聚丙烯/氧化石墨烯复合材料的制备、结构及性能
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摘要
以石墨、浓硫酸、高锰酸钾和双氧水等为原料,通过Hummers法制备了氧化石墨烯(GO)分散液,对其冷冻干燥得到GO粉体,将GO粉体与熔融聚丙烯(PP)树脂共混制备PP/GO复合材料,采用FTIR、AFM、TEM、XRD、DSC及导热仪和氧指数测定仪等对GO及PP/GO复合材料的结构和性能进行了表征。结果表明,GO能够以双片层形式均匀地分散在PP基体中,GO/PP复合材料具有致密均匀的微观结构,其力学性能、耐热、阻燃和热传导等性能比对照样品(单纯PP树脂)有显著提高。当GO掺量为0.4%(以PP的质量为基准,下同)时,PP/GO复合材料的拉伸强度、弯曲强度和冲击强度比对照样品分别提高了29.6%、33.6%和62.7%,熔点从154.5℃提高为174.2℃,热导率提升了205.3%,极限氧指数从18.0提高到27.6。
Graphite oxide(GO) dispersion in a aqueous solution was prepared by Hummers method using graphite, concentrated sulfuric acid, potassium permanganate and hydrogen peroxide as main raw materials.Then, GO powder was obtained by freeze drying of GO dispersion. Subsequently, polypropylene(PP)/GO composites were prepared by blending GO powder with melt PP. The structure and properties of GO and PP/GO composites were characterized using various testing methods such as FTIR, AFM, TEM, XRD,DSC, conductometer and oxygen index determinator. The results indicated that GO could be uniformly dispersed in PP matrix with double layers, which resulted in forming compact and even microstructure in PP/GO composites. The mechanical properties, heat resistance, flame resistance and thermal conductive of PP/GO composites had a significant improvement compared with that of the control sample(pure PP resin).When the dosage of GO was 0.4%(based on the mass of PP, the same below), the tensile strength, flexural strength and impact strength of the GO/PP composites were higher 29.6%, 33.6% and 62.7% than that of pure PP resin, respectively. Meanwhile, the melting point was increased from 154.5 ℃ to 174.2 ℃, the thermal conductivity increased by 205.3%, and the limiting oxygen index was increased from 18.0 to 27.6.
Graphite oxide(GO) dispersion in a aqueous solution was prepared by Hummers method using graphite, concentrated sulfuric acid, potassium permanganate and hydrogen peroxide as main raw materials.Then, GO powder was obtained by freeze drying of GO dispersion. Subsequently, polypropylene(PP)/GO composites were prepared by blending GO powder with melt PP. The structure and properties of GO and PP/GO composites were characterized using various testing methods such as FTIR, AFM, TEM, XRD,DSC, conductometer and oxygen index determinator. The results indicated that GO could be uniformly dispersed in PP matrix with double layers, which resulted in forming compact and even microstructure in PP/GO composites. The mechanical properties, heat resistance, flame resistance and thermal conductive of PP/GO composites had a significant improvement compared with that of the control sample(pure PP resin).When the dosage of GO was 0.4%(based on the mass of PP, the same below), the tensile strength, flexural strength and impact strength of the GO/PP composites were higher 29.6%, 33.6% and 62.7% than that of pure PP resin, respectively. Meanwhile, the melting point was increased from 154.5 ℃ to 174.2 ℃, the thermal conductivity increased by 205.3%, and the limiting oxygen index was increased from 18.0 to 27.6.
引文
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[26]Hao Yanping(郝艳萍).Preparation and properties of graphene oxides/polymer composites[D].Shanghai:Donghua University(东华大学),2017.
[27]Wang C C,Zhao Y Y,Ge H Y,et al.Enhanced mechanical and thermal properties of short carbon fiber reinforced polypropylene composites by graphene oxide[J].Polymer Composites,2018,39(2):405-413.
[28]Tao Shouliang(陶守亮),Wang Jihui(王继辉),Ni Aiqing(倪爱清).Synthesis of intumescent flame retardant and flame retardation of polypropylene[J].Journal of Wuhan University of Technology(武汉理工大学学报),2017,39(8):8-20.
[29]Sun Yanan(孙亚楠),Tian Guanghua(田广华).Influencing factors and improving methods of weatherability of polypropylene[J].Synthetic Materials Aging and Application(合成材料老化与应用),2018,47(1):97-100.
[30]Ni Linggui(倪玲贵),Mamatjan Yimit(买买提江·依米提),Riza Beken(热依扎·别坎),et al.Effect of different aging methods on aging degree of polypropylene[J].China Plastics Industry(塑料工业),2017,45(1):93-96.
[2]Ding Qian(丁茜),Zhang Zishou(章自寿),Luo Jianxin(罗建新),et al.Development status of the recycling technique of waste polypropylene[J].China Plastics Industry(塑料工业),2017,45(5):16-20.
[3]Woo J H,Park S Y.Polypropylene nanocomposite with polypropylene-grafted grapheme[J].Macromolecular Research,2016,24(6):508-514.
[4]Cai Bing(蔡冰),Hu Yuexin(胡跃鑫),Han Xiangyan(韩向艳),et al.Research progress in hemocompatibility of surface modified polypropylene[J].Polymer Bulletin(高分子通报),2016,(1):31-37.
[5]Zhou Pengxin(周鹏鑫),Huang Li(黄莉),Ma Delong(马德龙),et al.Preparation and performance of organo palygorskite intumscent flame retardant-type polypropylene composite[J].Fine Chemicals(精细化工),2015,32(9):961-967.
[6]Liu Chunlei(刘春磊).Research progress in expansibility antiflaming of modified polypropylene[J].Technical Innovation(科技创新),2017,(9):69-70.
[7]Tiwari S,Orao R,De Adhikari A,et al.Thermomechanical study on selective dispersion and different loading of graphene oxide in polypropylene/polycarbonate blends[J].Journal of Applied Polymer Science,2017,134(28):1123-1129.
[8]Zhou Man(周满),Du Hainan(杜海南),Zhang Jie(张杰).Research progress in toughening modify ions of polypropylene[J].Modern Plastics Progressing and Application(现代塑料加工),2016,28(6):60-64.
[9]Carzon C,Palza H.Electrical behavior of polypropylene composites melt mixed with carbon-based particles:Effect of the kind of particle and annealing process[J].Composites Science and Technology,2014,99,117-123.
[10]Li Denghai(李登海),Liu Shaoze(刘绍泽),Li Aiping(李爱平),et al.Research progress in modification of polypropylene flim[J].New Chemical Materials(化工新型材料),2017,45(1):44-46.
[11]Zhang Zhixiong(张志雄),Li Li(李莉),Ouyang Xinping(欧阳新平),et al.Preparation and properties of polypropylene separators modified by Al2O3/PVA[J].Fine Chemicals(精细化工),2017,34(8):925-929.
[12]Zhao Yumei(赵玉梅).Research progress of modified PP for automobile for lightweight[J].China Synthetic Resin and Plastics(合成树脂与塑料),2016,33(6):91-94.
[13]Chen H R,Ma W H,Xia Y P,et al.Improving amphiphilic polypropylenes by grafting poly(vinylpyrrolidone)and poly(ethylene glycol)methacrylate segments on a polypropylene microporous membrane[J].Applied Surface Science,2017,419:259-268.
[14]Lazim N H,Samat N.Effects of irradiated recycled polypropylene compatibilizer on the mechanical properties of microcrystalline cellulose reinforced recycled polypropylene composites[J].Procedia Engineering,2017,184:538-543.
[15]Wei Liangqiang(韦良强),Huang Anrong(黄安荣),Qi Yuanhui(戚远慧),et al.Research of polypropylene based dielectric composites[J].China Plastics Industry(塑料工业),2017,45(2):120-124.
[16]Atifi S,Miao C W,Hamad W Y.Surface modification of lignin for applications in polypropylene blends[J].Journal of Applied Polymer Science,2017,134(29):546-556.
[17]Lee B H,Cho J W,Kim K H.Crystallization,orientation,and mechanical properties of laser-heated photothermally drawn polypropylene/multi-walled carbon nanotube fibers[J].European Polymer Journal,2017,91:70-80.
[18]Bar M,Das A,Alagirusamy R.Studies on flax-polypropylene based low-twist hybrid yarns for thermoplastic composite reinforcement[J].Journal of Reinforced Plastics and Composites,2017,36(11):818-831.
[19]Xiao Shujuan(肖淑娟),Yu Shouwu(于守武),Tan Xiaoyao(谭小耀).Research progress and the applications of graphene materials[J].Chemical Industry and Engineering Progress(化工进展),2015,34(5):1345-1348.
[20]Shah R,Kausar A,Muhammad B,et al.Progression from graphene and graphene oxide to high performance polymer-based nanocomposite:A review[J].Polymer-Plastics Technology and Engineering,2015,54(2):173-183.
[21]Yuan B,Bao C,Song L,et al.Preparation of functionalized graphene oxide/polypropylene nanocomposite with significantly improved thermal stability and studies on the crystallization behavior and mechanical properties[J].Chemical Engineering Journal,2014,237:411-420.
[22]Yuan Zupei(袁祖培),Chen Jie(陈洁),Tang Junxiong(唐俊雄),et al.Preparation,properties and application of graphene-doped PPcomposites[J].China Synthetic Resin and Plastics(合成树脂及塑料),2017,34(3):88-92.
[23]Bian J,Wang Z J,Lin H L,et al.Thermal and mechanical properties of polypropylene nanocomposites reinforced with nano-SiO2functionalized graphene oxide[J].Composites,Part A:Applied Science and Manufacturing,2017,97:120-127.
[24]Huang Guojia(黄国家),Chen Zhigang(陈志刚),Li Maodong(李茂东),et al.Surface functional modification of graphene and graphene oxide[J].CIESC Journal(化工学报),2016,74:789-799.
[25]Dang Zhimin(党志敏).Preparation and characterization of graphene oxide and its composites[D].Nanjing:Nanjing University(南京大学),2010.
[26]Hao Yanping(郝艳萍).Preparation and properties of graphene oxides/polymer composites[D].Shanghai:Donghua University(东华大学),2017.
[27]Wang C C,Zhao Y Y,Ge H Y,et al.Enhanced mechanical and thermal properties of short carbon fiber reinforced polypropylene composites by graphene oxide[J].Polymer Composites,2018,39(2):405-413.
[28]Tao Shouliang(陶守亮),Wang Jihui(王继辉),Ni Aiqing(倪爱清).Synthesis of intumescent flame retardant and flame retardation of polypropylene[J].Journal of Wuhan University of Technology(武汉理工大学学报),2017,39(8):8-20.
[29]Sun Yanan(孙亚楠),Tian Guanghua(田广华).Influencing factors and improving methods of weatherability of polypropylene[J].Synthetic Materials Aging and Application(合成材料老化与应用),2018,47(1):97-100.
[30]Ni Linggui(倪玲贵),Mamatjan Yimit(买买提江·依米提),Riza Beken(热依扎·别坎),et al.Effect of different aging methods on aging degree of polypropylene[J].China Plastics Industry(塑料工业),2017,45(1):93-96.