall-Ozawa), and Crane equations. The results show that when 8% BDP and 2% CaT are added to EP, the composite exhibits good flame retardant performance. 34.5% of the limiting oxygen index is reached. V-0 rating of the vertical burning test is achieved. The peak heat release rate and the total heat release are reduced by 76.6% and 51.5% respectively compared to pure EP. The incorporation of CaT is found to be beneficial for the curing reaction. The optimal curing temperature could be determined by extrapolation from non-isothermal differential scanning calorimetry curves. It is an initial stage at 100 ℃, followed by 120 ℃, and finally 170 ℃. Analysis of non-isothermal thermogravimetric analysis curves and pyrolysis kinetics demonstrates that EP/PPO system exhibits lower activation energy.

Key words: flame retardant, epoxy resin (EP), low-molecular-weight polyphenylene oxide (PPO), curing kinetics, pyrolysis kinetics

中图分类号:

单雪影, 张家傅, 黄其鑫, 刁玉璇, 李锦春, 李玲玉. 阻燃型环氧树脂/低分子聚苯醚材料固化及热解动力学[J]. 中国安全科学学报, 2025, 35(7): 114-121.

SHAN Xueying, ZHANG Jiafu, HUANG Qixin, DIAO Yuxuan, LI Jinchun, LI Lingyu. Curing and pyrolysis kinetics of flame-retardant epoxy resin/low-molecular-weight polyphenylene oxide composites[J]. China Safety Science Journal, 2025, 35(7): 114-121.

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样品名称	EP/g	PPO/%	BDP/%	CaT/%	LOI/%	UL-94
EP	40	0	0	0	26.0	无等级
EP/PPO/BDP/CaT0	40	15	10	0	32.5	V-0
EP/PPO/BDP/CaT1	40	15	9	1.0	33.5	V-0
EP/PPO/BDP/CaT2	40	15	8	2.0	34.5	V-0

样品	热释放速率峰值/ (kW·m^-2)	总热释放/ (MJ·m^-2)	平均有效燃烧热/ (MJ·kg^-1)	CO₂产生速率峰值/ (g·s^-1)	总烟气释放量/m²	烟气释放速率峰值/ (m²·s^-1)	800 ℃残炭量/%
EP	948.0	101.7	23.4	0.573	52.8	0.39	12.7
EP/PPO/BDP/CaT0	251.0	39.7	12.0	0.209	35.6	0.26	20.5
EP/PPO/BDP/CaT1	261.5	42.7	12.4	0.238	13.4	0.48	24.1
EP/PPO/BDP/CaT2	222.0	49.3	10.7	0.203	11.9	0.21	20.7

样品	E_a/(kJ·mol^-1)			A/s^-1	n
样品	Kissinger	FWO	均值	A/s^-1	n
EP/PPO/BDP/CaT0	48.97	53.58	51.28	1.68×10⁵	0.869
EP/PPO/BDP/CaT1	41.35	46.13	43.74	2.72×10⁴	0.852
EP/PPO/BDP/CaT2	42.60	47.13	44.87	5.48×10⁴	0.859

β/ (℃·min^-1)	样品
	EP/PPO/BDP/CaT0			EP/PPO/BDP/CaT1			EP/PPO/BDP/CaT2
	θ₀/℃	θ_p/℃	θ_f/℃	θ₀/℃	θ_p/℃	θ_f/℃	θ₀/℃	θ_p/℃	θ_f/℃
5	101.9	153.3	215.1	99.3	137.7	184.9	89.9	127.8	167.9
10	119.7	168.8	233.5	112.8	157.2	218.8	106.5	151.9	216.2
15	135.4	187.6	238.7	124.2	171.4	237.8	115.2	159.6	217.7
20	140.0	190.0	239.6	138.5	182.0	240.7	122.9	169.1	227.3

β/(℃·min^-1)	样品
	EP/PPO/BDP/CaT0			EP/PPO/BDP/CaT1			EP/PPO/BDP/CaT2
	θ_-5%/℃	θ_max/℃	800℃残炭量/%	θ_-5%/℃	θ_max/℃	800℃残炭量/%	θ_-5%/℃	θ_max/℃	800℃残炭量/%
5	331.2	382.1	24.7	334.6	381.2	26.0	335.7	386.2	25.0
10	348.4	397.4	25.8	356.2	398.1	26.9	357.3	402.4	27.8
15	360.4	404.7	25.5	365.6	407.1	25.2	363.2	411.1	25.6
20	346.0	396.8	21.7	362.1	400.0	22.7	360.5	402.7	25.7