层状结构氧化石墨烯/聚丙烯接枝磺化苯乙烯/聚苯胺复合抗静电剂的制备及应用
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摘要
以苯胺、聚丙烯接枝磺化苯乙烯、氧化石墨烯为反应原料,以盐酸为掺杂剂,通过苯胺原位聚合及大分子反应制备了氧化石墨烯/聚丙烯接枝磺化苯乙烯/聚苯胺(GO/PP-g-SPS/PANI)层状结构的复合材料。研究了复合材料的体积电阻率及反应物配比对复合材料体积电阻的影响。分别采用FTIR、XPS对复合材料进行了结构分析,并采用SEM对复合材料结构形貌进行了表征,同时研究了将其添加到PP中的抗静电性能。研究结果表明:GO/PP-g-SPS/PANI制备最佳配比为质量比m_(PP-g-SPS):m_(GO):m_(ANI)=30:15:1时,材料体积电阻率最小为120?·mm。添加到PP中导电逾渗阈值为0.7%(质量分数),PP材料的体积电阻率达到最低值4.5×10~(10)?·mm,比纯PP降低了6个数量级,拉伸强度提高了2.8MPa。SEM形貌图表明GO/PP-g-SPS/PANI以GO为骨架表面层状蜂窝结构,聚合物大分子镶嵌在GO片层间,与PP共混物界面具有良好的相容性。
With polypropylene-grafted-sulfonated styrene, aniline and graphene oxide as raw materials with hydrochloric acid as the doping agent, the layered graphene oxide/polypropylene-graftedsulfonated styrene/polyaniline(GO/PP-g-SPS/PANI) composites was prepared by in situ polymerization of aniline and macromolecular. The volume resistivity of the composites and the effect of the ratio of reactants on the volume resistivity of the composites were studied. FTIR and XPS were used to charactered the structure of the composites and SEM was used to analyze the morphology of the composites. The antistatic properties of the adding it to PP were also studied. The results showed that the optimal synthesis ratio for GO/PP-g-SPS/PANI were as follows: mass ratio m_(PP-g-SPS):m_(GO):m_(ANI)=30:15:1, and the minimum volume resistivity of the material was 120?·mm. The conductivity threshold was 0.7% by mass in PP, and the volume resistivity of the PP material reached a minimum value of 4.5×10~(10)?·mm, which was 6 orders of magnitude lower than that of pure PP. The tensile strength of PP increased by 2.8 MPa. SEM showed that GO/PP-g-SPS/PANI had GO as the surface layered honeycomb structure, and polymer macromolecules were embedded between GO slices. The PP blend interface had good compatibility.
With polypropylene-grafted-sulfonated styrene, aniline and graphene oxide as raw materials with hydrochloric acid as the doping agent, the layered graphene oxide/polypropylene-graftedsulfonated styrene/polyaniline(GO/PP-g-SPS/PANI) composites was prepared by in situ polymerization of aniline and macromolecular. The volume resistivity of the composites and the effect of the ratio of reactants on the volume resistivity of the composites were studied. FTIR and XPS were used to charactered the structure of the composites and SEM was used to analyze the morphology of the composites. The antistatic properties of the adding it to PP were also studied. The results showed that the optimal synthesis ratio for GO/PP-g-SPS/PANI were as follows: mass ratio m_(PP-g-SPS):m_(GO):m_(ANI)=30:15:1, and the minimum volume resistivity of the material was 120?·mm. The conductivity threshold was 0.7% by mass in PP, and the volume resistivity of the PP material reached a minimum value of 4.5×10~(10)?·mm, which was 6 orders of magnitude lower than that of pure PP. The tensile strength of PP increased by 2.8 MPa. SEM showed that GO/PP-g-SPS/PANI had GO as the surface layered honeycomb structure, and polymer macromolecules were embedded between GO slices. The PP blend interface had good compatibility.
引文
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[2]SUZUKI M.Antistatic agent for synthetic polymer materials and method of application thereof:US6225386[P].2001-05-01.
[3]ANDERSON B J.Amine-free internal antistatic agent:US5348995[P].1994-09-20.
[4]施明,郑成,余习焕,等.十八烷基二羟基甲基溴化铵作为聚丙烯抗静电剂添加剂的研究[J].化工学报,2012,63(11):3723-3729.SHI Ming,ZHENG Cheng,YU Xihuan,et al.Reserch of octadecyl methyl dihydroxyethyl ammonium bromide as antistatic agent in polyropylene[J].CIESC Journal,2012,63(11):3723-3729.
[5]PUD A A,NIKOLAYEVA O A,VRETIK L O,et al.New nanocomposites of polystyrene with polyaniline doped with lauryl sulfuric acid[J].Nanoscale Research Letters,2017,12:493.
[6]范卫娟.一种烷醇酰胺类非离子型抗静电剂的合成及应用性能研究[J].塑料助剂,2009,75(3):26-28.FAN Weijuan.Study on synthesis and performance of a fat alkanolamides non-ionic antistatic agent[J].Plastics Additives,2009,75(3):26-28.
[7]吴逊,丁永红,俞强.几种非离子型抗静电剂在聚丙烯薄膜中的应用研究[J].中国塑料,2014,28(4):92-96.WU Xun,DING Yonghong,YU Qiang.Application of several non-ionic antistatic agents in polypropylene film[J].China Plastic,2014,28(4):92-96.
[8]XU X,XIAO H N,GUAN Y.Permanent antistatic polypropylene based on polyethylene wax/polypropylene wax grafting sodium acrylate[J].Journal of Applied Polymer Science,2012,126(1):83-90.
[9]胡洪超,舒绪刚,崔英德.聚苯胺的合成及机理研究进展[J].化工进展,2016,35(1):195-201.HU Hongchao,SHU Xugang,CUI Yingde.Progress in synthesis and mechanism of ployaniline[J].Chemical Industry and Engineering Progress,2016,35(1):195-201.
[10]景遐斌,王利祥,王献红,等.导电聚苯胺的合成、结构、性能和应用[J].高分子学报,2005,5(10):655-662.JING Xiabin,WANG Lixiang,WANG Xianhong,et al.Synthesis,structure,properties and applications of conducting polyaniline[J].Acta Polymerica Sinica,2005,5(10):655-662.
[11]MOHAMMAD F,BEHZAD P,MEHDI S,et al.Preparation of conductive,flexible and transparent films by in situ deposition of polypyrrole nanoparticles on polyethylene terephthalate[J].Polymer Science,Series B,2017,59(3):308-319.
[12]AMIN I,MAHBUBE A,GHOLAMALI F.Effect of in-situ oxidative preparation on electrical properties of epoxy/PANi/MWCNTs nanocomposites[J].Journal of Materials Science:Materials in Electronics,2016,27(10):10364-10370.
[13]贺天禄,李宝芳,罗英武,等.复合抗静电剂在PP上的应用研究[J].塑料工业,2003,31(5):43-45.HE Tianlu,LI Baofang,LUO Yingwu,et al.Study of application of complex antistatic agent to PP[J].China Plastics Industry,2003,31(5):43-45.
[14]郭静,沈新元,李福清,等.PEG-ZnO-PP复合抗静电剂及其对聚丙烯纤维的改性[J].合成纤维工业,2007,30(1):31-33.GUO Jing,SHEN Xinyuan,LI Fuqing,et al.PEG-ZnO-PP composite antistatic agent and its modification for polypropylene fiber[J].China Synthetic Fiber Industry,2007,30(1):31-33.
[15]SONG N,YANG J W,DING P,et al.Effect of covalentfunctionalized graphene oxide with polymer and reactive compatibilization on thermal properties of maleic anhydride grafted polypropylene[J].Ind.Eng.Chem.Res.,2014,53(51):19951-19960.
[16]SHENG X X,CAI W X,ZHONG L,et al.Synthesis of functionalized graphene/polyaniline nanocomposites with effective synergistic reinforcement on nticorrosion[J].Ind.Eng.Chem.Res.,2016,55(31):8576-8585.
[17]HUANG Y J,QIN Y W,ZHOU Y,et al.Graphene and its nanocomposite[J].Chem.Mater.,2010,22(13):4096-4102.
[18]FENG C P,NI H Y,CHEN J N.Facile method to fabricate highly thermally conductive graphite/PP composite with network structures[J].ACS Appl.Mater.Interfaces,2016,8:19732-19738.
[19]HE S H,ZHANG J J,XIAO X T,et al.Investigation of the conductive network formation of polypropylene/graphene nanoplatelets composites for different platelet sizes[J].Journal of Materials Science,2017,52(22):13103-13119.
[20]HEEDER N,CHAKRABORTY I,BOSE A,et al.Electro-mechanical behavior of graphene-polystyrene composites under dynamic loading[J].Journal of Dynamic Behavior of Materials,2015,1(1):43-54.
[21]祖立武,张晓宇,王雅珍,等.聚丙烯接枝苯乙烯磺酸-聚苯胺抗静电剂的制备和性能[J].材料研究学报,2012(6):610-614.ZU Liwu,ZHANG Xiaoyu,WANG Yazhen,et al.Preparation and properties of polypropylene grafted styrene sulfonic acid-polyaniline antistatic agents[J].Chinese Journal of Materials Research,2012(6):610-614.