酚醛泡沫的燃烧行为及阻燃研究进展

doi:10.11949/0438-1157.20220284

摘要/Abstract

摘要：

酚醛泡沫因兼具优异的保温性能和阻燃性能在工程领域得到广泛应用，但其经高温燃烧后质量残留率很低，炭层疏松、强度低，离开火焰后还易出现阴燃现象。目前有关酚醛泡沫燃烧行为的研究大多集中在如何进一步提高酚醛泡沫塑料的阻燃等级或在改善其脆性的同时不降低固有的阻燃性能，还未见关于酚醛泡沫燃烧全过程行为的综述报道。文章介绍了酚醛泡沫在明火燃烧和阴燃状态的燃烧行为，分析了影响酚醛泡沫燃烧行为的因素，并总结了现有酚醛泡沫阻燃研究的进展。目前酚醛泡沫的燃烧行为及阻燃研究主要集中在泡沫的明火燃烧，对酚醛泡沫阴燃问题的研究重视不足，缺乏针对酚醛泡沫燃烧全过程的行为和机理探究。因此，提出应加大对酚醛泡沫阴燃行为的研究投入，注重对酚醛泡沫燃烧全过程的机理探索与阻燃方案研究，设计并研发出解决酚醛泡沫燃烧全过程问题的有效途径。

关键词: 泡沫, 聚合物, 燃烧行为, 阻燃, 热解, 极限氧指数

Abstract:

Phenolic foam has been widely used in engineering field due to its excellent thermal insulation properties and flame retardant properties. However, phenolic foam has low mass residue yield, loose char layer and low strength after high temperature combustion, and tends to smolder after the flame leaves. The current research on the combustion behavior of phenolic foams mostly focuses on how to further improve the flame retardant level or improve the brittleness without reducing the inherent flame retardancy, and there is no review of the whole combustion process behavior of phenolic foam. This review introduces the flame combustion and smoldering of phenolic foam, analyzes the factors that affect the combustion behavior of phenolic foam, and summarizes the progress of phenolic foam flame retardant research. The foam shape of the char layer after flame combustion is basically retained but brittle, and smoldering also generates char layer but has low residual carbon rate. The combustion behavior of unmodified phenolic foam is mainly affected by the molar ratio of formaldehyde to phenol. According to the test data of limiting oxygen index and cone calorimeter, the synergistic flame retardant effect of phosphorus-nitrogen is the best. At present, the research on combustion behavior and flame retardant of phenolic foam mainly focuses on flame combustion. The research on smoldering problem of phenolic foam is insufficient, and the behavior and mechanism of the whole combustion process of phenolic foams are lacking. Therefore, this paper proposes to increase the research investment on the smoldering behavior of phenolic foam, pay attention to the mechanism exploration and flame retardant scheme research of the whole process of phenolic foam combustion, and design and develop an effective way to solve the problem of the whole process of phenolic foam combustion.

Key words: foam, polymers, combustion behavior, flame retardancy, pyrolysis, limiting oxygen index

中图分类号:

TQ 328.2

唐恺鸿, 何晓峰, 徐桂秋, 于洋, 刘啸凤, 葛铁军, 张爱玲. 酚醛泡沫的燃烧行为及阻燃研究进展[J]. 化工学报, 2022, 73(8): 3483-3500.

Kaihong TANG, Xiaofeng HE, Guiqiu XU, Yang YU, Xiaofeng LIU, Tiejun GE, Ailing ZHANG. Review on combustion behavior and flame retardant research of phenolic foams[J]. CIESC Journal, 2022, 73(8): 3483-3500.

图/表 15

图1 甲阶酚醛树脂分子结构[11]

Fig.1 Resole resin molecular structure[11]

图2 酚醛泡沫泡孔结构[5]

Fig.2 Phenolic foam cell structure[5]

图3 酚醛泡沫不同的泡孔壁结构[14]

Fig.3 Different phenolic foam cell wall structures [14]

图4 燃烧后的酚醛泡沫[16]

Fig.4 Phenolic foam after combustion[16]

图5 酚醛泡沫炭层形貌[17]

Fig.5 Morphology of phenolic foam char layer[17]

图6 阴燃火势蔓延示意图[21]

Fig.6 Diagram of fire spread of smoldering[21]

图7 酚醛泡沫温度曲线[22]

Fig.7 Phenolic foam temperature curve[22]

图8 酚醛泡沫主要热解路线示意图[24]

Fig.8 Schematic of the main pyrolysis route of phenolic foam[24]

图9 F/Pmr对酚醛泡沫泡孔结构的影响

Fig.9 Effect of F/Pmr on cell structure of phenolic foam

表1 加入不同阻燃剂的酚醛泡沫塑料阻燃性能

Table 1 Flame retardancy of phenolic foams with different flame retardants

阻燃剂类型	阻燃剂	LOI/%	pHRR变化率	文献
磷系阻燃剂	DOPO-木纤维	35.0	—	[31]
磷系阻燃剂	DOPO-木纤维	35.2	—	[35]
磷系阻燃剂	DOPO-微晶纤维素	46.0	—	[36]
磷系阻燃剂	DOPO-衣康酸-乙基纤维素	37.1	—	[37]
磷系阻燃剂	含磷聚醚增韧剂	49.5	41.5%↓	[38]
磷系阻燃剂	聚乙二醇磷酸盐	45.1	28.3%↓	[39]

图10 纳米级无机阻燃剂在酚醛泡沫中的阻燃机理示意图[53]

Fig.10 Schematic diagram of flame retardant mechanism of nanoscale inorganic flame retardants in phenolic foam[53]

表2 加入不同纳米级无机阻燃剂的酚醛泡沫塑料阻燃性能

Table 2 Flame retardancy of phenolic foams with different nanoscale inorganic flame retardants

阻燃剂类型	阻燃剂	LOI/%	pHRR 变化率	文献
纳米颗粒	TiN	34.2	—	[53]
纳米颗粒	SiO₂	38.0	—	[54]
纳米颗粒	Al₂O₃	39.3	8.3%↓	[55]
纳米颗粒	ZrO₂	38.9	2.8%↓	[55]
磷-氮系阻燃剂/ 纳米颗粒	APP/ZnO	73.0	>75.0%↓	[56]
磷-氮系阻燃剂/ 纳米颗粒	APP/MoO₃	71.0	>75.0%↓	[56]
磷-氮系阻燃剂/ 纳米颗粒	APP/CuCl₂	71.5	>75.0%↓	[56]
磷-氮系阻燃剂/ 纳米颗粒	APP/SnCl₂	72.0	>75.0%↓	[56]
纤维/纳米颗粒	玻璃纤维/ 纳米黏土	32.0	12.7%↓	[57]
—	氧化石墨烯	40.0	22.2%↓	[58]
纳米颗粒/氧化石墨烯	磷酸锆-氧化石墨烯	42.5	25.0%↓	[58]
纳米颗粒/氧化石墨烯	SiO₂-氧化石墨烯	41.0	21.4%↓	[59]
纳米颗粒/氧化石墨烯	CoAl-氧化石墨烯	38.5	8.4%↓	[60]

图11 酚醛树脂结构改性工艺路线示意图[11]

Fig.11 Schematic diagram of the process steps of phenolic resin structure modification[11]

表3 化学改性酚醛泡沫塑料的阻燃性能

Table 3 Flame retardancy of chemically modified phenolic foams

改性方法	改性剂	LOI/%	pHRR变化率	文献
整体投料	双氰胺	48.1	19.1%↓	[68]
羟甲基苯酚改性	双酚A二缩水甘油醚	—	133.0%↑	[69]
羟甲基苯酚改性	溴化双酚A环氧树脂	—	37.7%↓	[69]
羟甲基苯酚改性	蒙脱土/生物油	39.7	—	[65]
原材料替代	含羞草树皮单宁	—	88.7%↓	[71]
原材料替代	磺化落叶松单宁	47.8	—	[72]
原材料替代	硫酸盐木质素	34.0	0.4%↑	[74]
原材料替代	HBr催化木质素	43.6	—	[75]

图12 不同废泡沫颗粒添加量的酚醛泡沫炭层形貌[87]

Fig.12 Morphology of char layer of phenolic foams with different addition level of waste foam particles[87]

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