负载金属氧化物活性炭对阻燃橡胶硫化、 燃烧及热老化性能的影响

doi:10.7503/cjcu20150583

摘要/Abstract

摘要：

利用金属氧化物(MO)催化协效阻燃和改善热老化的作用, 以及竹基活性炭(AC)富孔、比表面积大的特性, 采用溶剂蒸发法将Fe₂O₃, CuO和ZnO负载于AC上, 得到了负载金属氧化物活性炭(AC-MO), 并研究了AC-MO协效聚磷酸铵/双季戊四醇膨胀阻燃乙烯-醋酸乙烯酯共聚物橡胶(EVM)的硫化、燃烧、热稳定性及耐热老化性能. 结果表明, AC-MO为目标产物且MO分散均匀, AC及AC-MO在阻燃EVM中分散均匀; AC-MO增大了阻燃EVM的最大扭矩并提高了阻燃性能及残炭量, 其中AC-Fe₂O₃效果最佳; 将Fe₂O₃负载于AC上提高了AC的催化成炭能力, 改善了阻燃EVM残炭的完整性、致密性, 最终阻燃性能得到提高. 热老化实验后, AC-MO提高了阻燃EVM热老化后的拉伸强度, 但断裂伸长率有所降低.

关键词: 活性炭, 金属氧化物, 逾渗作用, 催化阻燃, 橡胶

Abstract:

With the excellent catalytic synergistic flame retardancy of metal oxide(MO) and its effect of improving the thermal ageing property as well as the porous and large specific surface area characteristic of bamboo based active carbon(AC), a series of metal oxide(Fe₂O₃, CuO, ZnO) supported on active carbon(AC-MO) synergist was prepared by solvent evaporation method. The vulcanization, combustion, thermostability, and thermal ageing properties for synergistic intumescent flame retardant ethylene vinyl-acetate copolymer rubber(EVM) with AC-MO and ammonium polyphosphate/dipentaerythritol was studied. The results showed that AC-MO was the target product and MO dispersed well when supported on AC. AC and AC-MO had a uniform dispersion in the flame retardant EVM. The introduction of AC-MO improved the maximum torque, flame retardancy, and char residue, especially for AC-Fe₂O₃. A Fe₂O₃ supported on AC improved its catalytic charring effect, which improved the integrity and compactness of char residue of flame retardant EVM. As a result, the flame retardancy was improved. After thermal ageing test, the tensile strength of EVM/IFR/AC-MO increased while the elongation at break decreased.

Key words: Active carbon, Metal oxide, Percolation effect, Catalytic flame retardant, Rubber

中图分类号:

O631

TrendMD:

彭辉, 周友, 郝建薇, 李茁实, 邹红飞. 负载金属氧化物活性炭对阻燃橡胶硫化、燃烧及热老化性能的影响. 高等学校化学学报, 2015, 36(12): 2569.

PENG Hui, ZHOU You, HAO Jianwei, LI Zhuoshi, ZOU Hongfei. Effect of Metal Oxide Supported on Active Carbon on Vulcanization, Combustion and Thermal Ageing Properties of Flame Retardant Rubber^†. Chem. J. Chinese Universities, 2015, 36(12): 2569.

图/表 10

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Sample	LOI(%)	ΔLOI(%)	UL 94
Sample	LOI(%)	ΔLOI(%)	3.2 mm	1.6 mm
EVM	23.2	—	N. R.	N. R.
EVM/37IFR/3AC	33.6	10.4	V-0	V-0
EVM/37IFR/3AC-Fe₂O₃	34.1	10.9	V-0	V-0
EVM/37IFR/3AC-CuO	34.0	10.8	V-0	V-0
EVM/37IFR/3AC-ZnO	33.9	10.7	V-0	V-0

Sample	LOI(%)	ΔLOI(%)	UL 94
Sample	LOI(%)	ΔLOI(%)	3.2 mm	1.6 mm
EVM	23.2	—	N. R.	N. R.
EVM/37IFR/3AC	33.6	10.4	V-0	V-0
EVM/37IFR/3AC-Fe₂O₃	34.1	10.9	V-0	V-0
EVM/37IFR/3AC-CuO	34.0	10.8	V-0	V-0
EVM/37IFR/3AC-ZnO	33.9	10.7	V-0	V-0

Sample	TTI/s	PHRR / (kW·m^-2)	t_PHRR/s	THR/ (MJ·m^-2)	TSR/ (m²·m^-2)	av-CO/ (kg·kg^-1)	av-CO₂/ (kg·kg^-1)
EVM	45	1281.8	120	114.7	2108	0.092	1.82
EVM/40IFR	52	331.9	115	66.7	2059	0.084	1.85
EVM/37IFR/3AC	59	281.4	100	55.6	1940	0.078	1.77
EVM/37IFR/3AC-Fe₂O₃	56	255.7	215	50.8	1855	0.078	1.78
EVM/37IFR/3AC-CuO	57	253.7	160	57.8	1892	0.069	1.65
EVM/37IFR/3AC-ZnO	57	276.0	215	57.6	1867	0.071	1.55

Sample	TTI/s	PHRR / (kW·m^-2)	t_PHRR/s	THR/ (MJ·m^-2)	TSR/ (m²·m^-2)	av-CO/ (kg·kg^-1)	av-CO₂/ (kg·kg^-1)
EVM	45	1281.8	120	114.7	2108	0.092	1.82
EVM/40IFR	52	331.9	115	66.7	2059	0.084	1.85
EVM/37IFR/3AC	59	281.4	100	55.6	1940	0.078	1.77
EVM/37IFR/3AC-Fe₂O₃	56	255.7	215	50.8	1855	0.078	1.78
EVM/37IFR/3AC-CuO	57	253.7	160	57.8	1892	0.069	1.65
EVM/37IFR/3AC-ZnO	57	276.0	215	57.6	1867	0.071	1.55

Sample	T_5%/℃	[R_max/(%·min^-1)]/[T_max/℃]			CR(%)
Sample	T_5%/℃	Stage 1	Stage 2	Stage 3	Expt.	Calcd.
EVM/37IFR/3AC	291	15.7/348	14.0/474	—	16.3(1.4^*)	13.7
EVM/37IFR/3AC-Fe₂O₃	286	14.0/348	13.1/471	—	21.9(8.1^*)	13.8
EVM/37IFR/3AC-CuO	282	14.5/348	13.6/471	—	20.0	—
EVM/37IFR/3AC-ZnO	293	15.2/353	13.9/474	—	19.0	—
EVM	311	19.6/343	19.6/469	—	1.6	—
IFR	250	3.5/252	4.4/332	9.2/519	26.9	—
AC	—	—	—	—	93.0	—
EVM/3AC	316	18.2/354	16.9/481	—	5.8(0.6^*)	5.2
EVM/0.6Fe₂O₃	307	17.6/349	18.8/473	—	3.9(1.7^*)	2.2
37IFR/3AC	247	4.2/252	3.7/353	7.4/507	35.3(3.4^*)	31.9
37IFR/0.6Fe₂O₃	246	3.9/254	3.9/335	5.2/561	34.5(6.6^*)	27.9