石墨烯在聚合物阻燃材料中的应用及作用机理

doi:10.11944/j.issn.1000-0518.2018.03.170469

摘要/Abstract

摘要：

本文从聚合物基底的阻燃复合材料类别角度出发,详细介绍了石墨烯在不同种类聚合物阻燃材料中的应用现状与作用机理。包括有:石墨烯/聚乙烯、石墨烯/聚丙烯、石墨烯/聚苯乙烯、石墨烯/环氧树脂、石墨烯/聚氨酯、石墨烯/聚乙烯醇等多种石墨烯/聚合物复合阻燃材料。同时还介绍了石墨烯基材料在其中所发挥的作用,该综述为发展出新型的石墨烯基/聚合物复合阻燃材料提供了很好的理论支持。

关键词: 石墨烯, 聚合物, 阻燃, 纳米材料

Abstract:

In this paper, starting from the flame retardant composite materials of different polymer substrates, the application and mechanism of graphene in different kinds of polymer flame retardant materials are introduced in detail including graphene/polyethylene, graphene/polypropylene, graphene/polystyrene, graphene/epoxy resin, graphene/polyurethane, graphene/polyvinyl alcohol and graphene/other polymer composite flame retardant materials. The effect of graphene-based materials is also introduced in detail. This review provides a good theoretical support for the development of novel graphene-based/polymer composite flame retardant materials.

Key words: graphene, polymer, flame retardant, nanomaterials

陈南,钟贵林,张国峰. 石墨烯在聚合物阻燃材料中的应用及作用机理[J]. 应用化学, 2018, 35(3): 307-316.

CHEN Nan,ZHONG Guilin,ZHANG Guofeng. Application and Interaction Mechanism of Graphene in Polymer Flame Retardant Materials[J]. Chinese Journal of Applied Chemistry, 2018, 35(3): 307-316.

参考文献

[1]	ZHU Deqin,ZHENG Shouyang,SHENG Yu.Flame-retardant Synergistic Effect of Synergists on Intumescent Flame-retardant Wood Flour-Polypropylene Composites[J]. Chinese J Appl Chem,2017,34(2):195-203(in Chinese). 朱德钦,郑守扬,生瑜. 协效剂对膨胀阻燃聚丙烯基木塑复合材料的阻燃增效研究[J]. 应用化学,2017,34(2):195-203.
[2]	GAO Yuan,CHEN Guohua.Recent Progress in Preparation Method of the Polymer/Graphene Composites and It's Industrialization Status[J]. Acta Polym Sin,2014,(10):1314-1327(in Chinese). 高源,陈国华. 聚合物/石墨烯复合材料制备研究新进展及其产业化现状[J]. 高分子学报,2014,(10):1314-1327.
[3]	WANG Ziying,SHEN Yifeng,YANG Lei,et al.Application of Vinyl Nitrogen Phosphorus Flame Retardants on Silk Fabric[J]. J Text Res,2015,36(7):77-82(in Chinese). 王紫颖,沈一峰,杨雷,等. 乙烯基磷氮类阻燃剂在蚕丝织物上的应用[J]. 纺织学报,2015,36(7):77-82.
[4]	ZHANG Jinkai,MA Li,GE Weijuan,et al.Research Status of Intumescent Flame-retarded Polypropylene[J]. Mater Rev A,2015,29(5):68-72(in Chinese). 张金凯,马丽,葛维娟,等. 膨胀型阻燃剂阻燃聚丙烯的研究进展[J]. 材料导报A,2015,29(5):68-72.
[5]	FAN Quanbao,XIE Ting,YANG Eryan,et al.Effect of Carbonate Oligomer of Tetrabromobisphenol A on Flame Retardance of Polycarbonate[J]. Plast Sci Technol,2010,38(1):43-45(in Chinese). 范全保,谢婷,杨二钘,等. 苯氧基四溴双酚A聚碳酸酯齐聚物对聚碳酸酯阻燃性能的影响[J]. 塑料科技,2010,38(1):43-45.
[6]	LI Xingjian,ZHANG Yiheng,SUN Daoxing.Preparation and Properties of Magnesium Hydroxide/Aluminum Hydroxide/Melamine Phosphate Filled Flame Retardant Silicone Rubber[J]. China Rubber Ind,2013,60(6):344-350(in Chinese). 李兴建,张宜恒,孙道兴. 氢氧化镁/氢氧化铝/三聚氰胺磷酸盐协效无卤膨胀型阻燃硅橡胶的制备与性能研究[J]. 橡胶工业,2013,60(6):344-350.
[7]	Ran S,Guo Z,Han L,et al.Effect of Friedel-Crafts Reaction on the Thermal Stability and Flammability of High-Density Polyethylene/Brominated Polystyrene/Graphene Nanoplatelet Composites[J]. Polym Int,2014,63(10):1835-1841.
[8]	Ran S,Chen C,Guo Z,et al.Char Barrier Effect of Graphene Nanoplatelets on the Flame Retardancy and Thermal Stability of High-Density Polyethylene Flame-Retarded by Brominated Polystyrene[J]. J Appl Polym Sci,2014,131(15):4401-4404.
[9]	Hu W,Zhan J,Wang X,et al.Effect of Functionalized Graphene Oxide with Hyper-Branched Flame Retardant on Flammability and Thermal Stability of Cross-Linked Polyethylene[J]. Ind Eng Chem Res,2014,53(13):3073-3083.
[10]	Dittrich B,Wartig K,Hofmann D,et al.Flame Retardancy Through Carbon Nanomaterials: Carbon Black, Multiwall Nanotubes, Expanded Graphite, Multi-Layer Graphene and Graphene in Polypropylene[J]. Polym Degrad Stabil,2013,98(8):1495-1505.
[11]	Hofmann D,Wartig K,Thomann R,et al.Functionalized Graphene and Carbon Materials as Additives for Melt-Extruded Flame Retardant Polypropylene[J]. Macromol Mater Eng,2013,298(12):1322-1334.
[12]	Dittrich B,Wartig K,Hofmann D,et al.Carbon Black, Multiwall Carbon Nanotubes, Expanded Graphite and Functionalized Graphene Flame Retarded Polypropylene Nanocomposites[J]. Polym Adv Technol,2013,24(10):916-926.
[13]	Huang G,Wang S,Song P,et al.Combination Effect of Carbon Nanotubes with Graphene on Intumescent Flame-Retardant Polypropylene Nanocomposites[J]. Composites:Part A,2014,59:18-25.
[14]	Xu J,Liu J,Li K.Application of Functionalized Graphene Oxide in Flame-Retardant Polypropylene[J]. J Vinyl Addit Tech,2015,21(4):278-284.
[15]	Dong L,Hu C,Song L,et al.A Large-Area, Flexible, and Flame-Retardant Graphene Paper[J]. Adv Funct Mater,2016,26(9):1470-1476.
[16]	Hu C,Xue J,Dong L,et al.Scalable Preparation of Multifunctional Fire-Retardant Ultralight Graphene Foams[J]. ACS Nano,2016,10(1):1325-1332.
[17]	Chen W,Liu Y,Lin P,et al.The Preparation and Application of a Graphene-based Hybrid Flame Retardant Containing a Long-Chain Phosphaphenanthrene[J]. Sci Rep,2017,7(1):8759.
[18]	Yu B,Wang X,Qian X,et al.Functionalized Graphene Oxide/Phosphoramide Oligomer Hybrids Flame Retardant Prepared via in Situ Polymerization for Improving the Fire Safety of Polypropylene[J]. RSC Adv,2014,4(60):31782-31794.
[19]	Dittrich B,Wartig K,M lhaupt R,et al. Flame-Retardancy Properties of Intumescent Ammonium Poly(phosphate) and Mineral Filler Magnesium Hydroxide in Combination with Graphene[J]. Polymers,2014,6(11):2875-2895.
[20]	Nie L,Liu C,Liu L,et al.Study of the Thermal Stability and Flame Retardant Properties of Graphene Oxide-Decorated Zirconium Organophosphate Based on Polypropylene Nanocomposites[J]. RSC Adv,2015,5(112):92318-92327.
[21]	Yuan B,Bao C,Song L,et al.Preparation of Functionalized Graphene Oxide/Polypropylene Nanocomposite with Significantly Improved Thermal Stability and Studies on the Crystallization Behavior and Mechanical Properties[J]. Chem Eng J,2014,237:411-420.
[22]	Yuan B,Song L,Liew K,et al.Solid Acid-reduced Graphene Oxide Nanohybrid for Enhancing Thermal Stability, Mechanical Property and Flame Retardancy of Polypropylene[J]. RSC Adv,2015,5(51):41307-41316.
[23]	Yuan B,Sheng H,Mu X,et al.Enhanced Flame Retardancy of Polypropylene by Melamine-Modified Graphene Oxide[J]. J Mater Sci,2015,50(16):5389-5401.
[24]	Ren P G,Yan D X,Chen T,et al.Improved Properties of Highly Oriented Graphene/Polymer Nanocomposites[J]. J Appl Polym Sci,2011,121(6):3167-3174.
[25]	Bao C,Guo Y,Yuan B,et al.Functionalized Graphene Oxide for Fire Safety Applications of Polymers:A Combination of Condensed Phase Flame Retardant Strategies[J]. J Mater Chem,2012,22(43):23057-23063.
[26]	Han Y,Wu Y,Shen M,et al.Preparation and Properties of Polystyrene Nanocomposites with Graphite Oxide and Graphene as Flame Retardants[J]. J Mater Sci,2013,48(12):4214-4222.
[27]	Zhou K,Yang W,Tang G,et al.Comparative Study on the Thermal Stability, Flame Retardancy and Smoke Suppression Properties of Polystyrene Composites Containing Molybdenum Disulfide and Graphene[J]. RSC Adv,2013,3(47):25030-25040.
[28]	Attia N,Abd El-Aal N,Hassan M. Facile Synthesis of Graphene Sheets Decorated Nanoparticles and Flammability of Their Polymer Nanocomposites[J]. Polym Degrad Stabil,2016,126:65-74.
[29]	Hong N,Zhan J,Wang X,et al.Enhanced Mechanical, Thermal and Flame Retardant Properties by Combining Graphene Nanosheets and Metal Hydroxide Nanorods for Acrylonitrile-Butadiene-Styrene Copolymer Composite[J]. Composites:Part A,2014,64:203-210.
[30]	Higginbotham A,Lomeda J,Morgan A,et al.Graphite Oxide Flame-Retardant Polymer Nanocomposites[J]. ACS Appl Mater Interfaces,2009,1(10):2256-2261.
[31]	Hu W,Yu B,Jiang S,et al.Hyper-branched Polymer Grafting Graphene Oxide as an Effective Flame Retardant and Smoke Suppressant for Polystyrene[J]. J Hazard Mater,2015,300:58-66.
[32]	Zhuo D,Wang R,Wu L,et al.Flame Retardancy Effects of Graphene Nanoplatelet/Carbon Nanotube Hybrid Membranes on Carbon Fiber Reinforced Epoxy Composites[J]. J Nanomater,2013,2013(1):820901.
[33]	Li Q,Guo Y,Li W,et al.Ultrahigh Thermal Conductivity of Assembled Aligned Multilayer Graphene/Epoxy Composite[J]. Chem Mater,2014,26(15):4459-4465.
[34]	Luo F,Wu K,Guo H,et al.Anisotropic Thermal Conductivity and Flame Retardancy of Nanocomposite Based on Mesogenic Epoxy and Reduced Graphene Oxide Bulk[J]. Compos Sci Technol,2016,132:1-8.
[35]	Liu S,Yan H,Fang Z,et al.Effect of Graphene Nanosheets on Morphology, Thermal Stability and Flame Retardancy of Epoxy Resin[J]. Compos Sci Technol,2014,90:40-47.
[36]	Wang R,Zhuo D,Weng Z,et al.A Novel Nanosilica/Graphene Oxide Hybrid and Its Flame Retarding Epoxy Resin with Simultaneously Improved Mechanical, Thermal Conductivity, and Dielectric Properties[J]. J Mater Chem A,2015,3(18):9826-9836.
[37]	Wang X,Xing W,Feng X,et al.The Effect of Metal Oxide Decorated Graphene Hybrids on the Improved Thermal Stability and the Reduced Smoke Toxicity in Epoxy Resins[J]. Chem Eng J,2014,250:214-221.
[38]	Guan F,Gui C,Zhang H,et al.Enhanced Thermal Conductivity and Satisfactory Flame Retardancy of Epoxy/Alumina Composites by Combination with Graphene Nanoplatelets and Magnesium Hydroxide[J]. Composites Part B,2016,98:134-140.
[39]	Liu S,Yan H,Fang Z,et al.Effect of Graphene Nanosheets and Layered Double Hydroxides on the Flame Retardancy and Thermal Degradation of Epoxy Resin[J]. RSC Adv,2014,4(36):18652-18659.
[40]	Guo Y,Bao C,Song L,et al.In Situ Polymerization of Graphene, Graphite Oxide, and Functionalized Graphite Oxide into Epoxy Resin and Comparison Study of On-the-Flame Behavior[J]. Ind Eng Chem Res,2011,50(13):7772-7783.
[41]	Liu S,Fang Z,Yan H,et al.Superior Flame Retardancy of Epoxy Resin by the Combined Addition of Graphene Nanosheets and DOPO[J]. RSC Adv,2016,6(7):5288-5295.
[42]	Liao S,Liu P,Hsiao M,et al.One-Step Reduction and Functionalization of Graphene Oxide with Phosphorus-Based Compound to Produce Flame-Retardant Epoxy Nanocomposite[J]. Ind Eng Chem Res,2012,51(12):4573-4581.
[43]	Wang X,Song L,Pornwannchai W,et al.The Effect of Graphene Presence in Flame Retarded Epoxy Resin Matrix on the Mechanical and Flammability Properties of Glass Fiber-reinforced Composites[J]. Composites:Part A,2013,53:88-96.
[44]	Wang Z,Wei P,Qian Y,et al.The Synthesis of a Novel Graphene-based Inorganic Organic Hybrid Flame Retardant and Its Application in Epoxy Resin[J]. Composites:Part B,2014,60:341-349.
[45]	Yu B,Shi Y,Yuan B,et al, Enhanced Thermal and Flame Retardant Properties of Flame-retardant-wrapped Graphene/Epoxy Resin Nanocomposites[J]. J Mater Chem A,2015,3(15):8034-8044.
[46]	Qian X,Song L,Yu B,et al.Novel Organic inorganic Flame Retardants Containing Exfoliated Graphene:Preparation and Their Performance on the Flame Retardancy of Epoxy Resins[J]. J Mater Chem A,2013,1(23):6822-6830.
[47]	Wang X,Xing W,Feng X,et al.Functionalization of Graphene with Grafted Polyphosphamide for Flame Retardant Epoxy Composites:Synthesis, Flammability and Mechanism[J]. Polym Chem,2014,5(4):1145-1154.
[48]	Hu J,Zhang F.Self-assembled Fabrication and Flame-Retardant Properties of Reduced Graphene Oxide/Waterborne Polyurethane Nanocomposites[J]. J Therm Anal Calorim,2014,118(3):1561-1568.
[49]	Zhou K,Gui Z,Hu Y,et al.The Influence of Cobalt Oxide Graphene Hybrids on Thermal Degradation, Fire Hazards and Mechanical Properties of Thermoplastic Polyurethane Composites[J]. Composites:Part A,2016,88:10-18.
[50]	Wang Z,Li X. Mechanical Properties and Flame Retardancy of Rigid Polyurethane Foams Containing a SiO2 Nanospheres/Graphene Oxide Hybrid and Dimethyl Methylphosphonate[J/OL]. J Polym-Plast Technol Eng,2017-07-20.[2018-01-03]. https://doi.org/10.1080/03602559.2017.1354251.[published online ahead of print]
[51]	Pan H,Lu Y,Song L,et al.Fabrication of Binary Hybrid-Filled Layer-by-Layer Coatings on Flexible Polyurethane Foams and Studies on Their Flame-Retardant and Thermal Properties[J]. RSC Adv,2016,6(82):78286-78295.
[52]	Wei H,Zhu Z,Sun H,et al.Graphene and Poly(ionic liquid) Modified Polyurethane Sponges with Enhanced Flame-Retardant Properties[J]. J Appl Polym Sci,2017,134(44):45477.
[53]	Huang G,Gao J,Wang X,et al.How can Graphene Reduce the Flammability of Polymer Nanocomposites?[J]. Mater Lett,2012,66(1):187-189.
[54]	Huang G,Chen S,Liang H,et al. Combination of Graphene and Montmorillonite Reduces the Flammability of Poly(vinyl alcohol) Nanocomposites[J]. Appl Clay Sci,2013,s80/81:433-437.
[55]	Huang G,Liang H,Wang Y,et al.Combination Effect of Melamine Polyphosphate and Graphene on Flame Retardant Properties of Poly(vinyl alcohol)[J]. Mater Chem Phys,2012,132(2/3):520-528.
[56]	Huang G,Yang J,Gao J,et al.Thin Films of Intumescent Flame Retardant-Polyacrylamide and Exfoliated Graphene Oxide Fabricated via Layer-by-Layer Assembly for Improving Flame Retardant Properties of Cotton Fabric[J]. Ind Eng Chem Res,2012,51(38):12355-12366.
[57]	Zuo L,Fan W,Zhang Y,et al.Graphene/Montmorillonite Hybrid Synergistically Reinforced Polyimide Composite Aerogels with Enhanced Flame-Retardant Performance[J]. Compos Sci Technol,2017,139:57-63.
[58]	Gedler G,Antunes M,Realinho V,et al.Thermal Stability of Polycarbonate-Graphene Nanocomposite Foams[J]. Polym Degrad Stabil,2012,97(8):1297-1304.
[59]	Kuila T,Khanra P,Mishra A,et al.Functionalized-Graphene/Ethylene Vinyl Acetate Co-Polymer Composites for Improved Mechanical and Thermal Properties[J]. Polym Test,2012,31(2):282-289.
[60]	Huang G,Chen S,Tang S,et al.A Novel Intumescent Flame Retardant-functionalized Graphene:Nanocomposite Synthesis, Characterization, and Flammability Properties[J]. Mater Chem Phys,2012,135(2/3):938-947.
[61]	Wang Z,Xu S,Wu L,et al.Flammability and Thermal Degradation of PMMA/Graphene Composites[J]. Adv Mater Res,2014,910:31-34.
[62]	Huang G,Chen S,Song P,et al. Combination effects of Graphene and Layered Double Hydroxides on Intumescent Flame-Retardant Poly(methyl methacrylate) Nanocomposites[J]. Appl Clay Sci,2014,88/89(3):78-85.
[63]	Wang X,Song L,Yang H,et al.Synergistic Effect of Graphene on Antidripping and Fire Resistance of Intumescent Flame Retardant Poly(butylene succinate) Composites[J]. Ind Eng Chem Res,2011,50(9):5376-5383.
[64]	Wang X,Hu Y,Song L,et al.Comparative Study on the Synergistic Effect of POSS and Graphene with Melamine Phosphate on the Flame Retardance of Poly(butylene succinate)[J]. Thermochim Acta,2012,543:156-164.
[65]	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.
[66]	Nine M,Tran D,Tung T,et al.Graphene-Borate as an Efficient Fire Retardant for Cellulosic Materials with Multiple and Synergetic Modes of Action[J]. ACS Appl Mater Interfaces,2017,9(11):10160-10168.