含硅环三磷腈衍生物阻燃改性聚碳酸酯的性能
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摘要
将聚碳酸酯(PC)、滑石粉(Talc)、聚四氟乙烯(PTFE)及自制的含硅环三磷腈衍生物阻燃剂(HSPCTP)在密炼机上熔融共混,经模压制备HSPCTP阻燃PC/Talc/PTFE复合材料。通过垂直燃烧测试和极限氧指数(LOI)测试分析了复合材料的阻燃性能,采用热重分析、动态热机械分析、拉伸和冲击试验研究了阻燃剂含量对复合材料热稳定性、储能模量及玻璃化转变温度(T_g)和力学性能的影响。结果表明,HSPCTP的加入能够促进PC的热解,使其更早地产生炭层,有效提高复合材料的阻燃性能,当添加3份HSPCTP时,复合材料的LOI值达到28.4%并可以通过UL 94 V–0等级测试,断裂伸长率和冲击强度分别比纯PC提高了174%和135%,而此时的拉伸强度与纯PC相差不大。HSPCTP提高了低于T_g时的复合材料储能模量,但略微降低了复合材料的T_g。
The melt blending of polycarbonate(PC), talcum powder(Talc),polytetrafluoroethylene(PTFE) and siliconcontaining cyclotriphosphazene derivative ?ame retardant(HSPCTP) were done by internal mixer,the PC/Talc/PTFE composites?ame-retarded by HSPCTP were prepared by compression molding. The ?ame retardancy of the composite was analyzed by vertical burning performance and limiting oxygen index(LOI) test. The effects of HSPCTP content on the thermal stability,storage modulus,glass transition temperature(T_g) and mechanical properties of the composites were investigated by thermogravimetric analysis,dynamic thermomechanical analysis,tensile and impact test. The results show that,the incorporation of HSPCTP promotes the thermal decomposition of PC and lets the carbon layer form earlier,which improves the ?ame retardancy of the composite effectively.When the content of HSPCTP is 3 phr,the LOI value of the composite is up to 28.4% and the sample passes UL 94 V–0 test,compared with pure PC,the elongation at break and impact strength are increased by 174% and 135% respectively,the tensile strength has little difference. The addition of HSPCTP enhances the storage modulus of the composite below T_g,but reduces T_g of the composite slightly.
The melt blending of polycarbonate(PC), talcum powder(Talc),polytetrafluoroethylene(PTFE) and siliconcontaining cyclotriphosphazene derivative ?ame retardant(HSPCTP) were done by internal mixer,the PC/Talc/PTFE composites?ame-retarded by HSPCTP were prepared by compression molding. The ?ame retardancy of the composite was analyzed by vertical burning performance and limiting oxygen index(LOI) test. The effects of HSPCTP content on the thermal stability,storage modulus,glass transition temperature(T_g) and mechanical properties of the composites were investigated by thermogravimetric analysis,dynamic thermomechanical analysis,tensile and impact test. The results show that,the incorporation of HSPCTP promotes the thermal decomposition of PC and lets the carbon layer form earlier,which improves the ?ame retardancy of the composite effectively.When the content of HSPCTP is 3 phr,the LOI value of the composite is up to 28.4% and the sample passes UL 94 V–0 test,compared with pure PC,the elongation at break and impact strength are increased by 174% and 135% respectively,the tensile strength has little difference. The addition of HSPCTP enhances the storage modulus of the composite below T_g,but reduces T_g of the composite slightly.
引文
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[4]Yuan Dandan,Yin Haiqing,Cai Xufu.Effect of a novel flame retardant containing silicon and nitrogen on the thermal stability and flame retardancy of polycarbonate[J].Journal of Thermal Analysis&Calorimetry,2013,111(2):1 531-1 537.
[5]Xu Miaojun,Ma Kun,Jiang Dawei,et al.Hexa-[4-(glycidyloxycarbonyl)phenoxy]cyclotriphosphazene chain extender for preparing high-performance flame retardant polyamide 6 composites[J].Polymer,2018,146(1):63-72.
[6]苏兴勇,汪娇宁,毛志平.改性六氯环三聚磷腈在聚酯中的阻燃性能研究[J].工程塑料应用,2014,42(3):94-98.Su Xingyong,Wang Jiaoning,Mao Zhiping.Modified cyclotriphosphazene and its application as a flame retardant for polyester[J].Engineering Plastics Application,2014,42(3):94-98.
[7]游歌云,程之泉,彭浩,等.环三磷腈类阻燃剂的合成及应用研究进展[J].应用化学,2014,31(9):993-1 009.You Geyun,Cheng Zhiquan,Peng Hao,et al.Research progress on synthesis and application of cyclotriphosphazene-based flame retardants[J].Chinese Journal of Applied Chemistry,2014,31(9):993-1 009.
[8]Dong Meili,Wu Baolin,Xu Shidong,et al.Synergistic effect of hexaphenoxycyclotriphosphazene and aluminium tri-hydroxide on flame retardancy and smoke suppression of epoxy resin[J].Australian Journal of Chemistry,2018,71(5):325-333.
[9]Huang Tao,Zheng Xiangzhen,Fang Guihuang,et al.(4-methoxy)-phenoxy pentafluorocyclotriphosphazene as a novel flame retardant and overcharge protection additive for lithium-ion batteries[J].Rsc Advances,2017,7(75):47 775-47 780.
[10]Xu Guangrui,Xu Miaojun,Li Bin.Synthesis and characterization of a novel epoxy resin based on cyclotriphosphazene and its thermal degradation and flammability performance[J].Polymer Degradation&Stability,2014,109(109):240-248.
[11]单佳丽,宋荣君,李斌.一种新型含硅阻燃剂的制备及在聚碳酸酯中的应用研究[J].塑料科技,2016,44(4):90-94.Shan Jiali,Song Rongjun,Li Bin.Study on preparation of a novel silicon-containing flame retardant and its application in polycarbonate[J].Plastics Science and Technology,2016,44(4):90-94.
[12]Chen Yajun,Wang Wei,Liu Zhiqi,et al.Synthesis of a novel flame retardant containing phosphazene and triazine groups and its enhanced charring effect in poly(lactic acid)resin[J].Journal of Applied Polymer Science,2017,134(13).doi.org/10.1002/app.44660.
[13]Zhou Lisheng,Zhang Guangcheng,Li Jiantong,et al.The flame retardancy and thermal stability properties of flame-retarded epoxy resins based onα-hydroxyphosphonate cyclotriphosphazene[J].Journal of Thermal Analysis&Calorimetry,2017,129(11):1-12.
[14]Cao Xilei,Yang Yunyun,Luo Hang,et al.High efficiency intumescent flame retardancy between hexakis(4-nitrophenoxy)cyclotriphosphazene and ammonium polyphosphate on ABS[J].Polymer Degradation and Stability,2017,143:259-265.