KH570原位改性纳米SiO_2球状颗粒的制备及疏水效果评价
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摘要
为了制备疏水纳米SiO_2,提高在聚合物中的分散性,利用改进的Stber法合成出纳米SiO_2;依据脱醇缩合原理,用有机溶剂置换醇水溶剂,以γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)作为改性剂对其进行原位改性;通过红外光谱分析、扫描电镜、粒度分析及一系列疏水性能测试表征产物结构并评价疏水效果。结果表明,经表面改性纳米SiO_2成功接枝上有机基团,颗粒形貌呈规则的球形,粒度约为50 nm,团聚现象明显减弱。通过疏水效果测试,改性后的纳米SiO_2能在有机溶剂中均匀分散,且在石蜡溶剂中能稳定存在1年以上;因其吸水率减小至28%,亲油化度增大至62%,接触角由23. 1°增大至129. 8°,可见疏水效果大幅提高。通过研究改性条件得出:最佳改性剂浓度为60%,最佳改性温度为100℃,最佳改性时间为25 h。
In order to prepare hydrophobic nano-SiO_2 and improve the dispersibility in polymer materials,the nano-SiO_2 was synthesized by the modified Stber method. According to the principle of dealcohol condensation,organic solvents were used to replace alcohol water solvents,and γ-methacryloxypropyltrimethoxysilane (KH570) was used as modifier to modify in-situ. The infrared spectroscopy,scanning electron microscope,particle size analysis and a series of hydrophobic performance tests were used to characterize the product structure and evaluate the hydrophobic effect. The results show that the organic group is grafted onto the surface of nano-SiO_2 successfully through surface modification and the morphology of particle which size is about 50 nm with regularly spherical while agglomeration obviously reduces. The test of hydrophobic effect shows that the modified nano-SiO_2 can be uniformly dispersed in organic solvent and can be stable in paraffin solvent for more than 1 year. Owing to its water absorption decreases to 28% and lipophilicity increases to 62% as well as the contact angle increases from 23. 1° to 129. 8°,hydrophobic effect of the modified nano-SiO_2 is increased substantially.The investigation of the optimized modification show that the best modifier concentration is 60%,the best modification temperature is 100 ℃ and the best modification time is 25 h.
In order to prepare hydrophobic nano-SiO_2 and improve the dispersibility in polymer materials,the nano-SiO_2 was synthesized by the modified Stber method. According to the principle of dealcohol condensation,organic solvents were used to replace alcohol water solvents,and γ-methacryloxypropyltrimethoxysilane (KH570) was used as modifier to modify in-situ. The infrared spectroscopy,scanning electron microscope,particle size analysis and a series of hydrophobic performance tests were used to characterize the product structure and evaluate the hydrophobic effect. The results show that the organic group is grafted onto the surface of nano-SiO_2 successfully through surface modification and the morphology of particle which size is about 50 nm with regularly spherical while agglomeration obviously reduces. The test of hydrophobic effect shows that the modified nano-SiO_2 can be uniformly dispersed in organic solvent and can be stable in paraffin solvent for more than 1 year. Owing to its water absorption decreases to 28% and lipophilicity increases to 62% as well as the contact angle increases from 23. 1° to 129. 8°,hydrophobic effect of the modified nano-SiO_2 is increased substantially.The investigation of the optimized modification show that the best modifier concentration is 60%,the best modification temperature is 100 ℃ and the best modification time is 25 h.
引文
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[2]SI Y F,GUO Z G.Superwetting materials of oil-water emulsion separation[J].Chemistry Letters,2015,44(7):874-883.
[3]WANG X,WANG P,JIANG Y,et al.Facile surface modification of silica nanoparticles with a combination of noncovalent and covalent methods for composites application[J].Composites Science&Technology,2014,15(104):1-8.
[4]储艳兰,张凯.纳米二氧化硅的研究现状与进展[J].赤峰学院学报(自然科学版),2013,29(5):122-123.
[5]GHADIMI A,MOHAMMADI T,KASIRI N.A novel chemical surface modification for the fabrication of PEBA/Si O2nanocomposite membranes to separate CO2from syngas and natural gas streams[J].Industrial&Engineering Chemistry Research,2014,53(44):17476-17486.
[6]LIN Y F,ZHANG A Q,SUN J N,et al.Properties of natural rubber vulcanizates/nanosilica composites prepared based on the method of in-situ generation and coagulation[J].Journal of Macromolecular Science,Part B,2013,52(11):1494-1507.
[7]公绪强,王雅祺,张利,等.改性纳米二氧化硅增强增韧聚对苯二甲酸丁二醇酯[J].材料导报,2016,30(4):52-56.
[8]周鑫,杨飞,李传宪,等.无机纳米SiO2的表面改性研究[J].化工新型材料,2015,43(2):167-170.
[9]陈凯玲,赵蕴慧,袁晓燕.二氧化硅粒子的表面化学修饰:方法、原理及应用[J].化学进展,2013,25(1):95-104.
[10]何淑婷,刘宝春.纳米SiO2的表面改性[J].应用化工,2017,46(4):693-697.
[11]BURGEAT-LAMI E,ESPIARD P,GUYOT P A.Ethyl acrylate latexes encapsulating nanoparticles of silica:1.functionalization and dispersion of silica[J].Polymer,1995,36(23):4385-4389.
[12]ZHOU X C,ZHONG L P,XU Y P.Surface modification of silica aerogels with trimethylchlorosilane in the ambient pressure drying[J].Inorganic Materials,2008,44(9):976-979.
[13]武江红,杜志平,台秀梅.偶联剂改性纳米Si O2的制备与表征[J].印染助剂,2013,30(7):11-13.
[14]SHIN Y,LEE D,LEE K,et al.Surface properties of silica nanoparticles modified with polymers for polymer nanocomposite applications[J].Journal of Industrial and Engineering Chemistry,2008,14(4):515-519.
[15]任小明,赵辉,朱妍娇,等.纳米二氧化硅粒子的改性研究[J].湖北大学学报(自然科学版),2016,38(6):522-526.
[16]李小兵,刘莹.材料表面润湿性的控制与制备技术[J].材料工程,2008,52(4):74-80.
[17]JIANG L,WANG R,YANG B,et al.Binary cooperative complementary nanoscale interfacial materials[J].Pure and Applied Chemistry,2000,72(1/2):73-81.