改性白炭黑的制备及性能研究
摘要
本文以气相法白炭黑为原料,甲基三甲氧基硅烷和3-氯-2-羟丙基三甲基氯化铵为改性剂,采用连续干法和间歇干法分别对白炭黑表面进行了单一和复合改性,考察了改性剂用量、预处理温度、预处理时间、反应温度、反应时间、氮气流量、碱用量等因素对白炭黑表面改性效果的影响。通过测定白炭黑表面羟基数和电荷零点确定白炭黑的改性效果。
实验结果表明,甲基三甲氧基硅烷改性白炭黑时,提高预处理温度和延长预处理时间有利于白炭黑表面羟基数减少,连续干法改性较佳工艺条件为:甲基三甲氧基硅烷用量30%,预处理温度350℃,预处理时间10min,反应温度350℃,反应时间10min,氮气流量1.5m~3/h;间歇干法改性较佳工艺条件为:甲基三甲氧基硅烷用量15%,预处理温度120℃,预处理时间30min,反应温度160℃,反应时间30min;间歇干法的改性效果好于连续干法的。3-氯-2-羟丙基三甲基氯化铵改性白炭黑的表面电荷零点随着改性剂用量增加、反应温度的升高和反应时间的延长而增大,适宜工艺条件为:改性剂用量30%,反应温度120℃,反应时间30min,碱用量1.5%,用水量6%。复合改性白炭黑的适宜工艺条件为:甲基三甲氧基硅烷用量30%,3-氯-2-羟丙基三甲基氯化铵用量40%,反应温度130℃,反应时间30min,碱用量2%,用水量6%。
通过测定白炭黑比表面积和甲醇值表明,改性后的白炭黑比表面积下降,疏水性增强。红外光谱分析证明,白炭黑表面一部分羟基被改性剂的有机基团取代。乙醇中透光率测定和SEM测试表明,白炭黑表面羟基数越少,分散性越好,二次团聚体尺寸越小。抗菌性测试结果表明,接枝上季铵盐基团的白炭黑能抑制淀粉糊液生菌和提高淀粉糊液的储藏稳定性,其较佳用量为3%。
Surface single and composite modification of silica was studied by using fumed silica as raw material,methyl trimethoxysilane and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride as modified agent in this paper.The effect of factors such as amount of modified agent,preprocessing temperature,preprocessing time,reaction temperature, reaction time,flux of nitrogen gas,amount of alkali on surface modification degree was discussed by respectively using continuous dry method and periodic dry method. Modification degree was determined by measuring surface hydroxyl number and electric charge zero of fumed silica.
The experiment results showed that when silica is modified by using methyl trimethoxysilane,enhancing preprocessing temperature and extending preprocessing time are conducive to reducing surface hydroxyl number of silica,the better process conditions of silica modified by continuous dry method are that amount of methyl trimethoxysilane 30%,preprocessing temperature 350℃,preprocessing time 10min,reaction temperature 350℃,reaction time 10min,flux of nitrogen gas 1.5m~3/h;the better process conditions of silica modified by periodic dry method are that amount of methyl trimethoxysilane 15%, preprocessing temperature 120℃,preprocessing time 30min,reaction temperature 160℃, reaction time 30min;surface modification degree of periodic dry method is better than that of continuous dry method.Surface electric charge zero of silica modified by 3-chloro-2-hydroxypropyl trimethyl ammonium chloride increases with increasing amount of modified agent and reaction time,the better process conditions are that amount of modified agent 30%,reaction temperature 120℃,reaction time 30min,amount of alkali 1.5%,amount of adding water 6%.The better process conditions of composite modification are that amount of methyl trimethoxysilane 30%,amount of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride 40%,reaction temperature 130℃, reaction time 30min,amount of alkali 2%,amount of adding water 6%.
The results of ratio surface area and methanol value of silica showed that ratio surface area of modified silica decreases and hydrophobic property enhances.IR test proved that part of hydroxyl on silica surface is replaced by organic group of modified agent. Measurement of transmittance in ethanol and SEM showed that surface hydroxyl number of silica less,dispersion better,size of secondary aggregates smaller.The results of antibacterial measurement showed that silica with grafted quaternary ammonium group can restrain growing bacteria of starch paste and enhance storage stability of starch paste,the better adding amount is 3%.
实验结果表明,甲基三甲氧基硅烷改性白炭黑时,提高预处理温度和延长预处理时间有利于白炭黑表面羟基数减少,连续干法改性较佳工艺条件为:甲基三甲氧基硅烷用量30%,预处理温度350℃,预处理时间10min,反应温度350℃,反应时间10min,氮气流量1.5m~3/h;间歇干法改性较佳工艺条件为:甲基三甲氧基硅烷用量15%,预处理温度120℃,预处理时间30min,反应温度160℃,反应时间30min;间歇干法的改性效果好于连续干法的。3-氯-2-羟丙基三甲基氯化铵改性白炭黑的表面电荷零点随着改性剂用量增加、反应温度的升高和反应时间的延长而增大,适宜工艺条件为:改性剂用量30%,反应温度120℃,反应时间30min,碱用量1.5%,用水量6%。复合改性白炭黑的适宜工艺条件为:甲基三甲氧基硅烷用量30%,3-氯-2-羟丙基三甲基氯化铵用量40%,反应温度130℃,反应时间30min,碱用量2%,用水量6%。
通过测定白炭黑比表面积和甲醇值表明,改性后的白炭黑比表面积下降,疏水性增强。红外光谱分析证明,白炭黑表面一部分羟基被改性剂的有机基团取代。乙醇中透光率测定和SEM测试表明,白炭黑表面羟基数越少,分散性越好,二次团聚体尺寸越小。抗菌性测试结果表明,接枝上季铵盐基团的白炭黑能抑制淀粉糊液生菌和提高淀粉糊液的储藏稳定性,其较佳用量为3%。
Surface single and composite modification of silica was studied by using fumed silica as raw material,methyl trimethoxysilane and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride as modified agent in this paper.The effect of factors such as amount of modified agent,preprocessing temperature,preprocessing time,reaction temperature, reaction time,flux of nitrogen gas,amount of alkali on surface modification degree was discussed by respectively using continuous dry method and periodic dry method. Modification degree was determined by measuring surface hydroxyl number and electric charge zero of fumed silica.
The experiment results showed that when silica is modified by using methyl trimethoxysilane,enhancing preprocessing temperature and extending preprocessing time are conducive to reducing surface hydroxyl number of silica,the better process conditions of silica modified by continuous dry method are that amount of methyl trimethoxysilane 30%,preprocessing temperature 350℃,preprocessing time 10min,reaction temperature 350℃,reaction time 10min,flux of nitrogen gas 1.5m~3/h;the better process conditions of silica modified by periodic dry method are that amount of methyl trimethoxysilane 15%, preprocessing temperature 120℃,preprocessing time 30min,reaction temperature 160℃, reaction time 30min;surface modification degree of periodic dry method is better than that of continuous dry method.Surface electric charge zero of silica modified by 3-chloro-2-hydroxypropyl trimethyl ammonium chloride increases with increasing amount of modified agent and reaction time,the better process conditions are that amount of modified agent 30%,reaction temperature 120℃,reaction time 30min,amount of alkali 1.5%,amount of adding water 6%.The better process conditions of composite modification are that amount of methyl trimethoxysilane 30%,amount of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride 40%,reaction temperature 130℃, reaction time 30min,amount of alkali 2%,amount of adding water 6%.
The results of ratio surface area and methanol value of silica showed that ratio surface area of modified silica decreases and hydrophobic property enhances.IR test proved that part of hydroxyl on silica surface is replaced by organic group of modified agent. Measurement of transmittance in ethanol and SEM showed that surface hydroxyl number of silica less,dispersion better,size of secondary aggregates smaller.The results of antibacterial measurement showed that silica with grafted quaternary ammonium group can restrain growing bacteria of starch paste and enhance storage stability of starch paste,the better adding amount is 3%.
引文
[1]卢寿慈编.粉体加工技术.北京:中国轻工业出版社,1999.
[2]卢寿慈.矿物浮选原理.北京:冶金工业出版社,1987.
[3]郑水林编.粉体表面改性.北京:中国建材工业出版社,1995.
[4]赵凤起,王新华,鲍冠苓等.白炭黑对推进剂的硅橡胶包覆层材料性能的影响.含能材料,1997,(2):82.
[5]谢海安,戴宏程.超微细二氧化硅的改性研究及其应用.湖北化工,2001,(5):23.
[6]Krysztafkiewicz A,et al.Precipitated silicas modified with 3-aminopropyitriethoxysilane.Colloids and Surfaces A:Physicochemical and Engineering Aspects,2000,173(1-3):73.
[7]Spange S.Silica surface modification by cationic polymerization and carbenium intermediates.Prog.Polym.Sci.2000,25:781-849.
[8]荣葵一.关于石棉类矿物的若干问题.矿产保护与利用,1996,(6):21-24.
[9]陈烨璞等.表面活性剂的工业应用(一)碳酸钙的表面改性研究.表面活性剂工业,1997,(4):28-31.
[10]黄汉生.硅烷偶联剂及其应用技术动向.化工新型材料,1995,(11):23-26.
[11]杜仕国.复合材料用硅烷偶联剂的研究进展.玻璃钢/复合材料,1996,(4):32-36.
[12]Wood B J,Sanjurjo A,Tong G T,et al.Coating particles by chemical vapor deposition in fluidized bed reactors.Surface and Coating Technology,1991,49:228-232.
[13]李春忠,韩今依,华彬等.流态化CVD制备TiO_2-Al_2O_3复合粒子.无机材料学报,1994,9(4):404-410.
[14]朱以华,李春忠,吴秋芳.流化床反应器中α-FeOOH粒子表面水解包覆SiO-2过程研究.高等学校化学学报,1999,20(1):119-122.
[15]毋伟,卢寿慈.矿物颜填料机械力化学改性研究.矿产综合利用,2000,(6):22-25.
[16]卢寿慈编.工业悬浮液--性能,调制及加工.北京:化学工业出版社,2003.
[17]Jesionowski T,et al.The influence of filler modification on its aggregation and dispersion behaviour in silica/PBT composite.Composite Interfaces,2003,10(2-3):225-242.
[18]Zurawska J,et al.Effect of ammonium salts on dispersive and adsorptive parameters of silicas precipitated from sodium metasilicate solution.Colloids & Surfaces A:Phys.,2003,223(3):201-214.
[19]Jesionowski T.Preparation of colloidal silica from sodium metasilicate solution and sulphuric acid in emulsion medium.Colloids and Surfaces A,2001,190(1):153-165.
[20]Tsubokawa N,Ichioka Ⅰ,Satoh T,etc..Grafting of 'dendrimer-like' highly branched polymer onto ultrafine silica surface.Reactive & Functional polymers,1998,37(6):75-82.
[21]Krysztafkiewicz A,Jesionowski T,Binkowski S.Precipitated silicas modified with 3-aminopropyltriethoxysilane.Colloids and Surfaces A:Phys.,2000,173(1):73-84.
[22]Zhang K,Chen H T,Chen X,et al.Monodisperse silica-polymer core-shell microspheres via surface grafting and emulsion polymerization.Macromol Mater Eng,2003,288:380.
[23]伍林,易德莲,曹淑超等.六甲基二硅胺烷改性纳米二氧化硅.武汉科技大学学报(自然科学版),2005,28(1):32-34.
[24]欧阳兆辉.纳米二氧化硅的改性及其在丁基橡胶中应用研究:(硕士学位论文).武汉:武汉科技大学,2005.
[25]Barthel H.Surface interactions of dimethylsiloxy group-modified fumed silica.Hysicochemical and Engineering Aspect,1995,101:217-226.
[26]Etienne M,Walcarius A.Analytical investigation of the chemical reactivity and stability of aminopropyl-grafted silica in aqueous medium.Talanta,2003,59:1173-1188.
[27]何凯,陈宏刚.聚乙二醇对碳酸化法白炭黑的表面改性研究.化学反应工程与工艺,2006,22(2):181-184.
[28]姚英.表面活性剂对碳化法制备白炭黑的影响研究.天津化工,2006,20(4):36-37.
[29]陈云辉,李文芳,杜军等.纳米SiO_2粉体新型表面活性剂复合改性工艺研究.表面技术,2006,35(5):34-36.
[30]Tertykh V A,Yanishpolskii V V,Panova O Y.Covalent attachment of some phenol derivatives to the silica surface by use of single-stage aminomethylation.Journal of Thermal Analysis and Calorimetry,2000,(62):545-549.
[31]汪齐方,李春忠,王志庭等.六甲基二硅胺烷对气相法白炭黑的表面改性.华东理工大学学报,2001,27(6):626-630.
[32]Jesionowski T,Krysztafkiewicz A.Comparison of the techniques used to modify amorphous hydrated silicas.Jourmal of Non-Crystalline Solids,2000,277:45-57.
[33]Jesionowski T,Krysztafkiewicz A.Influence of silane coupling agents on surface properties of precipitated silicas.Applied Surface Science,2001,172:18-32.
[34]Mouanda B,Viel P,Blanche C.Surface characterization of a potential photoactive LC coupling agent.Thin solid film,1998,323:42-52.
[35]Kothe M,Muller M,Simon F,et al.Examination of poly(butadiene epoxide) -coatings on inorganic surfaces.Colloids and Surfaces A:Phys.,1999,154(1):75-85.
[36]毋伟,陈建峰,邵磊等.聚合物接枝改性超细二氧化硅表面状况及形成机理.北京化工大学学报(自然科学版),2003,30(2):1-4.
[37]潘懋.滴定法测定气相法白炭黑比表面积的讨论.化学世界,1993,(8):380-383.
[38]陆泗进.几种合成氧化物矿物电化学性质测定的研究:(硕士学位论文).武汉:华中农业大学,2004.
[39]王惠玲,宁延生.新型疏水二氧化硅的制备.无机盐工业,2002,34(2):33-35.
[40]孙秀果,魏雨,贾振斌.纳米二氧化钛粉体在水中的分散行为.电子组件与材料,2003,(5):11-13.
[41]陈宏,陶萍,陈晓丽等.两种气相法白炭黑水分测定方法的比较.橡胶工业,2000,47(2):103-105.
[42]Gun'ko V M,Voronin E F,Mironyuk I F,et al.The effect of heat,adsorption and mechanochemical treatments on stuck structure and adsorption properties of fumed silicas.Colloids and Surface A:Physicochemical Engineering Aspects,2003,(218):125-135.
[43]欧阳兆辉,伍林,李孔标等.气相法改性纳米二氧化硅表面.化工进展,2005,24(11):1265-1268.
[44]李爱蓉,周勇,石炎福等.原生纳米颗粒SiO_2中添加大粒径组分的流化性能.化工设计,2004,14(1):43-45.
[45]冯钦邦,刘莉,龙成坤.气相法白炭黑表面化学改性及其改性效果的表征.有机硅氟资讯,2008,(2):48-50.
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[2]卢寿慈.矿物浮选原理.北京:冶金工业出版社,1987.
[3]郑水林编.粉体表面改性.北京:中国建材工业出版社,1995.
[4]赵凤起,王新华,鲍冠苓等.白炭黑对推进剂的硅橡胶包覆层材料性能的影响.含能材料,1997,(2):82.
[5]谢海安,戴宏程.超微细二氧化硅的改性研究及其应用.湖北化工,2001,(5):23.
[6]Krysztafkiewicz A,et al.Precipitated silicas modified with 3-aminopropyitriethoxysilane.Colloids and Surfaces A:Physicochemical and Engineering Aspects,2000,173(1-3):73.
[7]Spange S.Silica surface modification by cationic polymerization and carbenium intermediates.Prog.Polym.Sci.2000,25:781-849.
[8]荣葵一.关于石棉类矿物的若干问题.矿产保护与利用,1996,(6):21-24.
[9]陈烨璞等.表面活性剂的工业应用(一)碳酸钙的表面改性研究.表面活性剂工业,1997,(4):28-31.
[10]黄汉生.硅烷偶联剂及其应用技术动向.化工新型材料,1995,(11):23-26.
[11]杜仕国.复合材料用硅烷偶联剂的研究进展.玻璃钢/复合材料,1996,(4):32-36.
[12]Wood B J,Sanjurjo A,Tong G T,et al.Coating particles by chemical vapor deposition in fluidized bed reactors.Surface and Coating Technology,1991,49:228-232.
[13]李春忠,韩今依,华彬等.流态化CVD制备TiO_2-Al_2O_3复合粒子.无机材料学报,1994,9(4):404-410.
[14]朱以华,李春忠,吴秋芳.流化床反应器中α-FeOOH粒子表面水解包覆SiO-2过程研究.高等学校化学学报,1999,20(1):119-122.
[15]毋伟,卢寿慈.矿物颜填料机械力化学改性研究.矿产综合利用,2000,(6):22-25.
[16]卢寿慈编.工业悬浮液--性能,调制及加工.北京:化学工业出版社,2003.
[17]Jesionowski T,et al.The influence of filler modification on its aggregation and dispersion behaviour in silica/PBT composite.Composite Interfaces,2003,10(2-3):225-242.
[18]Zurawska J,et al.Effect of ammonium salts on dispersive and adsorptive parameters of silicas precipitated from sodium metasilicate solution.Colloids & Surfaces A:Phys.,2003,223(3):201-214.
[19]Jesionowski T.Preparation of colloidal silica from sodium metasilicate solution and sulphuric acid in emulsion medium.Colloids and Surfaces A,2001,190(1):153-165.
[20]Tsubokawa N,Ichioka Ⅰ,Satoh T,etc..Grafting of 'dendrimer-like' highly branched polymer onto ultrafine silica surface.Reactive & Functional polymers,1998,37(6):75-82.
[21]Krysztafkiewicz A,Jesionowski T,Binkowski S.Precipitated silicas modified with 3-aminopropyltriethoxysilane.Colloids and Surfaces A:Phys.,2000,173(1):73-84.
[22]Zhang K,Chen H T,Chen X,et al.Monodisperse silica-polymer core-shell microspheres via surface grafting and emulsion polymerization.Macromol Mater Eng,2003,288:380.
[23]伍林,易德莲,曹淑超等.六甲基二硅胺烷改性纳米二氧化硅.武汉科技大学学报(自然科学版),2005,28(1):32-34.
[24]欧阳兆辉.纳米二氧化硅的改性及其在丁基橡胶中应用研究:(硕士学位论文).武汉:武汉科技大学,2005.
[25]Barthel H.Surface interactions of dimethylsiloxy group-modified fumed silica.Hysicochemical and Engineering Aspect,1995,101:217-226.
[26]Etienne M,Walcarius A.Analytical investigation of the chemical reactivity and stability of aminopropyl-grafted silica in aqueous medium.Talanta,2003,59:1173-1188.
[27]何凯,陈宏刚.聚乙二醇对碳酸化法白炭黑的表面改性研究.化学反应工程与工艺,2006,22(2):181-184.
[28]姚英.表面活性剂对碳化法制备白炭黑的影响研究.天津化工,2006,20(4):36-37.
[29]陈云辉,李文芳,杜军等.纳米SiO_2粉体新型表面活性剂复合改性工艺研究.表面技术,2006,35(5):34-36.
[30]Tertykh V A,Yanishpolskii V V,Panova O Y.Covalent attachment of some phenol derivatives to the silica surface by use of single-stage aminomethylation.Journal of Thermal Analysis and Calorimetry,2000,(62):545-549.
[31]汪齐方,李春忠,王志庭等.六甲基二硅胺烷对气相法白炭黑的表面改性.华东理工大学学报,2001,27(6):626-630.
[32]Jesionowski T,Krysztafkiewicz A.Comparison of the techniques used to modify amorphous hydrated silicas.Jourmal of Non-Crystalline Solids,2000,277:45-57.
[33]Jesionowski T,Krysztafkiewicz A.Influence of silane coupling agents on surface properties of precipitated silicas.Applied Surface Science,2001,172:18-32.
[34]Mouanda B,Viel P,Blanche C.Surface characterization of a potential photoactive LC coupling agent.Thin solid film,1998,323:42-52.
[35]Kothe M,Muller M,Simon F,et al.Examination of poly(butadiene epoxide) -coatings on inorganic surfaces.Colloids and Surfaces A:Phys.,1999,154(1):75-85.
[36]毋伟,陈建峰,邵磊等.聚合物接枝改性超细二氧化硅表面状况及形成机理.北京化工大学学报(自然科学版),2003,30(2):1-4.
[37]潘懋.滴定法测定气相法白炭黑比表面积的讨论.化学世界,1993,(8):380-383.
[38]陆泗进.几种合成氧化物矿物电化学性质测定的研究:(硕士学位论文).武汉:华中农业大学,2004.
[39]王惠玲,宁延生.新型疏水二氧化硅的制备.无机盐工业,2002,34(2):33-35.
[40]孙秀果,魏雨,贾振斌.纳米二氧化钛粉体在水中的分散行为.电子组件与材料,2003,(5):11-13.
[41]陈宏,陶萍,陈晓丽等.两种气相法白炭黑水分测定方法的比较.橡胶工业,2000,47(2):103-105.
[42]Gun'ko V M,Voronin E F,Mironyuk I F,et al.The effect of heat,adsorption and mechanochemical treatments on stuck structure and adsorption properties of fumed silicas.Colloids and Surface A:Physicochemical Engineering Aspects,2003,(218):125-135.
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