磷氮膨胀型改性水滑石阻燃剂的制备及其阻燃ABS复合材料的性能
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摘要
采用固相接枝反应的方法,以水滑石(LDHs)及γ–(2,3–环氧丙氧)丙基三甲氧基硅烷(KH–560)、氯磷酸二苯酯和聚乙烯亚胺等为原料,合成了磷氮膨胀型水滑石阻燃剂(IFR–LDHs)。借助傅立叶变换红外光谱仪、冷场发射扫描电子显微镜、透射电子显微镜以及能量色散X射线光谱仪测试,显示水滑石(LDHs)表面已接枝磷氮膨胀型阻燃剂(IFR)。将IFR–LDHs添加到丙烯腈–丁二烯–苯乙烯塑料(ABS)中,提高了阻燃ABS复合材料的阻燃性能。添加15份IFR–LDHs的阻燃ABS复合材料的垂直燃烧等级达到V–0级,LOI达到29.4%,拉伸强度提高了12.5%,断裂伸长率提高了120.0%,缺口冲击强度提高了57.9%。
Via the method of solid phase graft reaction,hydrotalcite(LDHs) modified with phosphorus-nitrogen intumescent flame retardant(IFR–LDHs) was synthesized with LDHs,γ–(2,3–epoxypropoxy) propytrimethoxysilane,diphenyl chlorophosphite and polyethyleneimine. It was tested by FTIR,SEM,TEM and EDX,and the results indicate that intumescent flame retardant is grafted onto the surface of LDHs. IFR-LDHs was added to acrylonitrile-butadiene-styrene plastic(ABS) to improve the flame retardancy of flame retardant ABS composites. When 15 phr IFR-LDHs are added,the vertical combustion grade of flame retardant ABS composite reaches V–0 grade,the LOI reaches 29.4%,the tensile strength increases by 12.5%,the elongation at break increases by 120.0%,the notch impact strength increases by 57.9%.
Via the method of solid phase graft reaction,hydrotalcite(LDHs) modified with phosphorus-nitrogen intumescent flame retardant(IFR–LDHs) was synthesized with LDHs,γ–(2,3–epoxypropoxy) propytrimethoxysilane,diphenyl chlorophosphite and polyethyleneimine. It was tested by FTIR,SEM,TEM and EDX,and the results indicate that intumescent flame retardant is grafted onto the surface of LDHs. IFR-LDHs was added to acrylonitrile-butadiene-styrene plastic(ABS) to improve the flame retardancy of flame retardant ABS composites. When 15 phr IFR-LDHs are added,the vertical combustion grade of flame retardant ABS composite reaches V–0 grade,the LOI reaches 29.4%,the tensile strength increases by 12.5%,the elongation at break increases by 120.0%,the notch impact strength increases by 57.9%.
引文
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[2]Zhao Hao,Zhao Jun,Yun Rongping,et al.Nanohybrids of organomodified layered double hydroxides and polyurethanes with enhanced mechanical,damping and UV absorption properties[J].RSCAdvances,2016,6(41):34 288-34 296.
[3]陈晓东,陈光伟.组分对PA6/PP/滑石粉三元复合材料的影响[J].工程塑料应用,2018,46(5):33-37.Chen Xiaodong,Chen Guangwei.Effect of composition on PA6/PP/talc composite[J].Engineering Plastics Application,2018,46(5):33-37.
[4]徐文,武小雷,孙伟福.聚合物/层状矿物纳米复合材料的研究进展[J].硅酸盐学报,2016,44(5):769-779.Xu Wen,Wu Xiaolei,Sun Weifu.Review on polymer/layered silicates nanocomposites[J].Journal of the Chinese Ceramic Society,2016,44(5):769-779.
[5]Liu Limin,Qi Zongneng,Zhu Xiaoguang.Studies on nylon 6/clay nanocomposites by melt intercalation process[J].Journal of Applied Polymer Science,2015,71(7):1 133-1 138.
[6]Liang Jizhao,Qiu Yulin.Thermal conductivity of graphite-filled LDPE composites[J].Polymer Bulletin,2015,72(7):1 723-1 734.
[7]Bidsorkhi H C,Adelnia H,Naderi N,et al.Ethylene vinyl acetate copolymer nanocomposites based on modified sepiolite:Flame retardancy,thermal,and mechanical properties[J].Polymer Composites,2017,38(7):1 302-1 310.
[8]孔祥文.共沉淀法制备赤泥基水滑石及其EVA复合材料的界面特性、阻燃与力学性能研究[D].青岛:青岛科技大学,2016.Kong Xiangwen.Synthesis of layered double hydroxides based on red mud by a oprecipitation method and its interfacial characrerization,flamere tardant and mechanical propertirs for ethylene vinyl acetate conposites[D].Qingdao:Qingdao University of Science&Technology,2016.
[9]魏涛,慈书亭,何敏,等.纳米蒙脱土、水滑石对阻燃型长玻纤增强聚丙烯阻燃性能及其降解动力学的影响[J].功能材料,2015,46(23):23 051-23 055.Wei Tao,Ci Shuting,He Min,et al.Effects of OMMT and LDH on the flammability and thermaloxidative degradation kinetics of long glass fiber reinforced polypropylene[J].Journal of Functional Materials,2015,46(23):23 051-23 055.
[10]Guo Bingtuo,Liu Yongzhuang,Zhang Qi,et al.Efficient Flameretardant and smoke-suppression properties of Mg-Al-Layered Double-Hydroxide Nanostructures on Wood Substrate[J].ACS Applied Materials&Interfaces,2017,9(27):23 039-23 040.
[11]李旭.水滑石类层状化合物的制备、微分析及应用研究[D].保定:河北大学,2015.Li Xu.Preparation,microanalysis and application study of the layered double hydroxides[D].Baoding:Hebei University,2015.
[12]Gómez--Fernández S,Ugarte L,Pe?a-Rodriguez C,et al.Flexible polyurethane foam nanocomposites with modified layered double hydroxides[J].Applied Clay Science,2016,123:109-120.
[13]李冉冉,徐冰,温阳,等.聚磷酸铵掺杂类水滑石阻燃材料研究[J].消防科学与技术,2017,36(8):1 116-1 119.Li Ranran,Xu Bing,Wen Yang,et al.Study on the ammonium polyphosphate doped hydrotalcite like flame retardant material[J].Fire Science and Technology,2017,36(8):1116-1119.
[14]隋晓彤,朱凤丽,赵静,等.PP/IFR/水滑石阻燃复合材料的研究[J].现代塑料加工应用,2017,29(6):38-41.Sui Xiaotong,Zhu Fengli,Zhao Jing,et al.Study on PP/IFR/hydrotalcite flame-retarded composites[J].Modern Plastics Processing and Applications,2017,29(6):38-41.
[15]Xie Hongyan,Ye Qing,Si Jingyu,et al.Synthesis of a carbon nanotubes/ZnAl‐layered double hydroxide composite as a novel flame retardant for flexible polyurethane foams[J].Polymers for Advanced Technologies,2016,27(5):651-656.
[16]黄昱臻,董银春,沈帆,等.水滑石表面改性对聚氯乙烯弹性体性能的影响[J].现代塑料加工应用,2018,30(3):42-45.Huang Yuzhen,Dong Yinchun,Shen Fan,et al.Effect of midified hydrotalcite on soft polyvinyl chloride[J].Modern Plastics Processing and Applications,2018,30(3):42-45.
[17]刘义林,韩得满,汪鹏飞,等.膨胀型阻燃剂功能化水滑石的制备及阻燃改性三元乙丙橡胶发泡材料的研究[J].特种橡胶制品,2016,37(3):1-6.Liu Yilin,Han Deman,Wang Pengfei,et al.Preparation of intumescent flame retardant-functionalized layered double hydroxides and its frame-retardant modification on EPDM foam materials[J].Special Perpose Rubber Products,2016,37(3):1-6.
[18]Zhang Sheng,Tang Wufei,Sun Jun,et al.Synergistic effects of modified hydrotalcite on improving the fire resistance of ethylene vinyl acetate containing intumescent flame retardants[J].Polymer Composites,2018,39(2):522-528.
[19]叶文娟,杜隆超.一种新型膨胀阻燃剂的合成及与层状双氢氧化物复合阻燃LLDPE[J].安徽大学学报:自然科学版,2016,40(5):87-96.Ye Wenjuan,Du Longchao.Synthesis of a novel intumescent flame retardant and its synergistic effect research with different layered double hydroxides in halogen free flame retardant LLDPE[J].Journal of Anhui University:Natural Science Edition,2016,40(5):87-96.
[20]王春锋.阻燃改性水滑石/聚乙烯纳米复合材料热降解与燃烧性能[D].哈尔滨:哈尔滨理工大学,2015.Wang Chunfeng.Thermal degradation and combustion behaviors of flame-retardant modified layered double hydrotalcides/polyethylene nanocomposites[D].Harbin:Harbin University of Science and Technology,2015.