改性纳米SiO_2/硅橡胶复合材料的制备及性能
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摘要
为提高纳米SiO_2在硅橡胶(SR)基体中的分散性及两相间的界面结合力,设计以羟基硅油(HSO)和γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)为纳米SiO_2的表面封端改性剂,并将改性SiO_2与双组份加成型液体SR复合得到改性纳米SiO_2/SR复合材料。通过一系列表征手段对改性纳米SiO_2的形貌结构及其在乙醇中的分散性等进行分析,研究了改性纳米SiO_2对纳米SiO_2/SR复合材料的断面形貌、力学性能及热稳定性的影响。结果表明:KH570成功接枝到纳米SiO_2表面并与SR基体间形成化学键。当HSO协同KH570改性纳米SiO_2时,可有效改善纳米SiO_2在SR基体中的分散性能及纳米SiO_2与SR两相间的界面结合性能,并显著提高纳米SiO_2/SR复合材料的力学性能和热稳定性。将SiO_2∶HSO∶KH570以质量比为2.0∶0.2∶0.6处理的改性纳米SiO_2粒子,得到的改性纳米SiO_2/SR复合材料起始热分解温度提高了230℃。当SiO_2∶HSO∶KH570质量比为2.0∶0.2∶0.45时,改性纳米SiO_2/SR复合材料的拉伸强度和断裂伸长率分别提高了约1倍。
To improve the dispersibility of nano SiO_2 particles in silicon rubber(SR)and the interfacial bonding performance of the two phases,the surface modification agent consisting of hydroxyl silicone oil(HSO)and 3-(trimethoxysilyl)propylmethacrylate(KH570)for nano SiO_2 was designed.And the modified nano SiO_2/SR composites were prepared.The morphology structure of nano SiO_2 and the dispersibility of nano SiO_2 in the ethanol were investigated,the fracture surface morphology,mechanical properties and thermal stability of the modified nano SiO_2/SR composites were also analyzed.The results show that KH570 is successfully grafted to the surface of nano SiO_2 and formes chemical bonds with the SR matrix.When the nano SiO_2 is treated by the hybrid surface modification agent(HSO cooperated with KH570),the dispersibility of SiO_2 in SR matrix,and the interface bonding performances between SiO_2 and SR are improved obviously,the mechanical properties and thermal stability of the SiO_2/SR composites are also enhanced significantly.When SiO_2∶HSO∶KH570 mass ratio is 2.0∶0.2∶0.6,the initial temperature of thermal decomposition of the modified nano SiO_2/SR composite increases to 230℃.When SiO_2∶HSO∶KH570 mass ratio is 2.0∶0.2∶0.45,the tensile strength and elongation at break of the modified nano SiO_2/SR composite increase twice,respectively.
To improve the dispersibility of nano SiO_2 particles in silicon rubber(SR)and the interfacial bonding performance of the two phases,the surface modification agent consisting of hydroxyl silicone oil(HSO)and 3-(trimethoxysilyl)propylmethacrylate(KH570)for nano SiO_2 was designed.And the modified nano SiO_2/SR composites were prepared.The morphology structure of nano SiO_2 and the dispersibility of nano SiO_2 in the ethanol were investigated,the fracture surface morphology,mechanical properties and thermal stability of the modified nano SiO_2/SR composites were also analyzed.The results show that KH570 is successfully grafted to the surface of nano SiO_2 and formes chemical bonds with the SR matrix.When the nano SiO_2 is treated by the hybrid surface modification agent(HSO cooperated with KH570),the dispersibility of SiO_2 in SR matrix,and the interface bonding performances between SiO_2 and SR are improved obviously,the mechanical properties and thermal stability of the SiO_2/SR composites are also enhanced significantly.When SiO_2∶HSO∶KH570 mass ratio is 2.0∶0.2∶0.6,the initial temperature of thermal decomposition of the modified nano SiO_2/SR composite increases to 230℃.When SiO_2∶HSO∶KH570 mass ratio is 2.0∶0.2∶0.45,the tensile strength and elongation at break of the modified nano SiO_2/SR composite increase twice,respectively.
引文
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[26]黎嘉炜.无机粉体增黏增强改性r-PET的研究[D].广州:华南理工大学,2015.LI J W.Study on intrinsic viscosity,crystallization and mechanical properties of r-PET/inorganic powder composite[D].Guangzhou:South China University of Technology,2015(in Chinese).
[27]秦玉升,顾林,王献红.二氧化碳基脂肪族聚碳酸酯的功能化研究进展[J].高分子学报,2013(5):600-608.QIN Y S,GU L,WANG X H.Progress in functional carbon dioxide based aliphatic polycarbonates[J].Acta Polymerica Sinica,2013(5):600-608(in Chinese).
[28]CHINN S,DETERESA S,SAWVEL A,et al.Chemical origins of permanent set in a peroxide cured filled silicone elastomer-tensile and 1 H NMR analysis[J].Polymer Degradation and Stability,2006,91(3):555-564.
[29]苏正涛,王景鹤.耐高低温硅橡胶的研究[J].航空材料学报,2006,26(3):207-212.SU Z T,WANG J H.Properties of silicone rubber at high or low temperature[J].Journal of Aeronautical Materials,2006,26(3):207-212(in Chinese).
[2]王芳,青双桂,罗仲宽,等.大功率LED封装材料的研究进展[J].材料导报,2010,24(3):56-59.WANG F,QING S G,LUO Z K,et al.Research progress of high-power LED encapulant[J].Materials Review,2010,24(3):56-59(in Chinese).
[3]PRADHAN B,ROY S,SRIVASTAVA S K,et al.Synergistic effect of carbon nanotubes and clay platelets in reinforcing properties of silicone rubber nanocomposites[J].Journal of Applied Polymer Science,2015,132(15):871-882.
[4]HEIDARIAN J,HASSAN A.Microstructural and thermal properties of fluoroelastomer/carbon nanotube composites[J].Composites Part B:Engineering,2014,58:166-174.
[5]穆晓东,崔雨果,方庆红,等.白炭黑的功能化改性及其改性橡胶基复合材料的制备与表征[J].复合材料学报,2017,34(1):67-74.MU X D,CUI Y G,FANG Q H,et al.Preparation and characterization of functionalization of silica and its rubber matrix composites[J].Acta Materiae Compositae Sinica,2017,34(1):67-74(in Chinese).
[6]SONG Y,SONG L,LU A,et al.Surface grafting vinyl on silica white surface and its effect on curing behavior of silicone rubber[J].Journal of the Chinese Ceramic Society,2013,41(5):674-678.
[7]YAN F,ZHANG X,LIU F,et al.Adjusting the properties of silicone rubber filled with nanosilica by changing the surface organic groups of nanosilica[J].Composites Part B:Engineering,2015,75:47-52.
[8]ZHANG X,GUAN Y,ZHAO Y,et al.Reinforcement of silicone rubber with raspberry-like SiO2@polymer composite particles[J].Polymer International,2015,64(8):992-998.
[9]LI Y,CHEN Z,LI X,et al.A new surface modification method to improve the dispersity of nano-silica in organic solvents[J].Journal of Sol-Gel Science and Technology,2011,58(1):290-295.
[10]LIU J,WU S,ZOU M,et al.Surface modification of silica and its compounding with polydimethylsiloxane matrix:Interaction of modified silica filler with PDMS[J].Iranian Polymer Journal,2012,21(9):583-589.
[11]SONG Y,YU J,DAI D,et al.Effect of silica particles modified by in-situ and ex-situ methods on the reinforcement of silicone rubber[J].Materials&Design,2014,64:687-693.
[12]MA X,LEE N H,OH H J,et al.Surface modification and characterization of highly dispersed silica nanoparticles by a cationic surfactant[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2010,358(13):172-176.
[13]FANG X L,HUANG X,LU Z,et al.Synthesis of new superhydrophobic nanosilica and investigation of their performance in reinforcement of polysiloxane[J].Polymer Composites,2010,31(9):1628-1636.
[14]赵永振,水兴瑶,董余兵,等.杂化涂层对玻璃纤维/环氧树脂复合材料高温场下界面性能的影响[J].浙江理工大学学报(自然科学版),2017,37(6):785-789.ZHAO Y Z,SHUI X Y,DONG Y B,et al.Effect of hybrid coating on the interfacial property of glass fiber/epoxy composite processed at high temperature[J].Journal of Zhejiang Sci-Tech University(Natural Sciences),2017,37(6):785-789(in Chinese).
[15]岑浩,杨洪斌,傅雅琴.硅溶胶改性碳纤维对碳纤维/环氧树脂复合材料界面性能影响[J].复合材料学报,2012,29(6):32-36.CEN H,YANG H B,FU Y Q.Effect of surface modification by silica sol on interfacial properties of carbon fiber/epoxy composite[J].Acta Materiae Compositae Sinica,2012,29(6):32-36(in Chinese).
[16]水兴瑶,刘猛,朱曜峰,等.水性上浆剂对碳纤维表面及碳纤维/环氧树脂复合材料界面性能的影响[J].复合材料学报,2016,33(2):273-279.SHUI X Y,LIU M,ZHU Y F,et al.Effect of waterborne sizing agent on carbon fiber surface and properties of carbon fiber/epoxy composite interface[J].Acta Materiae Compositae Sinica,2016,33(2):273-279(in Chinese).
[17]武江红.纳米二氧化硅的温敏改性及其性能研究[D].太原:中国日用化学工业研究院,2013.WU J H.Preparation and property of thermo-responsive silica nano-spheres[D].Taiyuan:China Research Institute of Daily Chemical Industry,2013(in Chinese).
[18]李玉平,王亚强,贺卫卫,等.纳米SiO2表面接枝及其在原位乳液聚合体系中的分散稳定性[J].湖南大学学报,2006,33(3):80-83.LI Y P,WANG Y Q,HE W W,et al.Graft of nano-silica and its dispersion stability in the in-suit emulsion polymerization[J].Journal of Hunan University,2006,33(3):80-83(in Chinese).
[19]李员.硅烷偶联剂改性白炭黑及在硅橡胶中的应用[D].济南:济南大学,2015.LI Y.Silane coupling agents modified silica nanoparticles and the application in silicone rubber[D].Jinan:University of Jinan,2015(in Chinese).
[20]戚云霞.加成型室温硫化硅橡胶的制备及改性[D].济南:山东大学,2006.QI Y X.Preparation and modification of room temperature vulcanized siliconerubber[D].Jinan:University of Shandong,2006(in Chinese).
[21]李亚,陈洪龄.含氢硅油机械化学法改性SiO2粉体[J].机械工程材料,2008,32(1):76-78+83.LI Y,CHEN H L.Modification of silica by mechanochemical treatment with polymethylhydrogensiloxane[J].Materials for Mechanical Engineering,2008,32(1):76-78+83(in Chinese).
[22]马志领,郝学辉,何佳音,等.羟基硅油原位改性制备疏水性沉淀二氧化硅[J].无机盐工业,2011,43(3):36-38.MA Z L,HAO X H,HE J Y,et al.Preparation of hydrophobic precipitated SiO2 by in-situ modification of hydrpxyl silicone oil[J].Inorganic Chemicals Industry,2011,43(3):36-38(in Chinese).
[23]杜高翔,左然芳,梅乐夫,等.硅烷偶联剂改性硅藻土及其对天然橡胶/丁苯橡胶补强效果的影响[J].稀有金属材料与工程,2013,42(1):412-417.DU G X,ZUO R F,MEI L F,et al.Surface modification of diatomite by silane coupling agent and its effect on the reinforcing efficiency of NR/SBR blend[J].Rare Metal Materials and Engineering,2013,42(1):412-417(in Chinese).
[24]王宝玉,张苏明,兰玉顺,等.KH-570表面改性超细SiO2的研究[J].北京化工大学学报,2010,37(5):30-34.WANG B Y,ZHANG S M,LAN Y S,et al.Experimental studies of the surface modification of silica by KH-570[J].Journal of Beijing University of Chemical Technology,2010,37(5):30-34(in Chinese).
[25]张云浩,翟兰兰,王彦,等.硅烷偶联剂KH-570表面改性纳米SiO2[J].材料科学与工程学报,2012,30(5):752-756.ZHANG Y H,ZHAI L L,WANG Y,et al.Surface modification of nano SiO2by silane coupling agent 3 methacryloyloxypropyltrimethoxysilane[J].Journal of Materials Science&Engineering,2012,30(5):752-756(in Chinese).
[26]黎嘉炜.无机粉体增黏增强改性r-PET的研究[D].广州:华南理工大学,2015.LI J W.Study on intrinsic viscosity,crystallization and mechanical properties of r-PET/inorganic powder composite[D].Guangzhou:South China University of Technology,2015(in Chinese).
[27]秦玉升,顾林,王献红.二氧化碳基脂肪族聚碳酸酯的功能化研究进展[J].高分子学报,2013(5):600-608.QIN Y S,GU L,WANG X H.Progress in functional carbon dioxide based aliphatic polycarbonates[J].Acta Polymerica Sinica,2013(5):600-608(in Chinese).
[28]CHINN S,DETERESA S,SAWVEL A,et al.Chemical origins of permanent set in a peroxide cured filled silicone elastomer-tensile and 1 H NMR analysis[J].Polymer Degradation and Stability,2006,91(3):555-564.
[29]苏正涛,王景鹤.耐高低温硅橡胶的研究[J].航空材料学报,2006,26(3):207-212.SU Z T,WANG J H.Properties of silicone rubber at high or low temperature[J].Journal of Aeronautical Materials,2006,26(3):207-212(in Chinese).
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