Research progress of lignin applied to flame retardant plastics

doi:10.16085/j.issn.1000-6613.2024-1517

Abstract

Abstract:

As a biomass material with high carbon content, excellent thermal stability, strong carbonization ability and easy modification, lignin is often used as a biomass flame retardant to apply in the plastics, to improve their flammability, reduce the generation of molten droplets and smoke emissions after heat absorption. However, there are many problems such as low flame retardant efficiency, large addition and smoke production, and poor durability. In order to better understand the application of lignin in the flame retardancy of plastics, its structure was firstly briefly described, and the mechanism of lignin improving the flame retardant performance of plastics was analyzed in detail. Then, the research status of unmodified and modified lignin based flame retardants in the application of plastic flame retardancy was systematically reviewed, and the advantages and disadvantages of different flame retardant applications were analyzed. Moreover, it was proposed that the future development focus of lignin in plastic flame retardant application was to construct multi-level nano microphase separation structure in plastic matrix, and to construct dynamic energy sacrificial bonds between lignin nanoparticles and the plastic phase interface to improve interfacial forces and solve the problems of poor compatibility and difficult dispersion between lignin and plastic. In addition, to ensure the original physical and mechanical properties of the plastic, reducing the amount of lignin and ensuring flame retardant effect were also one of the development directions of this type of flame retardants.

Key words: lignin, flame retardant plastics, physical synergy, chemical modification, flame retardant mechanism

摘要：

木质素作为含碳量高、热稳定性好、成炭能力强和易于改性的生物质材料，常被用来作为生物质阻燃剂阻燃塑料，以改善塑料的易燃性、减少塑料受热时熔滴的生成和烟雾的释放，但存在阻燃效率低、添加量和产烟量大以及耐久性差等诸多问题。为更好地了解木质素在阻燃塑料中的应用情况，本文首先简述了木质素的结构，详细分析了木质素提升塑料阻燃性能的机理，然后系统回顾了未改性和改性木质素基阻燃剂在阻燃塑料应用中的研究现状，分析了不同阻燃应用的优缺点。提出未来木质素在阻燃塑料应用中的发展重点是在塑料基体中构建多级纳米微相分离结构，并在木质素纳米粒子与塑料相界面间构建动态能量牺牲键以提高界面作用力，解决木质素与塑料相容性差、不易分散的难题，此外，在保证阻燃效果的同时减少木质素的用量以确保塑料原有的物理力学性能也是该类阻燃剂的发展方向之一。

关键词: 木质素, 阻燃塑料, 物理协同, 化学改性, 阻燃机理

CLC Number:

TQ314.1

WANG Hui, LIU Shuping, LIAO Xilin, CHENG Xiaowen, LIU Rangtong. Research progress of lignin applied to flame retardant plastics[J]. Chemical Industry and Engineering Progress, 2025, 44(11): 6413-6426.

王慧, 刘淑萍, 廖喜林, 程晓雯, 刘让同. 木质素在阻燃塑料应用中的研究进展[J]. 化工进展, 2025, 44(11): 6413-6426.

Figures/Tables 9

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样品^①	Ad^②/%	残炭率/%	PHRR/kW·m^-2	THR/MJ·m^-2	烟密度/%	参考文献
PE-0	0	18.00（600℃）	263.00	—	86	[40]
PE-10	10.00	—	242.00	—	73	[40]
PE-15	15.00	—	232.00	—	61	[40]
PE-20	20.00	—	215.00	—	52	[40]
PE-25	25.00	31.00（600℃）	226.00	—	58	[40]
ABS-0	0	1.90（650℃）	775.00	71.20	—	[41]
ABS-5	5.00	4.90（650℃）	640.00	69.10	—	[41]
ABS-10	10.00	7.00（650℃）	550.00	65.40	—	[41]
ABS-20	20.00	14.50（650℃）	526.00	65.10	—	[41]

样品^①	Ad^②/%	残炭率/%	PHRR/kW·m^-2	THR/MJ·m^-2	烟密度/%	参考文献
PE-0	0	18.00（600℃）	263.00	—	86	[40]
PE-10	10.00	—	242.00	—	73	[40]
PE-15	15.00	—	232.00	—	61	[40]
PE-20	20.00	—	215.00	—	52	[40]
PE-25	25.00	31.00（600℃）	226.00	—	58	[40]
ABS-0	0	1.90（650℃）	775.00	71.20	—	[41]
ABS-5	5.00	4.90（650℃）	640.00	69.10	—	[41]
ABS-10	10.00	7.00（650℃）	550.00	65.40	—	[41]
ABS-20	20.00	14.50（650℃）	526.00	65.10	—	[41]

样品	Ad/%	LOI/%	UL-94	是否产生熔滴	残炭率/%	PHRR/kW·m^-2	THR/MJ·m^-2	TSR/m²·m^-3	参考文献
PP	0	18.00	无级别	有	0（800℃）	588.00	105.00	—	[45]
PP/IFR	30.00	31.00	V-0级	没有	7.30（800℃）	253.00	104.00	—	[45]
PF	0	35.60	V-0级	没有	43.80（800℃）	—	—	—	[39]
PF/IFR	50.00	46.40	V-0级	没有	52.30（800℃）	—	—	—	[39]
PUF	0	19.10	无级别	有	21.10（700℃）	215.90	11.40	—	[46]
PUF/IFR1	34.00	31.60	V-0级	没有	39.70（700℃）	74.40	5.50	—	[46]
PUF	0	18.70	无级别	有	0（700℃）	—	—	884.00	[47]
PUF/IFR2	30.00	26.30	V-0级	没有	33.80（700℃）	—	—	538.00	[47]
EP	0	22.20	无级别	有	6.76（800℃）	1501.70	—	121.00	[48]
EP/IFR	20.00	27.50	V-0级	没有	10.78（800℃）	598.99	—	125.00	[48]
RPUF	0	18.60	无级别	有	—	179.49	4.23	12.50	[49]
RPUF/IFR	30.00	27.20	V-0级	没有	—	87.00	2.20	11.70	[49]

样品	Ad/%	LOI/%	UL-94	是否产生熔滴	残炭率/%	PHRR/kW·m^-2	THR/MJ·m^-2	TSR/m²·m^-3	参考文献
PP	0	18.00	无级别	有	0（800℃）	588.00	105.00	—	[45]
PP/IFR	30.00	31.00	V-0级	没有	7.30（800℃）	253.00	104.00	—	[45]
PF	0	35.60	V-0级	没有	43.80（800℃）	—	—	—	[39]
PF/IFR	50.00	46.40	V-0级	没有	52.30（800℃）	—	—	—	[39]
PUF	0	19.10	无级别	有	21.10（700℃）	215.90	11.40	—	[46]
PUF/IFR1	34.00	31.60	V-0级	没有	39.70（700℃）	74.40	5.50	—	[46]
PUF	0	18.70	无级别	有	0（700℃）	—	—	884.00	[47]
PUF/IFR2	30.00	26.30	V-0级	没有	33.80（700℃）	—	—	538.00	[47]
EP	0	22.20	无级别	有	6.76（800℃）	1501.70	—	121.00	[48]
EP/IFR	20.00	27.50	V-0级	没有	10.78（800℃）	598.99	—	125.00	[48]
RPUF	0	18.60	无级别	有	—	179.49	4.23	12.50	[49]
RPUF/IFR	30.00	27.20	V-0级	没有	—	87.00	2.20	11.70	[49]

木质素的化学改性方法	反应式	反应条件及目的	参考文献
胺化反应	图3(a)	利用木质素苯环上活泼的氢基与甲醛和胺缩合在木质素的苯环上引入含氮阻燃化合物，增强木质素在塑料中的阻燃效能	[50,52]
酯化反应	图3(b)	木质素在催化剂1-甲基咪唑的作用下，与丁酸酐发生化学反应。通过该反应，木质素的分子结构得到了优化，使其在高温环境下更加稳定，不易分解，提高热稳定性	[50,53]
羟甲基化反应	图3(c)	在80℃的条件下，木质素与甲醛在氢氧化钠溶液中发生反应。随后，通过添加盐酸调节pH至2，从而在木质素的苯环上引入羟甲基。这一过程增加了活性基团的数量，便于进一步引入磷、氮和金属离子等阻燃元素，从而提升材料的阻燃性能	[50,54]
席夫碱反应	图3(d)	主要是利用木质素分子结构中的羰基与三乙烯四胺（TETA）在水溶液中先发生亲核加成反应，后能脱水缩合以引入磷氮等其他阻燃元素，抑制火焰的传播，提高整体阻燃性能	[50,55]
硅烷化反应	图3(e)	将有机硅溶解于水和乙醇的混合溶剂中，使其与木质素进行反应，以引入硅元素，从而延缓燃烧速度并提升材料的阻燃耐久性	[50,56]