聚磷酸酯阻燃剂对PC/ABS合金阻燃性能影响
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摘要
以聚苯氧基磷酸-2-10-氢-9-氧杂-磷杂菲基对苯二酚酯(POPP)为阻燃剂,对PC/ABS合金进行阻燃改性。通过极限氧指数(LOI)测试、垂直燃烧(UL-94)测试、热重分析(TGA)测试、锥形量热(CONE)测试和扫描电镜(SEM)测试等表征方法研究其阻燃性能。结果表明,当阻燃剂添加量为15%时可以达到UL94 V-0级,LOI值为21.1%;最大热释放速率(Pk-HRR)下降41.7%,热释放总量(THR)下降31.1%;TGA和SEM分析显示改性PC/ABS合金具有更好的成炭效果,燃烧后能促进表面生成致密多孔炭层,有效的隔绝氧气提高材料的阻燃性能。
A novel flame retardant, poly(2-10-hydrogen-9-oxa-phosphaphenanthrene hydroquinone phenyl phosphate)(POPP), was incorporated to PC/ABS to improve the flame retardancy of PC/ABS. Flame retardant properties of PC/ABS were investigated by limited oxygen index test, vertical combustion test, thermal gravimetric analysis test, cone calorimetric test and scanning electron microscopy test. The results showed that the addition of 15% POPP to PC/ABS could achieve UL-94 V-0 grade with LOI value of 21.1%. The cone test showed that peak of heat release rate and total heat release decreased by 41.7% and 31.1%, respectively. TGA and SEM analysis demonstrated that the modified PC/ABS alloy exhibited better char forming effect, which promoted the formation of dense porous carbon layer on the surface after combustion, and effectively insulated the oxygen to improve the flame retardant properties of the material.
A novel flame retardant, poly(2-10-hydrogen-9-oxa-phosphaphenanthrene hydroquinone phenyl phosphate)(POPP), was incorporated to PC/ABS to improve the flame retardancy of PC/ABS. Flame retardant properties of PC/ABS were investigated by limited oxygen index test, vertical combustion test, thermal gravimetric analysis test, cone calorimetric test and scanning electron microscopy test. The results showed that the addition of 15% POPP to PC/ABS could achieve UL-94 V-0 grade with LOI value of 21.1%. The cone test showed that peak of heat release rate and total heat release decreased by 41.7% and 31.1%, respectively. TGA and SEM analysis demonstrated that the modified PC/ABS alloy exhibited better char forming effect, which promoted the formation of dense porous carbon layer on the surface after combustion, and effectively insulated the oxygen to improve the flame retardant properties of the material.
引文
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[16] Fang Keyi,Li Juan,Ke Chenhao.Effect of hyperbranched polyphosphate flame retardant on the char formation of nylon 6[J].Acta Polymerica Sinica,2011(1):55-62(in Chinese).方科益,李娟,柯晨皓,等.超支化聚磷酸酯阻燃剂对尼龙6的成炭促进作用[J].高分子学报,2011(1):55-62.
[17] Wang N,Xu G,Wu Y,et al.The influence of expandable graphite on double-layered microcapsules in intumescent flame-retardant natural rubber composites[J].Journal of Thermal Analysis & Calorimetry,2016,123(2):1-13.
[2] Zhang Ning,Guo Qiang.Effect of oxidation degradation of polyethylene on morphology and mechanical property of high density polyethylene/polyamide 6 blends[J].Polymeric Materials Science and Engineering,2014,30(5):81-86(in Chinese).张宁,郭强.丙烯酸酯类共聚物与纳米CaCO3协同改性聚碳酸酯/丙烯腈-丁二烯-苯乙烯三元共聚物合金[J].高分子材料科学与工程,2014,30(5):81-86.
[3] Li Guangxian,Wang Wei,Luo Yong.The study of miscibility and optical properties of PC San binary blends[J].Acta Polymerica Sinica,2003,1(2):247-250(in Chinese).李光宪,王伟,罗勇.聚碳酸酯与苯乙烯-丙烯腈共聚物共混体系相容性及其对光学性能的影响[J].高分子学报,2003,1(2):247-250.
[4] Jiang H,Sun D,Zheng Y,et al.Research of PC/ABS flame retardant properties with triphenyl phosphate/microcrystalline cellulose[J].Modern Plastics Processing & Applications,2018,30(2):38-41(in Chinese).姜慧敏,孙东立,郑燕,等.磷酸三苯酯/纤维素阻燃PC/ABS的研究[J].现代塑料加工应用,2018,30(2):38-41.
[5] Wu N,Lang S.Flame retardancy and toughness modification of flame retardant polycarbonate/acrylonitrile-butadiene-styrene/AHP composites[J].Polymer Degradation & Stability,2016,123:26-35.
[6] Liu Yanqin,Li Jianchang,Ding Xuejia.Recent advances in flame retardant of polycarbonate/acrylonitrile-butadiene-styrene (PC/ABS) alloy[J].China Plastics,2014,28(5):11- 15(in Chinese).刘燕琴,李建厂,丁雪佳,等.阻燃双酚A型聚碳酸酯/丙烯腈-丁二烯-苯乙烯共聚物合金研究进展[J].中国塑料,2014,28(5):11-15.
[7] Li Xiaotang,Bai Jiulin,Chuai Chengzhi.Application of environmental friendly flame retardant RXP in PC/ABS alloy[J].Journal of Tianjin University of Science & Technology,2017,32(1):48-51(in Chinese).李晓唐,白久林,揣成智.RXP环保阻燃剂在PC/ABS合金中的应用[J].天津科技大学学报,2017,32(1):48-51.
[8] Wang Yuxuan,Jiang Hongwei.Preparation of triazine based crosslinked polymers and their charring properties[J].Acta Polymerica Sinica,2009,1(4):325-330(in Chinese).王宇旋,姜宏伟.交联三嗪类聚合物的制备及其成炭性研究[J].高分子学报,2009,1(4):325-330.
[9] Wu Na,Yang Rongjie,Hao Jianwei,et al.Synergistic effect of metal oxides on intumescent flame-retardant PP systems[J].Acta Polymerica Sinica,2009 (12):1205-1210(in Chinese).吴娜,杨荣杰,郝建薇,等.金属氧化物对聚丙烯膨胀阻燃体系阻燃性能的影响[J].高分子学报,2009(12):1205-1210.
[10] Li Pei,Fu Hai,Zhao Ou.Influence of polyphosphate flame retardant couple with ammonium polyphosphate on epoxy resin[J].Chemical Journal of Chinese Universities,2017,38(2):294-302(in Chinese).李霈,付海,赵欧,等.聚磷酸酯阻燃剂复配聚磷酸铵对环氧树脂阻燃性能的影响[J].高等学校化学学报,2017,38(2):294-302.
[11] Ban D M,Qi H L,Zhao O,et al.The manufacturing methods and applications of 10-(2,5-di-hydroxyphenyl ) -9,10-dihydro-9-xa-10-phosphaphenanthrene-10-oxide based polyphosphate esters flame retardants:CN 102796253A[P].2012-11-28(in Chinese).班大明,秦好丽,赵欧,等.联苯二酚聚磷酸酯阻燃剂及其制备方法和用途:CN102786694A[P].2012-11-28.
[12] Yan Shiya,Xu Yuan,Guo Zhenghong.Synergistic flame retardant of acid or alkali-treated montmrillonite /phosphate flame retardant in PC/ABS blends[J].Chemical Journal of Chinese Universities,2013,34(2):467-473(in Chinese).冉诗雅,许远远,郭正虹,等.酸碱处理蒙脱土与磷酸酯阻燃剂复配阻燃PC/ABS合金[J].高等学校化学学报,2013,34(2):467-473.
[13] Wei Zhenjie,Liu Weiqu,Li Hongjing.Properties of phosphosphorus-containing organic silicon/epoxy hybrid resin[J].Acta Polymerica Sinica,2012(2):148-153(in Chinese).魏振杰,刘伟区,李宏静,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.
[14] Usta N.Investigation of fire behavior of rigid polyurethane foams containing fly ash and intumescent flame retardant by using a cone calorimeter[J].Journal of Applied Polymer Science,2012,124(4):3372-3382.
[15] Guo Zhenghong,Shao Jiali,Fang Zhengping.Interaction between stalks nanocellose and natural rubber reinforced by carbon black[J].Polymeric Materials Science and Engineering,2017,33(11):101-107(in Chinese).郭正虹,邵佳丽,方征平.磷酸锆与磷酸三苯酯复配阻燃聚碳酸酯/丙烯腈-丁二烯-苯乙烯合金[J].高分子材料科学与工程,2017,33(11):101-107.
[16] Fang Keyi,Li Juan,Ke Chenhao.Effect of hyperbranched polyphosphate flame retardant on the char formation of nylon 6[J].Acta Polymerica Sinica,2011(1):55-62(in Chinese).方科益,李娟,柯晨皓,等.超支化聚磷酸酯阻燃剂对尼龙6的成炭促进作用[J].高分子学报,2011(1):55-62.
[17] Wang N,Xu G,Wu Y,et al.The influence of expandable graphite on double-layered microcapsules in intumescent flame-retardant natural rubber composites[J].Journal of Thermal Analysis & Calorimetry,2016,123(2):1-13.
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