六苯氧基环三磷腈阻燃PC/ABS合金及其高性能化研究
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摘要
采用熔融挤出法制备了阻燃聚碳酸酯/丙烯腈-丁二烯-苯乙烯共聚物(PC/ABS)合金材料。利用热失重分析仪、氧指数测试仪、垂直燃烧仪、锥形量热仪、电子万能试验机和冲击试验机研究了相容剂马来酸酐接枝聚乙烯共聚物(PE-g-MAH)以及阻燃剂六苯氧基环三磷腈(HPCTP)的加入对PC/ABS合金材料的热稳定性、阻燃性能和力学性能的影响,并采用扫描电子显微镜对材料的残炭形貌进行分析。结果表明,当PC/ABS的质量比为7/3,以PE-g-MAH为相容剂,且HPCTP添加量为15%时,阻燃PC/ABS合金材料的综合性能最好,其极限氧指数为26.4%,热释放速率峰值及热释放总量达到最小值,且能够达到UL 94V-0级,拉伸强度和缺口冲击强度分别为55MPa和32.9kJ/m~2。
The flame-retardantcompounds based on polycarbonate(PC)/acrylonitrile-butadienestyrene copolymer(ABS)alloys and hexaphenoxycyclotriphosphazene(HPCTP)were prepared by a melt extrusion method,and the effects of polyethylene grafted maleic anhydride(PE-g-MAH)and HPCTP on the thermal stability,flame-retardant performance and mechanical properties of PC/ABS alloys were investigated by thermogravimetric analysis,limited oxygen index(LOI),vertical burning experiment,cone calorimeter test,electronic universal testing machine and impact testing machine.Furthermore,the morphology of residual char was analyzed by scanning electron microscopy after combustion of PC/ABS alloys,and the relevant flame-retardant mechanisms were discussed.The results indicated that the flame retardant PC/ABS alloys achieved the optimum comprehensive properties by using PE-g-MAH as a compatibilizer when the mass ratio of PC/ABS was set to 7/3 and the content of HPCTP set as 15 wt%.In this case,the PC/ABS alloy obtained an LOI of 26.4 vol%.Furthermore,the PC/ABS alloys achieved the minimum values in heat release rate and total heat release as well as a V-0 classification in the vertical burning experiment.The alloys also gained the tensile strength of 55 MPa and the notched impact strength of 32.9 kJ/m~2.
The flame-retardantcompounds based on polycarbonate(PC)/acrylonitrile-butadienestyrene copolymer(ABS)alloys and hexaphenoxycyclotriphosphazene(HPCTP)were prepared by a melt extrusion method,and the effects of polyethylene grafted maleic anhydride(PE-g-MAH)and HPCTP on the thermal stability,flame-retardant performance and mechanical properties of PC/ABS alloys were investigated by thermogravimetric analysis,limited oxygen index(LOI),vertical burning experiment,cone calorimeter test,electronic universal testing machine and impact testing machine.Furthermore,the morphology of residual char was analyzed by scanning electron microscopy after combustion of PC/ABS alloys,and the relevant flame-retardant mechanisms were discussed.The results indicated that the flame retardant PC/ABS alloys achieved the optimum comprehensive properties by using PE-g-MAH as a compatibilizer when the mass ratio of PC/ABS was set to 7/3 and the content of HPCTP set as 15 wt%.In this case,the PC/ABS alloy obtained an LOI of 26.4 vol%.Furthermore,the PC/ABS alloys achieved the minimum values in heat release rate and total heat release as well as a V-0 classification in the vertical burning experiment.The alloys also gained the tensile strength of 55 MPa and the notched impact strength of 32.9 kJ/m~2.
引文
[1]WANG W H,ZHAO G Q,GUAN Y J,et al.Study on Effects of Short Glass Fiber Reinforcement on the Mechanical and Thermal Properties of PC/ABS Composites[J].Journal of Applied Polymer Science,2014,131(17):40 697.
[2]ZHANG B B,CHEN Y,WANG F,et al.Surface Modification of Carbon Black for the Reinforcement of Polycarbonate/Acrylonitrile-butadiene-styrene Blends[J].Applied Surface Science,2015,351:280-288.
[3]WEI P,TIAN G H,YU H Z,et al.Synthesis of a Novel Organic-inorganic Hybrid Mesoporous Silica and Its Flame Retardancy Application in PC/ABS[J].Polymer Degradation and Stability,2013,98(5):1 022-1 029.
[4]JIAN R K,CHEN L,HU Z,et al.Flame-retardant Polycarbonate/Acrylonitrile-butadiene-styrene Based on Red Phosphorus Encapsulated by Polysiloxane:Flame Retardance,Thermal Stability,and Water Resistance[J].Journal of Applied Polymer Science,2012,123(5):2 867-2 874.
[5]LEVCHIK S V,WEIL E D.Overview of Recent Developments in the Flame Retardancy of Polycarbonates[J].Polymer International,2005,54(7):981-998.
[6]ZHANG W C,LI X M,YANG R J.Flame Retardancy Mechanisms of Phosphorus-containing Polyhedral Oligomeric Silsesquioxane(DOPO-POSS)in Polycarbonate/Acrylonitrile-butadiene-Styrene Blends[J].Polymers for Advanced Technologies,2012,23(3):588-595.
[7]欧育湘.阻燃剂[M].北京:兵器工业出版社,1997:26-30.
[8]彭华乔,夏祖西,于新华,等.无卤阻燃PC及PC/ABS合金研究进展[J].工程塑料应用,2008,36(8):75-78.PENG H Q,XIA Z X,YU X H,et al.Development of Halogen-free Flame-retardant PC and PC/ABS[J].Engineering Plastics Application,2008,36(8):75-78.
[9]POUR R H,SOHEILMOGHADDAM M,HASSAN A,et al.Flammability and Thermal Properties of Polycarbonate/Acrylonitrile-butadiene-styrene Nanocomposites Reinforced with Multilayer Graphene[J].Polymer Degradation and Stability,2015,120:88-97.
[10]高烽,韦平,李林科,等.硅系阻燃剂阻燃PC及PC/ABS复合材料研究进[J].工程塑料应用,2013,41(5):103-106.GAO F,WEI P,LI L K,et al.ResearchProgress of Silicone-containing Flame Retardant in PC and PC/ABSComposites[J].Engineering Plastics Application,2013,41(5):103-106.
[11]王伟,钱立军,陈雅君.磷腈化合物阻燃高分子材料研究进展[J].中国科学:化学,2016,46(8):723-731.WANG W,QIAN L J,CHEN Y J.Recent Advances in Application of Phosphazenes for Flame Retardant Polymer Materials[J].Scientia Sinica(Chimica),2016,46(8):723-731.
[12]徐建中,杜卫义,王春征,等.六苯氧基环三磷腈阻燃PC/ABS合金及其热解研究[J].中国塑料,2011,25(12):21-25.XU J Z,DU,W Y,WANG C Z,et al.Flame Retardancy and Thermal Decomposition of Polycarbonate/Acrylonitrile-butadiene-styrene/Hexaphenoxycyclotriphosphazene[J].China Plastics,2011,25(12):21-25.
[13]BREHME S,SCHARTEL B,GOEBBELS J,et al.Phosphorus Polyester Versus Aluminium Phosphinate in Poly(butylene terephthalate)(PBT):Flame Retardancy Performance and Mechanisms[J].Polymer Degradation and Stability,2011,96(5):875-884.
[14]WANG J Y,QIAN J J,XU B,et al.Synthesis and Characterization of Aluminum Poly-hexamethylenephosphinate and Its Flame-retardant Application in Epoxy Resin[J].Polymer Degradation and Stability,2015,122:8-17.
[15]徐路,李学,苏倩,等.六苯氧基环三磷腈对PC/ABS合金的阻燃作用[J].天津化工,2014,28(2):15-19.XU L,LI X,SU Q,et al.FlameRetardancy of Hexaphenoxycyclotriphosphazene in PC/ABS Alloy[J].Tianjin Chemical Industry,2014,28(2):15-19.
[16]成国亮,柯杨,赵静,等.苯氧基磷腈的组成对其阻燃PC/ABS的影响[J].化工科技,2016,24(1):1-6.CHENG G L,KE Y,ZHAO J,et al.Effect of Composition of Phenoxyphosphazene on Its Flame Retardancy in PC/ABS[J].Science and Technology in Chemical Industry,2016,24(1):1-6.
[17]赫妮娜,刘俊龙.相容剂及其在PC/ABS合金中的应用[J].塑料科技,2007,35(5):70-75.HE N N,LIU J L.Application of Compatibilizers in PC/ABS Alloy[J].Plastics Science and Technology,2007,35(5):70-75.
[18]唐颂超,蒋丽霞,周达飞.PC/ABS及PC/ABS/PE-gMAH共混体系相容性的研究[J].功能高分子学报,2000,13(1):24-28.TANG S C,JIANG L X,ZHOU D F.Comatibility of PC/ABS and PC/ABS/PE-g-MAH Blends[J].Journal of Functional Polymers,2000,13(1):24-28.
[2]ZHANG B B,CHEN Y,WANG F,et al.Surface Modification of Carbon Black for the Reinforcement of Polycarbonate/Acrylonitrile-butadiene-styrene Blends[J].Applied Surface Science,2015,351:280-288.
[3]WEI P,TIAN G H,YU H Z,et al.Synthesis of a Novel Organic-inorganic Hybrid Mesoporous Silica and Its Flame Retardancy Application in PC/ABS[J].Polymer Degradation and Stability,2013,98(5):1 022-1 029.
[4]JIAN R K,CHEN L,HU Z,et al.Flame-retardant Polycarbonate/Acrylonitrile-butadiene-styrene Based on Red Phosphorus Encapsulated by Polysiloxane:Flame Retardance,Thermal Stability,and Water Resistance[J].Journal of Applied Polymer Science,2012,123(5):2 867-2 874.
[5]LEVCHIK S V,WEIL E D.Overview of Recent Developments in the Flame Retardancy of Polycarbonates[J].Polymer International,2005,54(7):981-998.
[6]ZHANG W C,LI X M,YANG R J.Flame Retardancy Mechanisms of Phosphorus-containing Polyhedral Oligomeric Silsesquioxane(DOPO-POSS)in Polycarbonate/Acrylonitrile-butadiene-Styrene Blends[J].Polymers for Advanced Technologies,2012,23(3):588-595.
[7]欧育湘.阻燃剂[M].北京:兵器工业出版社,1997:26-30.
[8]彭华乔,夏祖西,于新华,等.无卤阻燃PC及PC/ABS合金研究进展[J].工程塑料应用,2008,36(8):75-78.PENG H Q,XIA Z X,YU X H,et al.Development of Halogen-free Flame-retardant PC and PC/ABS[J].Engineering Plastics Application,2008,36(8):75-78.
[9]POUR R H,SOHEILMOGHADDAM M,HASSAN A,et al.Flammability and Thermal Properties of Polycarbonate/Acrylonitrile-butadiene-styrene Nanocomposites Reinforced with Multilayer Graphene[J].Polymer Degradation and Stability,2015,120:88-97.
[10]高烽,韦平,李林科,等.硅系阻燃剂阻燃PC及PC/ABS复合材料研究进[J].工程塑料应用,2013,41(5):103-106.GAO F,WEI P,LI L K,et al.ResearchProgress of Silicone-containing Flame Retardant in PC and PC/ABSComposites[J].Engineering Plastics Application,2013,41(5):103-106.
[11]王伟,钱立军,陈雅君.磷腈化合物阻燃高分子材料研究进展[J].中国科学:化学,2016,46(8):723-731.WANG W,QIAN L J,CHEN Y J.Recent Advances in Application of Phosphazenes for Flame Retardant Polymer Materials[J].Scientia Sinica(Chimica),2016,46(8):723-731.
[12]徐建中,杜卫义,王春征,等.六苯氧基环三磷腈阻燃PC/ABS合金及其热解研究[J].中国塑料,2011,25(12):21-25.XU J Z,DU,W Y,WANG C Z,et al.Flame Retardancy and Thermal Decomposition of Polycarbonate/Acrylonitrile-butadiene-styrene/Hexaphenoxycyclotriphosphazene[J].China Plastics,2011,25(12):21-25.
[13]BREHME S,SCHARTEL B,GOEBBELS J,et al.Phosphorus Polyester Versus Aluminium Phosphinate in Poly(butylene terephthalate)(PBT):Flame Retardancy Performance and Mechanisms[J].Polymer Degradation and Stability,2011,96(5):875-884.
[14]WANG J Y,QIAN J J,XU B,et al.Synthesis and Characterization of Aluminum Poly-hexamethylenephosphinate and Its Flame-retardant Application in Epoxy Resin[J].Polymer Degradation and Stability,2015,122:8-17.
[15]徐路,李学,苏倩,等.六苯氧基环三磷腈对PC/ABS合金的阻燃作用[J].天津化工,2014,28(2):15-19.XU L,LI X,SU Q,et al.FlameRetardancy of Hexaphenoxycyclotriphosphazene in PC/ABS Alloy[J].Tianjin Chemical Industry,2014,28(2):15-19.
[16]成国亮,柯杨,赵静,等.苯氧基磷腈的组成对其阻燃PC/ABS的影响[J].化工科技,2016,24(1):1-6.CHENG G L,KE Y,ZHAO J,et al.Effect of Composition of Phenoxyphosphazene on Its Flame Retardancy in PC/ABS[J].Science and Technology in Chemical Industry,2016,24(1):1-6.
[17]赫妮娜,刘俊龙.相容剂及其在PC/ABS合金中的应用[J].塑料科技,2007,35(5):70-75.HE N N,LIU J L.Application of Compatibilizers in PC/ABS Alloy[J].Plastics Science and Technology,2007,35(5):70-75.
[18]唐颂超,蒋丽霞,周达飞.PC/ABS及PC/ABS/PE-gMAH共混体系相容性的研究[J].功能高分子学报,2000,13(1):24-28.TANG S C,JIANG L X,ZHOU D F.Comatibility of PC/ABS and PC/ABS/PE-g-MAH Blends[J].Journal of Functional Polymers,2000,13(1):24-28.