镁铝层状双氢氧化物/三聚氰胺磷酸盐复配阻燃剂对中密度纤维板的协效阻燃机理分析

doi:10.11707/j.1001-7488.20220515

摘要/Abstract

摘要：

目的: 探究镁铝层状双氢氧化物(MgAl-LDHs)与三聚氰胺磷酸盐(MP)复配阻燃剂的协同阻燃机理，为MgAl-LDHs与磷氮阻燃剂复配阻燃剂应用于阻燃纤维板制备提供理论基础。方法: 采用氧指数仪和锥形量热仪测试阻燃中密度纤维板的阻燃性能，通过氧指数、热释放速率、总热释放量、烟释放速率、烟释放总量变化和协效比计算，分析复配阻燃剂的释热性能及其在生烟特性方面的协效作用，运用热重分析、傅里叶红外光谱分析以及热重-傅里叶红外光谱联用分析技术探讨MgAl-LDHs与MP之间的凝聚相和气相阻燃机理。结果: 复配阻燃剂制备出中密度纤维板的氧指数为31.9%，复配阻燃剂在氧指数协效比计算中未表现出协效作用，而锥形量热仪协效比计算表现出协效作用，热解分析表明复配阻燃剂对木粉的阻燃效果优于MgAl-LDHs和MP单独阻燃作用。燃烧过程中MP催化MgAl-LDHs快速分解，释放大量水蒸气和CO₂，吸收纤维板热量，降低表面温度，使燃烧难以维持，同时水蒸气和CO₂稀释可燃气体和氧气浓度，降低燃烧速率。复配阻燃剂的阻燃机理主要为气相阻燃，凝聚相阻燃作用不明显，气相阻燃是“冷却效应”和“稀释效应”共同作用的结果，320 ℃前主要为气相阻燃，380 ℃后复配阻燃剂进入凝聚相阻燃。结论: MgAl-LDHs与MP复配阻燃剂的协同阻燃作用机理表现在3方面：1) 温度范围增大，MgAl-LDHs低温分解，与MP复配后复配阻燃剂初始分解温度为198 ℃；2) MgAl-LDHs分解释放水蒸气和CO₂，MP分解释放氨气冲淡燃烧表面可燃气体，协同发挥“稀释效应”作用；3) MP催化成炭和MgAl-LDHs高温熔融的覆盖协同作用。

关键词: 镁铝层状双氢氧化物, 三聚氰胺磷酸盐, 中密度纤维板, 阻燃, 协效作用

Abstract:

Objective: The objective of this study was to analyze synergistic flame retardant mechanism of magnesium-aluminum layered double hydroxides(MgAl-LDHs) and melamine phosphate(MP), and to provide theoretical bases of MgAl-LDHs and MP compound flame retardant for fiberboard. Method: The flame retardant performance of medium density fiberboard was tested using oxygen index meter and cone calorimeter. The synergistic effect on heat release performance and smoke generation characteristics of compound flame retardants was performed through synergy ratio of limiting oxygen index (LOI), heat release rate(HRR), total heat release(THR), smoke production rate(SPR) and total smoke release(TSR). Furthermore, the thermogravimetric, fourier infrared spectroscopy and thermogravimetric-fourier infrared spectroscopy combined techniques were used to discuss the condensed phase and gas phase flame retardant mechanisms between MgAl-LDHs and MP. Result: The oxygen index of medium density fiberboard that produced with MgAl-LDHs and MP compound flame retardant was 31.9%. The compound flame retardant did not show a synergistic effect in the calculation of the oxygen index synergy ratio. However, the ratio calculation of cone calorimeter showed a synergistic effect. The pyrolysis analysis showed that the flame retardant effect of compound flame retardant on wood powder was better than that using MgAl-LDHs or MP alone. During the combustion process, MP catalyzed MgAl-LDHs rapid decomposition to release a large amount of water vapor and carbon dioxide, and to absorb the heat of the medium density fiberboard to further reduce the surface temperature. The result led to the combustion difficult to maintain, and simultaneously water vapor and carbon dioxide diluted the combustible gas and oxygen concentration for reducing combustion rate. The flame retardant mechanisms of compound flame retardant were mainly the gas phase flame retardant, and there was not an obvious condensed phase. The gas phase flame retardant was the result of the combined action from a cooling effect and a dilution effect. The compound flame retardant was mainly gas phase flame retardant before 320 ℃ and transformed into condensed phase flame retardant after 380 ℃. Conclusion: The synergistic mechanisms of MgAl-LDHs and MP compound flame retardant shown in three aspects: 1) The decompose temperature range of compound flame retardant was increased and its initial decompose temperature was 198 ℃, meaning that the MgAl-LDHs would decompose in a lower temperature. 2) MgAl-LDHs and MP were released a large amount of water vapor, carbon dioxide and ammonia gas during thermal decomposition, these gas diluted the combustible gas on combustion surface and presented dilution effects. 3) Synergistic effect of MP catalyzed carbon formation and MgAl-LDHs high temperature melting coverage.

Key words: magnesium-aluminum layered double hydroxides (MgAl-LDHs), melamine phosphate (MP), medium density fiberboard, flame retardant, saynergistic effect

中图分类号:

S781.9

张丽芳,梁善庆,姜鹏,张龙飞. 镁铝层状双氢氧化物/三聚氰胺磷酸盐复配阻燃剂对中密度纤维板的协效阻燃机理分析[J]. 林业科学, 2022, 58(5): 140-150.

Lifang Zhang,Shanqing Liang,Peng Jiang,Longfei Zhang. Synergistic Mechanism Analysis of MgAl-LDHs/MP Compound Flame Retardant in Medium Density Fiberboard[J]. Scientia Silvae Sinicae, 2022, 58(5): 140-150.

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名称 Name	镁铝层状双氢氧化物 MgAl-LDHs(%)	三聚氰胺磷酸盐 MP(%)	密度 Density/(g·cm^-3)	氧指数 LOI(%)	氧指数差值 LOI difference(%)
对照样Control	0	0	0.75	23.5	—
MgAl-LDHs	15	0	0.74	26.0	2.5
MP	0	15	0.77	34.6	11.1
LM11	15	15	0.76	31.9	8.4

名称 Name	镁铝层状双氢氧化物 MgAl-LDHs(%)	三聚氰胺磷酸盐 MP(%)	热释放速率 HRR/(kW·m^-2)	热释放总量 THR/(MJ·m^-2)	烟释放速率 SPR/(m²·s^-1)	总烟释放量 TSR/(m²·m^-2)
对照样Control	0	0	528.42	110.94	0.053	5.75
MgAl-LDHs	15	0	497.11	107.68	0.037	4.99
MP	0	15	469.54	106.37	0.040	5.25
LM11	15	15	431.86	101.39	0.024	4.60

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