木质素基阻燃剂的研究进展

doi:10.3969/j.issn.1673-5854.2023.02.009

摘要/Abstract

摘要：

木质素化学结构中含有丰富的碳原子, 其本身可作为高分子材料中的填料, 在高分子材料燃烧过程中提供碳源并促进阻燃; 木质素的分子结构含有芳香基、酚羟基、醇羟基等活性基团, 通过化学改性将具有阻燃作用的元素或基团引入到木质素的化学结构中, 可以获得一系列木质素基阻燃剂。本文从木质素结构入手, 概述了国内外未改性木质素, 氮、磷改性木质素和掺入金属铜或非金属硅的氮磷改性木质素在不同聚合物材料中做阻燃剂的研究进展, 包括物理协同阻燃配方、化学改性制备方法、处理前后的阻燃效果对比。同时, 解释了相应阻燃剂的阻燃机理, 包括: 释放出的不可燃气体对氧气的隔绝作用, 形成致密不可燃炭层, 以及对热量传递的阻碍作用等。并对木质素基阻燃剂的应用前景进行了展望。

关键词: 木质素, 阻燃剂, 聚合物, 化学改性, 阻燃机理

Abstract:

Lignin contained abundant carbon atoms in its chemical structure, which could be used as filler in polymer materials to provide carbon source and promote flame retardant in the combustion process of polymer materials. The molecular structure of lignin contained active groups such as aromatic group, phenolic hydroxyl group and alcohol hydroxyl group. A series of lignin-based flame retardants could be obtained by introducing flame retardant elements or groups into the chemical structure of lignin through chemical modification. Starting from the structure of lignin, this paper summarized the domestic and foreign research progress of unmodified lignin, nitrogen and phosphorus modified lignin, and nitrogen and phosphorus modified lignin doped with copper or non-metallic elements like silicon as flame retardants in different polymeric materials, including physical synergistic flame retardant formulations, chemical modification preparation process and the comparison of flame retardancy effect before and after treatment. The flame retardant mechanism of the corresponding flame retardants was analyzed, including the oxygen isolation effect by the released non-combustible gas, the formation of dense non-combustible carbon layer, and the hindering effect on heat transfer. Additionally, the application prospect of lignin-based flame retardants was prospected.

Key words: lignin, fire retardant, polymer, chemical modification, flame retardant mechanism

中图分类号:

TQ35

贝钰, 翁述贤, 贾普友, 薄采颖, 胡立红, 周永红. 木质素基阻燃剂的研究进展[J]. 生物质化学工程, 2023, 57(2): 71-78.

Yu BEI, Shuxian WENG, Puyou JIA, Caiying BO, Lihong HU, Yonghong ZHOU. Research Progress on Lignin-based Flame Retardants[J]. Biomass Chemical Engineering, 2023, 57(2): 71-78.

图/表 6

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参考文献 50

1	陶磊, 黄元波, 郑云武, 等. 木质素制备低成本碳纤维的研究进展[J]. 高分子材料科学与工程, 2017, 33 (1): 179- 185.179-185, 190
2	FEOFILOVA E P , MYSYAKINA I S . Lignin: Chemical structure, biodegradation, and practical application(A review)[J]. Applied Biochemistry and Microbiology, 2016, 52 (6): 573- 581. doi: 10.1134/S0003683816060053
3	任苗苗, 吕惠生, 张敏华, 等. 木质素资源利用的研究进展[J]. 高分子通报, 2012, (8): 44- 49.
4	PRIEUR B , MEUB M , WITTEMANN M , et al. Phosphorylation of lignin to flame retard acrylonitrile butadiene styrene(ABS)[J]. Polymer Degradation and Stability, 2016, 127, 32- 43. doi: 10.1016/j.polymdegradstab.2016.01.015
5	CORREA C C , STOLLOVSKY M , HEHR T , et al. Influence of the carbonization process on activated carbon properties from lignin and lignin-rich biomasses[J]. ACS Sustainable Chemistry & Engineering, 2017, 5 (9): 8222- 8233.
6	BREBU M , TAMMINEN T , SPIRIDON I . Thermal degradation of various lignins by TG-MS/FTIR and Py-GC-MS[J]. Journal of Analytical and Applied Pyrolysis, 2013, 104, 531- 539. doi: 10.1016/j.jaap.2013.05.016
7	KIM J Y , OH S , HWANG H , et al. Structural features and thermal degradation properties of various lignin macromolecules obtained from poplar wood(Populus albaglandulosa)[J]. Polymer Degradation and Stability, 2013, 98 (9): 1671- 1678. doi: 10.1016/j.polymdegradstab.2013.06.008
8	杨云峰, 张现军, 胡国胜. 无卤阻燃剂的研究现状[J]. 山西化工, 2010, 30 (1): 50- 53. doi: 10.3969/j.issn.1004-7050.2010.01.013
9	张翔宇, 黄琰, 游歌云, 等. 无卤阻燃剂研究进展[J]. 精细化工中间体, 2011, 41 (3): 1- 8.
10	CAYLA A, RAULT F, GIRAUD S, et al. PLA with intumescent system containing lignin and ammonium polyphosphate for flame retardant textile[J/OL]. Polymers, 2016, 8(9): 331[2021-11-10]. https://doi.org/10.3390/polym8090331.
11	RÉTI C , CASETTA M , DUQUESNE S , et al. Flammability properties of intumescent PLA including starch and lignin[J]. Polymers for Advanced Technologies, 2008, 19 (6): 628- 635. doi: 10.1002/pat.1130
12	CARRETIER V, DELCROIX J, PUCCI M, et al. Influence of sepiolite and lignin as potential synergists on flame retardant systems in polylactide(PLA) and polyurethane elastomer(PUE)[J/OL]. Materials, 2020, 13(11): 2450[2022-11-22]. https://www.mdpi.com/1996-1944/13/11/2450#app1-materials-13-02450.
13	MANDLEKAR N, CAYLA A, RAULT F, et al. Valorization of industrial lignin as biobased carbon source in fire retardant system for polyamide 11 blends[J/OL]. Polymers(Basel), 2019, 11(1): 180[2022-11-22]. https://pubmed.ncbi.nlm.nih.gov/30960166/.
14	高濂, 刘阳桥. 碳纳米管的分散及表面改性[J]. 硅酸盐通报, 2005, 24 (5): 114- 119. doi: 10.3969/j.issn.1001-1625.2005.05.021
15	SHVARTZMAN-COHEN R , LEVI-KALISMAN Y , NATIV-ROTH E , et al. Generic approach for dispersing single-walled carbon nanotubes: The strength of a weak interaction[J]. Langmuir, 2004, 20 (15): 6085- 6088. doi: 10.1021/la049344j
16	GOODMAN S M , FERGUSON N , DICHIARA A B . Lignin-assisted double acoustic irradiation for concentrated aqueous dispersions of carbon nanotubes[J]. RSC Advances, 2017, 7 (9): 5488- 5496. doi: 10.1039/C6RA25986C
17	DICHIARA A B , SHERWOOD T J , BENTON-SMITH J , et al. Free-standing carbon nanotube/graphene hybrid papers as next generation adsorbents[J]. Nanoscale, 2014, 6 (12): 6322- 6327. doi: 10.1039/c4nr01028k
18	LI W K , DICHIARA A , BAI J B . Carbon nanotube-graphene nanoplatelet hybrids as high-performance multifunctional reinforcements in epoxy composites[J]. Composites Science and Technology, 2013, 74, 221- 227. doi: 10.1016/j.compscitech.2012.11.015
19	SONG K L, GANGULY I, EASTIN I, et al. Lignin-modified carbon nanotube/graphene hybrid coating as efficient flame retardant[J/OL]. International Journal of Molecular Sciences, 2017, 18(11): 2368[2022-11-22]. https://pubmed.ncbi.nlm.nih.gov/29117109/.
20	LAVOINE N , DESLOGES I , DUFRESNE A , et al. Microfibrillated cellulose——Its barrier properties and applications in cellulosic materials: A review[J]. Carbohydrate Polymer, 2012, 90 (2): 735- 764. doi: 10.1016/j.carbpol.2012.05.026
21	ZU G Q , SHEN J , ZOU L P , et al. Nanocellulose-derived highly porous carbon aerogels for supercapacitors[J]. Carbon, 2016, 99, 203- 211. doi: 10.1016/j.carbon.2015.11.079
22	WICKLEIN B , KOCJAN A , SALAZAR-ALVAREZ G , et al. Thermally insulating and fire-retardant lightweight anisotropic foams based on nanocellulose and graphene oxide[J]. Nat Nanotechnol, 2015, 10 (3): 277- 283. doi: 10.1038/nnano.2014.248
23	TONG C C, ZHANG S, ZHONG T H, et al. Highly fibrillated and intrinsically flame-retardant nanofibrillated cellulose for transparent mineral filler-free fire-protective coatings[J/OL]. Chemical Engineering Journal, 2021, 419: 129440[2022-11-22]. https://www.sciencedirect.com/science/article/pii/S1385894721010275.
24	GUO Y B, CHENG C Z, HUO T G, et al. Highly effective flame retardant lignin/polyacrylonitrile composite prepared via solution blending and phosphorylation[J/OL]. Polymer Degradation and Stability, 2020, 181: 109362[2022-11-22]. https://www.sciencedirect.com/science/article/pii/S0141391020302937.
25	XING W Y , YUAN H X , ZHANG P , et al. Functionalized lignin for halogen-free flame retardant rigid polyurethane foam: Preparation, thermal stability, fire performance and mechanical properties[J]. Journal of Polymer Research, 2013, 20 (9): 1- 12.
26	COSTES L , LAOUTID F , AGUEDO M , et al. Phosphorus and nitrogen derivatization as efficient route for improvement of lignin flame retardant action in PLA[J]. European Polymer Journal, 2016, 84, 652- 667. doi: 10.1016/j.eurpolymj.2016.10.003
27	YU Y M , FU S Y , SONG P A , et al. Functionalized lignin by grafting phosphorus-nitrogen improves the thermal stability and flame retardancy of polypropylene[J]. Polymer Degradation and Stability, 2012, 97 (4): 541- 546. doi: 10.1016/j.polymdegradstab.2012.01.020
28	张红, 冯钠, 张桂霞, 等. 磷氮接枝木质素磺酸盐的合成及成炭阻燃热塑性聚烯烃弹性体[J]. 高分子材料科学与工程, 2015, 31 (9): 11- 16.
29	ZHOU S , TAO R , DAI P , et al. Two-step fabrication of lignin-based flame retardant for enhancing the thermal and fire retardancy properties of epoxy resin composites[J]. Polymer Composites, 2020, 41 (5): 2025- 2035. doi: 10.1002/pc.25517
30	刘亚青, 赵贵哲. 原位聚合法制备红磷微胶囊阻燃剂[J]. 华北工学院学报, 2002, 23 (3): 219- 221.
31	李剑秋, 葛世成. 白度化微胶囊化红磷阻燃剂的制备及其在塑料中的应用[J]. 塑料, 1994, 23 (5): 33- 36.
32	胡海波, 刘亚雄, 李一龙, 等. 新型木质素基膨胀型阻燃剂的合成及其在LLDPE/EVA中的性能研究[J]. 金属材料与冶金工程, 2016, 44 (3): 3- 7.3-7, 14
33	钟柔潮, 林修端, 黄少淮, 等. 哌嗪改性木质素/磷酸铝双重包覆红磷的制备与阻燃性能[J]. 高分子材料科学与工程, 2019, 35 (12): 143- 148.143-148, 154
34	ZHANG Y M , ZHAO Q , LI L , et al. Synthesis of a lignin-based phosphorus-containing flame retardant and its application in polyurethane[J]. RSC Advances, 2018, 8 (56): 32252- 32261.
35	HU W, ZHANG Y M, QI Y X, et al. Improved mechanical properties and flame retardancy of wood/PLA all-degradable biocomposites with novel lignin-based flame retardant and TGIC[J/OL]. Macromolecular Materials and Engineering, 2020, 305(5): 1900840[2022-11-22]. https://onlinelibrary.wiley.com/doi/abs/10.1002/mame.201900840.
36	DAI P , LIANG M , MA X , et al. Highly efficient, environmentally friendly lignin-based flame retardant used in epoxy resin[J]. ACS Omega, 2020, 5 (49): 32084- 32093.
37	HALPERN Y , MOTT D M , NISWANDER R H . Fire retardancy of thermoplastic materials by intumescence[J]. Industrial & Engineering Chemistry Product Research and Development, 1984, 23 (2): 233- 238.
38	YANG H , SHI B , XUE Y , et al. Molecularly engineered lignin-derived additives enable fire-retardant, UV-shielding, and mechanically strong polylactide biocomposites[J]. Biomacromolecules, 2021, 22 (4): 1432- 1444.
39	CHEN S , LIN S , HU Y , et al. A lignin-based flame retardant for improving fire behavior and biodegradation performance of polybutylene succinate[J]. Polymers for Advanced Technologies, 2018, 29 (12): 3142- 3150.
40	ZHANG R , XIAO X F , TAI Q L , et al. Preparation of lignin-silica hybrids and its application in intumescent flame-retardant poly(lactic acid) system[J]. High Performance Polymers, 2012, 24 (8): 738- 746.
41	SONG Y, ZONG X, WANG N, et al. Preparation of gamma-divinyl-3-aminopropyltriethoxysilane modified lignin and its application in flame retardant poly(lactic acid)[J/OL]. Materials(Basel), 2018, 11(9): 1505[2022-11-22]. https://www.mdpi.com/1996-1944/11/9/1505.
42	CHOLLET B, LOPEZ-CUESTA J M, LAOUTID F, et al. Lignin nanoparticles as a promising way for enhancing lignin flame retardant effect in polylactide[J/OL]. Materials(Basel), 2019, 12(13): 2132[2022-11-22]. https://www.mdpi.com/1996-1944/12/13/2132.
43	LAOUTID F , BONNAUD L , ALEXANDRE M , et al. New prospects in flame retardant polymer materials: From fundamentals to nanocomposites[J]. Materials Science and Engineering R: Reports, 2009, 63 (3): 100- 125.
44	ZHANG J F , FLEURY E , CHEN Y , et al. Flame retardant lignin-based silicone composites[J]. RSC Advances, 2015, 5 (126): 103907- 103914.
45	LIU L N , HUANG G B , SONG P A , et al. Converting industrial alkali lignin to biobased functional additives for improving fire behavior and smoke suppression of polybutylene succinate[J]. ACS Sustainable Chemistry & Engineering, 2016, 4 (9): 4732- 4742.
46	TIAN B, LI J, LI Z, et al. Preparation of polypropylene with high melt strength by wet reaction blending of lignin[J/OL]. Journal of Applied Polymer Science, 2022, 139(1): 51224[2022-11-22]. https://onlinelibrary.wiley.com/doi/epdf/10.1002/app.51224.
47	RECEPOGLU Y K, GOREN A Y, OROOJI Y, et al. Carbonaceous materials for removal and recovery of phosphate species: Limitations, successes and future improvement[J/OL]. Chemosphere, 2022, 287: 132177[2022-11-22]. https://www.sciencedirect.com/science/article/pii/S0045653521026497.
48	CHEN F G , LIU W S , SHAHABADI S I S , et al. Sheet-like lignin particles as multifunctional fillers in polypropylene[J]. ACS Sustainable Chemistry & Engineering, 2016, 4 (9): 4997- 5004.
49	YU Y M , SONG P A , JIN C D , et al. Catalytic effects of nickel(cobalt or zinc) acetates on thermal and flammability properties of polypropylene-modified lignin composites[J]. Industrial & Engineering Chemistry Research, 2012, 51 (38): 12367- 12374.
50	LIU L N , QIAN M B , SONG P A , et al. Fabrication of green lignin-based flame retardants for enhancing the thermal and fire retardancy properties of polypropylene/wood composites[J]. ACS Sustainable Chemistry & Engineering, 2016, 4 (4): 2422- 2431.

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