星型绿色磷腈阻燃剂的制备及阻燃环氧树脂性能

doi:10.7503/cjcu20180339

摘要/Abstract

摘要：

从分子结构设计出发, 以六氯环三磷腈、对羟基苯甲醛、三氯氧磷及新戊二醇等为原料, 制备了一种新型阻燃剂六[4-(5,5-二甲基-1,3,2-二氧杂己内磷酰基)苯氧基]环三磷腈(HDDCPPCP), 并将其与聚磷酸铵(APP)和多壁碳纳米管(MWCNT)复配, 应用于环氧树脂(EP)中, 制备了HDDCPPCP/APP/MWCNT/EP阻燃复合材料. 利用极限氧指数(LOI)、水平燃烧(UL-94)、锥形量热(CONE)、拉伸、弯曲和冲击等方法研究该阻燃复合材料的燃烧性能、热性能及力学性能. 实验结果表明, 保持阻燃体系总质量分数为30%, 当MWCNT质量分数为2%时, EP2(HDDCPPCP/APP/MWCNT/EP)的各项燃烧参数综合表现较好, 其LOI值达到42.8%, 热释放速率峰值(pk-HRR)、热释放速率平均值(av-HRR)、有效燃烧热平均值(av-EHC)及一氧化碳释放率平均值(av-CO)相对EP0分别降低92.5%, 93.0%, 65.2%和66.6%, 呈现出良好的阻燃、抑烟和抑毒性能; EP2的拉伸强度、断裂伸长率、弯曲强度和弯曲模量较好, 分别为110.46 MPa, 6.24%, 1259.99 MPa, 377.72 MPa.

关键词: 环磷腈阻燃剂, 环氧树脂, 阻燃性能, 力学性能, 多壁碳纳米管

Abstract:

Based on the molecular structure design, a new type of flame retardant named six[4-(5,5-methyl-1,3,2-dioxanone endophosphoryl) phenoxy] cyclotriphosphazene(HDDCPPCP) was prepared by hexachloro-cyclotriphosphazene, p-hydroxybenzaldehyde, phosphorus oxychloride and neopentyl glycol. This new flame retardant, ammonium polyphosphate(APP) and multi walled carbon nanotubes(MWCNT) were added to epoxy resin(EP). After that, the HDDCPPCP/APP/MWCNT/EP flame-retardant composites were prepared. Limiting oxygen index(LOI), horizontal burning(UL-94), cone calorimetry(CONE), tensile, bending and impact methods were used to study the combustion, thermal and mechanical properties of the flame-retardant composites. The experimental results show that the combustion parameters of EP2(HDDCPPCP/APP/MWCNT/EP) composites perform better when the total mass of fraction of flame retardant system is 30% and the mass fraction of MWCNT is 2%. The LOI of EP2 is 42.8%, it shows good flame retardancy, smoke suppression and anti-poisoning properties. The peak heat release rate(pk-HRR), average heat release rate(av-HRR), average effective heat combustion(av-EHC), and average CO release rate(av-CO) of EP2 are respectively reduced by 92.5%, 93.0%, 65.2%, and 66.6% compared with EP0. EP2 have good tensile strength, break elongation, bending strength and bending modulus, which are respectively 110.46 MPa, 6.24%, 1259.99 MPa and 377.72 MPa.

Key words: Cyclophosphazene flame retardant, Epoxy resin, Flame retardancy, Mechanical property, Multi walled carbon nanotubes

中图分类号:

O634.5

TrendMD:

卢林刚, 程哲, 丘新铭, 王会娅, 杨守生, 钱小东, 王学宝. 星型绿色磷腈阻燃剂的制备及阻燃环氧树脂性能. 高等学校化学学报, 2018, 39(12): 2789.

LU Lingang,CHENG Zhe,QIU Xinming,WANG Huiya,YANG Shousheng,QIAN Xiaodong,WANG Xuebao. Preparation of Green Star-topology Phosphazene Flame Retardant and Properties of Flame-retardant Epoxy Resin^†. Chem. J. Chinese Universities, 2018, 39(12): 2789.

图/表 13

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Sample	Mass fraction(%)					LOI(%)	UL94-FH	UL94-FV
Sample	EP	m-PDA	HDDCPPCP	APP	MWCNT	LOI(%)	UL94-FH	UL94-FV
EP0	90.9	9.1	0	0	0	23.0	FH-2	No rating
EP1	63.6	6.4	10.0	20.0	0	43.8	FH-1	V-0
EP2	63.6	6.4	9.3	18.7	2	42.8	FH-1	V-0

Sample	Mass fraction(%)					LOI(%)	UL94-FH	UL94-FV
Sample	EP	m-PDA	HDDCPPCP	APP	MWCNT	LOI(%)	UL94-FH	UL94-FV
EP0	90.9	9.1	0	0	0	23.0	FH-2	No rating
EP1	63.6	6.4	10.0	20.0	0	43.8	FH-1	V-0
EP2	63.6	6.4	9.3	18.7	2	42.8	FH-1	V-0

Sample	TTI/s	pk-HRR/ (kW·m^-2)	av-HRR/ (kW·m^-2)	av-EHC/ (MJ·kg^-1)	av-MLR/ (g·s^-1)	av-SEA/ (m²·kg^-1)	av-CO/ (kg·kg^-1)
EP0	91	634.40(235 s)	261.30	20.43	0.12	1888.45	0.06
EP1	85	38.33(215 s)	10.97	4.42	0.02	2393.47	0.02
EP2	81	47.39(200 s)	18.26	7.11	0.02	2285.00	0.02

Sample	TTI/s	pk-HRR/ (kW·m^-2)	av-HRR/ (kW·m^-2)	av-EHC/ (MJ·kg^-1)	av-MLR/ (g·s^-1)	av-SEA/ (m²·kg^-1)	av-CO/ (kg·kg^-1)
EP0	91	634.40(235 s)	261.30	20.43	0.12	1888.45	0.06
EP1	85	38.33(215 s)	10.97	4.42	0.02	2393.47	0.02
EP2	81	47.39(200 s)	18.26	7.11	0.02	2285.00	0.02

Sample	FGI/(kW·m^-2·s^-1)	THRI_{6 min}/(MJ·m^-2)	TSPI_{6 min}/(m²·g·kg^-1·s^-1)	ToxPI_{6 min}/(g·s^-1)
EP0	2.70	3.85	7.44	4.21
EP1	0.18	2.64	6.11	3.33
EP2	0.24	2.73	6.98	3.53