复合抑熔滴剂对阻燃聚酯共混物燃烧性能的影响
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摘要
针对磷系阻燃聚酯存在耐熔滴差的问题,采用自制膨胀型阻燃剂(IFR)与聚四氟乙烯(PTFE)以不同的质量比配制成复合抑熔滴剂,将其与含磷阻燃聚酯(FRPET)切片通过熔融共混的方法制备阻燃抑熔滴聚酯共混物。借助差示扫描量热仪、热重分析仪、极限氧指数仪、水平燃烧测试仪、微型量热仪、锥形量热仪对共混物的热性能及阻燃性能进行表征。结果表明:当复合抑熔滴剂质量分数为15%,IFR和PTFE的质量比为1∶2时,二者的协同作用最为明显,熔滴的抑制作用也最显著;此时FRPET的极限氧指数从25%提高到30%,1 min内的熔滴数从46滴减少到21滴;700℃时的残炭量相对增加了68.8%,总燃烧释放热和总烟释放量都明显降低。
In view of the melt-dripping problem for phosphorus-containing flame retardant polyethylene terephthalate( FRPET) during combustion, combined anti-dripping additive was prepared via combination of intumescent flame retardants( IFR) and polytetrafluoroethylene( PTFE). Then combined anti-dripping additive were melt blended into phosphorous-containing flame retardant polyester( FRPET)to obtain modified polyester samples. The thermal properties and flame retardant properties were characterized by means of differential scanning calorimetry,thermogravimetry,limiting oxygen index,horizontal burning test,micro combustion calorimeter( MCC),cone calorimetry. The results show that FRPET with 15% of combined anti-dripping additive( mass ratio of IFR and PTFE is 1∶ 2) can achieve the optimal flame retardancy. Combined anti-dripping additive system has obvious synergistic effect between IFR and PTFE to improve the dripping resistance. The limiting oxygen index value increases to30% from 25% and the numbers of melt-drops fell to 21 from 46 in 1 min. The char residue at 700 ℃increases by 68. 8% compared with the control sample( FRPET). In addition,the total heat release and total smoke release decrease significantly according to the MCC and CONE tests.
In view of the melt-dripping problem for phosphorus-containing flame retardant polyethylene terephthalate( FRPET) during combustion, combined anti-dripping additive was prepared via combination of intumescent flame retardants( IFR) and polytetrafluoroethylene( PTFE). Then combined anti-dripping additive were melt blended into phosphorous-containing flame retardant polyester( FRPET)to obtain modified polyester samples. The thermal properties and flame retardant properties were characterized by means of differential scanning calorimetry,thermogravimetry,limiting oxygen index,horizontal burning test,micro combustion calorimeter( MCC),cone calorimetry. The results show that FRPET with 15% of combined anti-dripping additive( mass ratio of IFR and PTFE is 1∶ 2) can achieve the optimal flame retardancy. Combined anti-dripping additive system has obvious synergistic effect between IFR and PTFE to improve the dripping resistance. The limiting oxygen index value increases to30% from 25% and the numbers of melt-drops fell to 21 from 46 in 1 min. The char residue at 700 ℃increases by 68. 8% compared with the control sample( FRPET). In addition,the total heat release and total smoke release decrease significantly according to the MCC and CONE tests.
引文
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[4]唐林川.高分子材料阻燃技术的研究[J].新材料与新技术,2016,42(5):81-82.TANG Linchuan.Studies of polymer materials flame retardant technology[J].New Material and New Technology,2016,42(5):81-82.
[5]王新良.阻燃聚酯现状及发展趋势[J].聚酯工业,2012,25(5):5-7.WANG Xinliang.Current status and development trends of flame-retardant polyester[J].Polyester Industry,2012,25(5):5-7.
[6]汤朔,靳玉娟,钱立军.膨胀型阻燃剂的研究进展[J].中国塑料,2012,26(8):1-8.TANG Shuo,JIN Yujuan,QIAN Lijun.Study process of intumescent flame retardant[J].China Plastics,2012,26(8):1-8.
[7]汤存对,吕建平,膨胀阻燃PP的制备及其阻燃性能研究[J].塑料科技,2015,43(8):43-47.TANG Cundui,LJianping.Study on preparation and properties of intumescent flame retardant polypropylene materials[J].Plastics Science and Technology,2015,43(8):43-47.
[8]钱明球,潘晓娣.抗熔滴涤纶纤维的研究及应用[J].合成技术及应用,2013,28(4):21-24.QIAN Mingqiu,PAN Xiaodi.Research and application of the anti-dripping PET fiber[J].Synthetic Technology and Application,2013,28(4):21-24.
[9]HAMCIUC C,VLADBUBULAC T,PETREUS O,et al.Synthesis and characterization of new aromatic polyesters and poly(ester-imide)s containing phosphorous cyclic bulky groups[J].Polymer Bulletin,2008,60(5):657-664.
[10]CHEN W Y,YUAN S S,SHENG Y,et al.Effect of charring agent THEIC on flame retardant properties of polypropylene[J].Journal of Applied Polymer Science,2014,132(1),doi:10.1002/app.41214.
[11]陈雅君,毛小军.膨胀型阻燃聚丙烯中协同效应的研究进展[J],塑料工业,2014,42(4):1-6.CHEN Yajun,MAO Xiaojun.Recent advances study on the synergy effect of intumescent flame-retardant polypropylene[J].China Plastics Industry,2014,42(4):1-6.
[12]魏丽菲,朱志国,靳昕怡,等.基于三(2-羟乙基)异氰尿酸酯的膨胀型阻燃剂对聚合物燃烧性能的影响[J].纺织学报,2017,38(9):24-31.WEI Lifei,ZHU Zhiguo,JIN Xinyi,et al.Effects of THEIC-based intumescent flame retardants on polymers[J].Journal of Textile Research,2017,38(9):24-31.