纳米二氧化硅表面接枝9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物以及对聚甲基丙烯酸甲酯复合材料阻燃性能和透明性的影响
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摘要
聚甲基丙烯酸甲酯(PMMA)是一种重要的透明高分子材料,但是PMMA的易燃性限制了其应用。本工作在纳米二氧化硅表面接枝含磷阻燃剂9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO),并用于聚甲基丙烯酸甲酯(PMMA)的改性。极限氧指数(LOI)、垂直燃烧(UL-94)和锥形量热(CCT)测试结果表明,制备的PMMA复合材料的阻燃性能大幅度提高,这主要归因于纳米粒子和含磷阻燃剂的协同阻燃作用,形成致密的炭保护层结构。同时,二氧化硅接枝DOPO的加入可以保持PMMA良好的透明性,这有利于材料在光学透明性要求较高的领域的应用。
Polymethyl methacrylate (PMMA) is one of important polymer materials with good transparency,but the poor flame retardancy of PMMA greatly limits its application. In this work,9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) was grafted onto the surface of silica nanoparticles that were employed to prepare PMMA nanocomposites. The results from limiting oxygen index (LOI),vertical burning (UL-94)and cone calorimeter test (CCT) indicate that the modified silica can effectively improve the flame retardancy of PMMA,which is mainly attributed to the synergistic effect between nanoparticles and phosphorous flame retardant to form compact protective carbon layer. Meanwhile,similar to pure PMMA,the as-prepared PMMA nanocomposites keep good transparency,which is positive to the wide applications of PMMA with high demand of optical transparency.
Polymethyl methacrylate (PMMA) is one of important polymer materials with good transparency,but the poor flame retardancy of PMMA greatly limits its application. In this work,9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) was grafted onto the surface of silica nanoparticles that were employed to prepare PMMA nanocomposites. The results from limiting oxygen index (LOI),vertical burning (UL-94)and cone calorimeter test (CCT) indicate that the modified silica can effectively improve the flame retardancy of PMMA,which is mainly attributed to the synergistic effect between nanoparticles and phosphorous flame retardant to form compact protective carbon layer. Meanwhile,similar to pure PMMA,the as-prepared PMMA nanocomposites keep good transparency,which is positive to the wide applications of PMMA with high demand of optical transparency.
引文
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[11]Yan W,Yu J,Zhang M Q,et al.Enhanced Flame Retardancy of Epoxy Resin Containing a Phenethyl-bridged DOPODerivative/Montmorillonite Compound[J].J Fire Sci,2018,36(1):47-62.
[12]Buczko A,Stelzig T,Bommer L,et al.Bridged DOPO Derivatives as Flame Retardants for PA6[J].Polym Degrad Stab,2014,107:158-165.
[13]Wen X,Lin Y,Han C Y,et al.Thermomechanical and Optical Properties of Biodegradable Poly(L-lactide)/Silica Nanocomposites by Melt Compounding[J].J Appl Polym Sci,2009,114(6):3379-3388.
[14]Qian X D,Pan H F,Yi X W,et al.Thermal Properties of Novel 9,10-Dihydro-9-oxa-10-phosphaphenanthrene 10-Oxidebased Organic/Inorganic Hybrid Materials Prepared by Sol-gel and UV-curing Processes[J].Ind Eng Chem Res,2011,51(1):85-94.
[15]Cao Y,Wang X L,Zhang W Q,et al.Bi-DOPO Structure Flame Retardants with or Without Reactive Group:Their Effects on Thermal Stability and Flammability of Unsaturated Polyester[J].Ind Eng Chem Res,2017,56(20):5913-5924.
[16]Yang H F,Ye L,Gong J,et al.Simultaneously Improving the Mechanical Properties and Flame Retardancy of Polypropylene Using Functionalized Carbon Nanotubes by Covalently Wrapping Flame Retardants Followed by Linking Polypropylene[J].Mater Chem Front,2017,1(4):716-726.
[2]WANG Miao.Study on the Preparation and Properties of Transparent Magnesium Hydroxide Nanodispersion and Its Nanocomposites[D].Beijing:Beijing University of Chemical Technology,2016(in Chinese).王淼.氢氧化镁透明分散体及其聚合物基阻燃材料的制备和性能研究[D].北京:北京化工大学,2016.
[3]JIANG Saihua.Design,Preparation and Property Studies of Novel Transparent Flame-retardant Polymethyl Methacrylate with Enhanced Thermal Property[D].Hefei:University of Science and Technology of China,2014(in Chinese).江赛华.新型透明阻燃耐热聚甲基丙烯酸甲酯材料的设计制备与性能研究[D].合肥:中国科学技术大学,2014.
[4]Zhu L Y,Su S,Hossenlopp J M.Thermal Stability and Fire Retardancy of PMMA(nano)Composites with Layered Metal Hydroxides Containing Dodecyl Sulfate Anions[J].Polym Adv Technol,2012,23(2):171-181.
[5]YUAN Xinqiang,JIANG Peng,ZHANG Yingtang.Investigation on Fire Retardant and Heat Insulation Performance of PMMA/Fly Ash/Mg(OH)2Composite[J].China Plast,2014,28(1):84-87(in Chinese).袁新强,蒋鹏,张营堂.PMMA/粉煤灰/Mg(OH)2复合材料的阻燃隔热性能研究[J].中国塑料,2014,28(1):84-87.
[6]Jiang S H,Yang H Y,Qian X D,et al.A Novel Transparent Cross-linked Poly(methyl methacrylate)-based Copolymer with Enhanced Mechanical,Thermal,and Flame-Retardant Properties[J].Ind Eng Chem Res,2014,53(10):3880-3887.
[7]Jiang S H,Zhu Y L,Hu Y,et al.In Situ Synthesis of a Novel Transparent Poly(methyl methacrylate)Resin with Markedly Enhanced Flame Retardancy[J].Polym Adv Technol,2016,27(2):266-272.
[8]Basuli U,Palaninathan E,Chaki T K,et al.Effect of Plasma,Gamma and Chemically Surface Modified MWNTs on the Rheological and Electrical Properties of Ethylene Methyl Acrylate(EMA)Nanocomposites[J].J Nanosci Nanotechnol,2018,18(7):4621-4633.
[9]Jahan Z,Niazi M B K,GregersenW.Mechanical,Thermal and Swelling Properties of Cellulose Nanocrystals/PVANanocomposites Membranes[J].J Ind Eng Chem,2018,57:113-124.
[10]Sakakibara K,Moriki Y,Yano H,et al.Strategy for the Improvement of the Mechanical Properties of Cellulose NanofiberReinforced High-Density Polyethylene Nanocomposites Using Diblock Copolymer Dispersants[J].ACS Appl Mater Interfaces,2017,9(50):44079-44087.
[11]Yan W,Yu J,Zhang M Q,et al.Enhanced Flame Retardancy of Epoxy Resin Containing a Phenethyl-bridged DOPODerivative/Montmorillonite Compound[J].J Fire Sci,2018,36(1):47-62.
[12]Buczko A,Stelzig T,Bommer L,et al.Bridged DOPO Derivatives as Flame Retardants for PA6[J].Polym Degrad Stab,2014,107:158-165.
[13]Wen X,Lin Y,Han C Y,et al.Thermomechanical and Optical Properties of Biodegradable Poly(L-lactide)/Silica Nanocomposites by Melt Compounding[J].J Appl Polym Sci,2009,114(6):3379-3388.
[14]Qian X D,Pan H F,Yi X W,et al.Thermal Properties of Novel 9,10-Dihydro-9-oxa-10-phosphaphenanthrene 10-Oxidebased Organic/Inorganic Hybrid Materials Prepared by Sol-gel and UV-curing Processes[J].Ind Eng Chem Res,2011,51(1):85-94.
[15]Cao Y,Wang X L,Zhang W Q,et al.Bi-DOPO Structure Flame Retardants with or Without Reactive Group:Their Effects on Thermal Stability and Flammability of Unsaturated Polyester[J].Ind Eng Chem Res,2017,56(20):5913-5924.
[16]Yang H F,Ye L,Gong J,et al.Simultaneously Improving the Mechanical Properties and Flame Retardancy of Polypropylene Using Functionalized Carbon Nanotubes by Covalently Wrapping Flame Retardants Followed by Linking Polypropylene[J].Mater Chem Front,2017,1(4):716-726.