含硫功能聚磷腈微纳米球的合成及其在环氧树脂阻燃中的应用
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摘要
以六氯环三磷腈(HCCP)、4,4’-二羟基二苯硫醚(TDP)为原料合成了一种环交联型的聚磷腈(PTP)微纳米球,并将其加入到环氧树脂(EP)中制备成PTP微纳米球/EP(PTP/EP)复合材料,研究其阻燃性能。采用FTIR和SEM对PTP微纳米球进行表征;TG分析考察PTP/EP复合材料的热稳定性;极限氧指数(LOI)和锥型量热分析(CONE)对PTP/EP复合材料进行阻燃性能测试。研究结果表明,PTP微纳米球具有不溶不熔的特性,粒径在500nm～3μm之间,且拥有优异的热稳定性和成炭性,起始热分解温度高达453.2℃,800℃残炭为74.3%。PTP微球的加入显著提高了EP的阻燃性能。当PTP微纳米球添加量仅为5wt%时,PTP/EP的热释放速率峰值降低了55.43%;LOI值从纯EP的25.6%提高到了30.4%。PTP微球的加入还提高了EP的力学性能。PTP微纳米球因其不溶不熔的特点在EP中充当增强剂,在受热燃烧时充当高效的阻燃剂。本研究为功能性阻燃剂的研发提供了新思路。
The cyclic crosslinking poly(cyclotriphosphazene-co-4,4'-thiobisphenol)(PTP)micro-nano spheres were synthesized using hexachlorocyclotriphosphazene(HCCP)and 4,4'-thiobisphenol(TDP)as raw materials.The obtained PTP spheres were applied in flame retarded epoxy resin(EP)to prepare PTP/EP composites.The PTP spheres were characterized by FTIR and SEM.The thermal stability of PTP/EP composites was investigated by TG,and the flame retardancy was carried out by limiting oxygen index test(LOI)and cone calorimetry(CONE)tests.The results show that the PTP spheres are neither soluble in any organic solvents nor meltable at high temperature.The sphere size is about 500 nm-3μm and possesses excellent thermal stability and charring ability.The initial decomposition temperature is as high as 453.2℃ and the char residue is 74.3% at 800℃.The addition of PTP spheres can significantly improve the flame retardancy of EP.The peak heat release rate(PHRR)of PTP/EP composite is reduced by 55.43%and the LOI value is increased from 25.6%to 30.4% when merely 5 wt% of PTP added.The addition of PTP microspheres also enhanced the mechanical strength of EP.The mechanical strength of PTP/EP composites is also improved with the incorporation of PTP spheres.The PTP spheres can act as a reinforcing agent at room temperature due to the insolubility and infusibility,and also acts as the flame retardant under combustion.The study provides a new ideas and methods for functional flame retardants.
The cyclic crosslinking poly(cyclotriphosphazene-co-4,4'-thiobisphenol)(PTP)micro-nano spheres were synthesized using hexachlorocyclotriphosphazene(HCCP)and 4,4'-thiobisphenol(TDP)as raw materials.The obtained PTP spheres were applied in flame retarded epoxy resin(EP)to prepare PTP/EP composites.The PTP spheres were characterized by FTIR and SEM.The thermal stability of PTP/EP composites was investigated by TG,and the flame retardancy was carried out by limiting oxygen index test(LOI)and cone calorimetry(CONE)tests.The results show that the PTP spheres are neither soluble in any organic solvents nor meltable at high temperature.The sphere size is about 500 nm-3μm and possesses excellent thermal stability and charring ability.The initial decomposition temperature is as high as 453.2℃ and the char residue is 74.3% at 800℃.The addition of PTP spheres can significantly improve the flame retardancy of EP.The peak heat release rate(PHRR)of PTP/EP composite is reduced by 55.43%and the LOI value is increased from 25.6%to 30.4% when merely 5 wt% of PTP added.The addition of PTP microspheres also enhanced the mechanical strength of EP.The mechanical strength of PTP/EP composites is also improved with the incorporation of PTP spheres.The PTP spheres can act as a reinforcing agent at room temperature due to the insolubility and infusibility,and also acts as the flame retardant under combustion.The study provides a new ideas and methods for functional flame retardants.
引文
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[3]MARIAPPAN T AND WILKIE C A.Flame retardant epoxy resin for electrical and electronic applications[J].Fire and Materials,2014,38(5):588-598.
[4]TAN Y,SHAO Z B,CHEN X F,et al.Novel multifunctional organic inorganic hybrid curing agent with high flameretardant efficiency for epoxy resin[J].ACS Applied Materials&Interfaces,2015,7(32):17919-17928.
[5]卢林刚,陈英辉,赵瑾,等.DOPOMPC-APP-MWCNTs协同阻燃环氧树脂的制备[J].复合材料学报,2015,32(1):101-107.LU L G,CHEN Y H,ZHAO J,et al.Preparation of DO-POMPC-APP-MWCNTs intumescent flame-retardant epoxy resin[J].Acta Materiae Compositae Sinica,2015,32(1):101-107(in Chinese).
[6]袁小亚.纳米膨胀阻燃季戊四醇二磷酸酯双磷酰蜜胺-有机改性蒙脱土/聚乳酸复合材料的制备及阻燃性能[J].复合材料学报,2012,29(3):36-41.YUAN X Y.Preparation and intumescently flame-retardant properties of spirocyclic pentaerythritol bisphosphorate disphosphoryl melamine organomodified montmorillonite/polylactide nanocomposite[J].Acta Materiae Compositae Sinica,2012,29(3):36-41(in Chinese).
[7]CARJA I D,SERBEZEANU D,VLAD-BUBULAC T,et al.A straightforward,eco-friendly and cost-effective approach towards flame retardant epoxy resins[J].Journal of Materials Chemistry A,2014,2(38):16230-16241.
[8]TANG S,WACHTENDORF V,KLACK P,et al.Enhanced flame-retardant effect of a montmorillonite/phosphaphenanthrene compound in an epoxy thermoset[J].RSCAdvances,2017,7(2):720-728.
[9]ZHAO X M,XIAO D,ALONSO J P,et al.Inclusion complex between beta-cyclodextrin and phenylphosphonicdiamide as novel bio-based flame retardant to epoxy:Inclusion behavior,characterization and flammability[J].Materials&Design,2017,114:623-632.
[10]MA C,YU B,HONG N N,et al.Facile synthesis of a highly efficient,halogen-free,and intumescent flame retardant for epoxy resins:thermal properties,combustion behaviors,and flame-retardant mechanisms[J].Industrial&Engineering Chemistry Research,2016,55(41):10868-10879.
[11]HUANG Y W,SONG S Q,YANG Y,et al.Decomposable double-walled hybrid nanorods:formation mechanism and their effect on flame retardancy of epoxy resin composites[J].Journal of Materials Chemistry A,2015,3(31):15935-15943.
[12]QIU S L,XING W Y,FENG X M,et al.Self-standing cuprous oxide nanoparticles on silica@polyphosphazene nanospheres:3Dnanostructure for enhancing the flame retardancy and toxic effluents elimination of epoxy resins via synergistic catalytic effect[J].Chemical Engineering Journal,2017,309:802-814.
[13]魏振杰,刘伟区,李宏,等.含磷有机硅杂化环氧树脂固化体系性能研究[J].高分子学报,2012(2):148-153.WEI Z J,LIU W Q,LI H J,et al.Properties of phosphoruscontaining organic silicon/epoxy hybrid resin[J].Acta Polymerica Sinica,2012(2):148-153(in Chinese).
[14]YANG S,ZHANG Q X,HU Y F.Synthesis of a novel flame retardant containing phosphorus,nitrogen and boron and its application in flame-retardant epoxy resin[J].Polymer Degradation and Stability,2016,133:358-366.
[15]JIAN R,WANG P,DUAN W,et al.Synthesis of a novel P/N/S-containing flame retardant and its application in epoxy resin:Thermal property,flame retardance,and pyrolysis behavior[J].Industrial&Engineering Chemistry Research,2016,55(44):11520-11527.
[16]QIU S L,XING W Y,MU X W,et al.A 3Dnanostructure based on transition-metal phosphide decorated heteroatomdoped mesoporous nanospheres interconnected with graphene:Synthesis and applications[J].ACS Applied Materials&Interfaces,2016,8(47):32528-32540.
[17]YANG S,WANG J,HUO S Q,et al.Synthesis of a phosphorus/nitrogen-containing compound based on maleimide and cyclotriphosphazene and its flame-retardant mechanism on epoxy resin[J].Polymer Degradation and Stability,2016,126:9-16.
[18]ZHAO B,LIANG W J,WANG J S,et al.Synthesis of a novel bridged-cyclotriphosphazene flame retardant and its application in epoxy resin[J].Polymer Degradation and Stability,2016,133:162-173.
[19]国家技术监督局.塑料燃烧性能试验方法氧指数法:GB/T2406-1993[S].北京:中国标准出版社,1994.State Bureau of Technical Supervision.Plastics-Determination of fammability by oxygen index:GB/T 2406-1993[J].Beijing:China Standards Press,1994(in Chinese).
[20]ASTM International.Standard test method for tensile properties of plastics:ASTM D638-14[S].West Conshohocken:ASTM International,2014.