季戊四醇磷酸酯/二乙基次磷酸锌协同阻燃聚酰胺6的制备及其性能
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摘要
为提高聚酰胺6(PA6)纤维的阻燃性及可纺性,设计了季戊四醇磷酸酯(PEPA)/二乙基次磷酸锌(ZDP)协同阻燃体系,采用熔融挤出方法制备了PA6/PEPA/ZDP阻燃复合物,研究了不同质量分数的阻燃剂对PA6阻燃性的影响规律,以及最优阻燃配比时的纺丝工艺及纤维性能。结果表明:PEPA可降低PA6的热稳定性,但ZDP可提高复合物的热稳定性,二者同时使用可起到互补作用;当PEPA与ZDP的质量比为10∶5时,复合物的极限氧指数达到28%,垂直燃烧测试的有焰燃烧时间明显缩短,锥形量热残炭量增加了6.56%,总热释放量降低了34.5%,此配比下复合物具有优良可纺性;将初生丝经3倍牵伸热定型后,其断裂强度为1.34 c N/dtex,断裂伸长率为33.99%。
In order to improve the flame retardance and spinnability of polyamide 6( PA6) fibers,a synergetic flame-retardant system of pentaerythritol phosphate( PEPA)/zinc diethyl phosphate( ZDP) was designed. Flame retardant polyamide 6( PA6)/PEPA/ZDP composites were prepared by a melt blending method in a twin-screw extruder. The influences of different flame retardant components on the flame retardancy and the spinning process and properties of the optimal flame retardant ratio were studied by scanning electron microscopy,differential scanning calorimetry,thermo gravimetry,cone calorimetry,limit oxygen index( LOI) and UL-94 rating. The results indicate that PEPA can decrease the thermal stability of PA6,but ZDP can improve the thermal stability of the composites,which can be complementary with each other. When the mass ratio of PEPA and ZDP is 10∶ 5 in PA6,the value of LOI reaches 28%,and the flame burning time of the UL-94 is reduced obviously. The residual carbon amount of cone calorimetry increases by 6. 56%,and the value of total heat release decreases by 34. 5%. It is found that the composites have excellent spinnability. The breaking strength is 1. 34 c N/dtex and the as-spun fibers elongation at break is 33. 99% after as-spun fibers are subjected to hot stretching by three times.
In order to improve the flame retardance and spinnability of polyamide 6( PA6) fibers,a synergetic flame-retardant system of pentaerythritol phosphate( PEPA)/zinc diethyl phosphate( ZDP) was designed. Flame retardant polyamide 6( PA6)/PEPA/ZDP composites were prepared by a melt blending method in a twin-screw extruder. The influences of different flame retardant components on the flame retardancy and the spinning process and properties of the optimal flame retardant ratio were studied by scanning electron microscopy,differential scanning calorimetry,thermo gravimetry,cone calorimetry,limit oxygen index( LOI) and UL-94 rating. The results indicate that PEPA can decrease the thermal stability of PA6,but ZDP can improve the thermal stability of the composites,which can be complementary with each other. When the mass ratio of PEPA and ZDP is 10∶ 5 in PA6,the value of LOI reaches 28%,and the flame burning time of the UL-94 is reduced obviously. The residual carbon amount of cone calorimetry increases by 6. 56%,and the value of total heat release decreases by 34. 5%. It is found that the composites have excellent spinnability. The breaking strength is 1. 34 c N/dtex and the as-spun fibers elongation at break is 33. 99% after as-spun fibers are subjected to hot stretching by three times.
引文
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[2]王学利,李光,彭治汉,等.磷系阻燃剂在PA6树脂和纤维中应用及阻燃机理研究[J].纺织导报,2008(8):50-54.WANG Xueli,LI Guang,PENG Zhihan,et al.Study on application and flame retardant mechanism of phosphorus-based flame retardant on PA6 resin and fiber[J].China Textile Leader,2008(8):50-54.
[3]PRICE D,PYRAH K,HULL T R,et al.Flame retarding poly(methyl methacrylate)with phosphorus-containing compounds:comparison of an additive with a reactive approach[J].Polymer Degradation&Stability,2001,74(3):441-447.
[4]FANG K Y,KE C C.Synergistic effect between a novel hyperbranched flame retardant and melamine pyrophosphate on the char forming of polyamide 6[J].Polymer-Plastics Technology and Engineering,2010,49(14):1489-1497.
[5]李昕,欧育湘.双环笼状磷酸酯阻燃环氧树脂的燃烧行为研究[J].北京理工大学学报,2001(3):388-391.LI Xin,OU Yuxiang.Combustion behavior of epoxy resin flame retarded with caged bicyclic phosphate[J].Journal of Beijing Institute of Technology,2001,21(3):388-391.
[6]祝焕,何文涛,于杰,等.有机次膦酸铝复配型阻燃剂/MMT协同阻燃LGFPA6的阻燃性能[J].塑料,2014,43(6):1-4.ZHU Huan,HE Wentao,YU Jie,et al.Flame retardancy of LGFPA6 synergistic flame retarded by novel organophosphinate complex flame retardant/MMT[J].Plastics,2014,43(6):1-4.
[7]王卫明,章震.二乙基次磷酸盐的发展以及应用[J].浙江化工,2015(9):39-42.WANG Weiming,ZHANG Zhen.Synthesis and optical properties of a new BODIPY-based fluorescent dye[J].Zhejiang Chemical Industry,2015(9):39-42.
[8]司明明,丁率,郝建薇,等.纳米Sb2O3与次膦酸铝阻燃聚对苯二甲酸乙二醇酯协同作用研究[J].高分子学报,2013(12):1483-1491.SI Mingming,DING Shuai,HAO Jianwei,et al.Syergistic effect of nano-Sb2O3and aluminium phosphinate on flame retardancy of PET[J].Acta Polymerica Sinica,2013(12):1483-1491.
[9]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.Influence of tris(2-hydroxyethyl)isocyanurate-based intumescent flame retardants on combustion performance of polymers[J].Journal of Textile Research,2017,38(9):24-31.
[10]朱德振,刘可,李圆圆,等.ZDP与EPT/ATO协同阻燃PA6的性能[J].工程塑料应用,2016,44(12):8-13.ZHU Dezhen,LIU Ke,LI Yuanyuan,et al.Properties of PA6 synergistic flame retarded by ZDP combined with EPT/ATO[J].Engineering Plastics Application,2016.44(12):8-13.
[11]张玉梅.聚酯熔体直纺超细旦长丝POY可纺性研究[D].天津:天津大学,2012:8.ZHANG Yumei.Study on spinnability of polyethylene terephthalate microfilaments pre-oriented yarn by direct melt spinning[D].Tianjin:Tianjin University,2012:8.
[12]杨旭俭,王学晨,崔河,等.EVA/PP共混物皮芯复合中空纤维的熔融纺丝工艺[J].天津工业大学学报,2007,26(1):15-19.YANG Xujian,WANG Xuechen,CUI He,et al.Meltspinning of hollow sheath-core composite fibers of EVA/PP blend[J].Journal of Tianjin University,2007,26(1):15-19.
[13]蔡晓霞.乙烯-醋酸乙烯酯共聚物的膨胀阻燃体系研究[D].成都:四川大学,2007:57.CAI Xiaoxia.Flame-retardation of poly(ethylene-covinylacetate)via intumescent flame retardants[D].Chengdu:Sichuan University,2007:57.
[14]张雄,占珊,韩克清,等.超支化聚合物对尼龙6结晶及力学性能的影响[J].东华大学学报(自然科学版),2008,34(1):15-19.ZHANG Xiong,ZHAN Shan,HAN Keqing et al.The effect of hyperbranched polymers on the crystalline and mechanical properties of nylon 6[J].Journal of Donghua University(Nature Science Edition),2008,34(1):15-19.