膨润土有机凝胶的制备与特性的研究
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摘要
膨润土有机凝胶是一种触变性凝胶，主要用作有机分散体系的增稠剂、粘度调节剂、触变剂、悬浮剂、乳胶稳定剂和吸附剂，目前已在深井钻井泥浆、油漆、油墨、润滑脂、日用化学品工业、药膏方面得到了广泛应用。此外，还是制备性能优异的聚合物／蒙脱石纳米复合材料的原料。本文以辽宁钙基膨润土为原料，首先对其钠化提纯，然后以十八／十六烷基氯化铵为有机复合剂，采用水热合成技术对膨润土进行有机改性，将改性膨润土充分分散于二甲苯-甲醇体系中制备出产品质量稳定、性能国内领先的膨润土高档有机凝胶矿物材料。利用XRD、TEM等测试分析手段和现代胶体化学理论表征其结构和性能，探讨了材料的形成机理、凝胶特性、纳米特性、触变性以及在环氧防锈漆中的应用等。论文的研究内容及主要结果为：
1．在系统研究膨润土原矿物理性质、矿物组成和化学成分的基础上进行钠化提纯，确定了钠化提纯适宜的工艺流程和工艺参数。研究表明：膨润土原矿经过钠化提纯后，其物理化学性能均发生了明显改善，杂质矿物含量显著降低，蒙脱石含量提高至90.0％，钠化提纯效果良好；提纯工艺采用连续动态离心技术，能保证钠化提纯产品质量的稳定，从而为后续的有机改性、凝胶的制备提供性能优异、质量稳定的基料。
2．以钠化改型高纯膨润土为基料，十八／十六烷基氯化铵为有机复合剂，采用二甲苯-甲醇为有机分散体系，通过水热合成、压滤脱水、粉碎干燥、凝胶的制备等工艺，制备出质量稳定、动力粘度5.0Pa·s的膨润土有机凝胶。研究了影响膨润土有机凝胶性能的主要因素：水热合成反应作业反应釜中设置温度自动控制系统；粉碎干燥采用强力粉碎干燥工艺，使干燥与碎散同时进行，既提高了干燥效率，又避免过分干燥而降低产品质量；膨润土基料选择低层电荷膨润土；通过不同覆盖剂用量、不同反应时间、不同矿浆pH值的正交试验及显著因素的单因素优化试验，确定了有机改性最佳的工艺条件；考察了产品水分对膨润土有机凝胶性能的影响，确定了有机改性产品水分适宜的控制范围。通过上述工艺流程的优化和工艺条件的试验，可保证膨润土有机凝胶产品质量稳定、性能优良，工业化后经济效益较好。
3．利用XRD、TEM等测试分析手段和现代胶体化学理论研究膨润土有机凝胶的特性和结构。研究表明：膨润土有机凝胶是分散的有机蒙脱石以端-端、端-面结合形成包裹大量溶剂的网架结构的假塑性体，为一种弹性冻胶；有机覆盖剂十八／十六烷基氯化铵在蒙脱石晶层间呈倾斜单层排布，其直链与硅氧层面的夹角α=25.9°；温度对凝胶性能的影响也较为显著；通过电镜照片分析及对分散凝胶的观察，有机改性膨润土在有机介质中，被分散成具透明性的纳米凝胶，用于高档油漆、化妆品及聚合物／蒙脱石纳米复合材料等高新技术领域，市场前景广阔；膨润土有机凝胶的触变性较好，触变值为1.6。膨润土有机凝胶溶胀的动力学理论模型可表述为：
(1)凝胶表面线性扩散过程，动力学方程为：W_t／W_m=k_0／(C_0d)t；
(2)凝胶内部网络的溶胀过程，可用Li-Tanaka方程处理，动力学方程为：
4．膨润土有机凝胶在环氧防锈漆中的应用试验表明：将膨润土有机凝胶在环氧防锈漆中进行应用后发现，环氧防锈漆制漆过程中分散性、研磨效果都较好，油漆研磨后不易沉底，涂膜主要机械物理性能均优良，对于提高涂料的贮存稳定性效果更佳，在油漆中推广应用具备显著的性能竞争优势。
The organic bentonite gel is a kind of thixotropic gel. It is mainly used as the thickener, viscosity regulator, thixotrope, agent for suspension, emulsion stabilizer and adsorbent in organic disperse system. It has been used extensively in oil-based drill slurry, paint, print ink, lubricant grease, household chemical industrial products and ointment, etc. In addition, it is a raw material for polymer/ montmorillonite nanometer compound material. In this paper, using Liaoning's Ca-bentonite as matrices, modifying with sodium compound at first, organically modifying with Octadecyl/Hexadecyl ammonium chloride as the cover agent, based on hydrothermal process, and dispersing the modified bentonite into the dimethyl benzene-methyl alcohol system fully, we synthesized the high-grade organic bentonite gel with stable quality and excellent characteristics. By some test and analyze methods as XRD, TEM etc., and by modern colloid chemistry theories, we investigated the structure and properties of the gel, the synthesized mechanism of the material, the gel characteristics, the nanometer characteristics, the thixotropy of the organic gel and its application in the epoxy-resin anti-rusting paint etc. The main contents and results of the paper are included as following:
1. The suitable modification and purification process and process parameters are selected by sodium modification and purification experiment based on studying systematically the physical properties, mineral and chemical compositions of the bentonite run-of mine. The results show that after the sodium purification, the physical and chemical properties are improved significantly; the impurity in the bentonite sample has obviously decreased; the montmorillonite content are raised to 90%; the sodium purification has a remarkable effect. The purification process uses the continuous dynamic centrifugal separation technique to guarantee the quality stability of sodium purified product, so it can provide the matrix with excellent properties and stable quality to the next organic modification and gel synthesis.
2. The organic bentonite gel with 5.0Pa·s and stable quality is synthesized using sodium purified bentonite as matrix, octadecyl/Hexadecyl ammonium chloride as the cover agent, dimethyl benzene-methyl alcohol as the organic dispersant, based on hydrothermal process, filtering, grinding and drying, gel synthesis process etc. The main influence elements on the gel properties are studied. The hydrothermal process uses the auto control system of the temperature in the reaction kettle. The grinding and drying process uses strong-power grinding and drying process. It makes grinding and drying carry out at the same time to promote the drying efficiency and avoid the excessive dry and reduce the product quality. The bentonite matrix selects the low layer charge bentonite. The optimum process conditions of organic modification are determined by the orthogonal tests with different cover agent dosages and pulp pH values and different reaction time and the single element optimization test. The influence of the moisture content of the organic bentonite product on the gel characteristics is studied, so the suitable range of the moisture content is determined. The quality stability and excellent properties of the organic bentonite gel can be guaranteed by the above-mentioned process optimization and process conditions experiment. The economic benefit is good if the organic bentonite product is industrial.
3. By some test and analyze methods as XRD, TEM etc., and by modern colloid chemistry theories, we investigated the structure and properties of the gel. The results show that the organic bentonite gel is an artificial space-truss-structure plastomer with large quantity of solution, which is formed by dispersed organic montmorillonite with end-to-end and end-to-face combination and it is a kind of elastic and jelly gel. The organic cover agent Octadecyl/Hexadecyl ammonium chloride configurated in montmorillonite interlayer with paraffin-type monolayer. The angle between the straight chain and the Si-0 layer is 25.9°. The influence of gel temperature on the gel properties is remarkable. By analyzing the TEM photos and observing the dispersed gel, the organic bentonite gel has favorable transparence and nanometer effect. It can be used in such high-new technical fields as high-grade paint, cosmetic and polymer/ montmorillonite nanometer compound material etc. The thixotropy of the organic bentonite gel is good and the thixotropy value is about 1.6.The dynamic theory models of the organic bentonite gel swelling can be described:
(1) the linear diffusion of the surface region swelling, the dynamic equation
(2) the swelling in the gel internal space-truss-structure is described withLi-Tanaka equation, the dynamic equation is
4. The application experiment in the epoxy-resin anti-rusting paint of the organic bentonite gel indicates: After the organic bentonite gel is used in the paint, it can make the dispersive and grinding effect of the paint better, make the paint not easy to sink to the bottom, make the main mechanical physical properties excellent, and it can improve the storage stability of the paint more effectively, so it would have a properties advantage if it would be used in the paint extensively.
1．在系统研究膨润土原矿物理性质、矿物组成和化学成分的基础上进行钠化提纯，确定了钠化提纯适宜的工艺流程和工艺参数。研究表明：膨润土原矿经过钠化提纯后，其物理化学性能均发生了明显改善，杂质矿物含量显著降低，蒙脱石含量提高至90.0％，钠化提纯效果良好；提纯工艺采用连续动态离心技术，能保证钠化提纯产品质量的稳定，从而为后续的有机改性、凝胶的制备提供性能优异、质量稳定的基料。
2．以钠化改型高纯膨润土为基料，十八／十六烷基氯化铵为有机复合剂，采用二甲苯-甲醇为有机分散体系，通过水热合成、压滤脱水、粉碎干燥、凝胶的制备等工艺，制备出质量稳定、动力粘度5.0Pa·s的膨润土有机凝胶。研究了影响膨润土有机凝胶性能的主要因素：水热合成反应作业反应釜中设置温度自动控制系统；粉碎干燥采用强力粉碎干燥工艺，使干燥与碎散同时进行，既提高了干燥效率，又避免过分干燥而降低产品质量；膨润土基料选择低层电荷膨润土；通过不同覆盖剂用量、不同反应时间、不同矿浆pH值的正交试验及显著因素的单因素优化试验，确定了有机改性最佳的工艺条件；考察了产品水分对膨润土有机凝胶性能的影响，确定了有机改性产品水分适宜的控制范围。通过上述工艺流程的优化和工艺条件的试验，可保证膨润土有机凝胶产品质量稳定、性能优良，工业化后经济效益较好。
3．利用XRD、TEM等测试分析手段和现代胶体化学理论研究膨润土有机凝胶的特性和结构。研究表明：膨润土有机凝胶是分散的有机蒙脱石以端-端、端-面结合形成包裹大量溶剂的网架结构的假塑性体，为一种弹性冻胶；有机覆盖剂十八／十六烷基氯化铵在蒙脱石晶层间呈倾斜单层排布，其直链与硅氧层面的夹角α=25.9°；温度对凝胶性能的影响也较为显著；通过电镜照片分析及对分散凝胶的观察，有机改性膨润土在有机介质中，被分散成具透明性的纳米凝胶，用于高档油漆、化妆品及聚合物／蒙脱石纳米复合材料等高新技术领域，市场前景广阔；膨润土有机凝胶的触变性较好，触变值为1.6。膨润土有机凝胶溶胀的动力学理论模型可表述为：
(1)凝胶表面线性扩散过程，动力学方程为：W_t／W_m=k_0／(C_0d)t；
(2)凝胶内部网络的溶胀过程，可用Li-Tanaka方程处理，动力学方程为：
4．膨润土有机凝胶在环氧防锈漆中的应用试验表明：将膨润土有机凝胶在环氧防锈漆中进行应用后发现，环氧防锈漆制漆过程中分散性、研磨效果都较好，油漆研磨后不易沉底，涂膜主要机械物理性能均优良，对于提高涂料的贮存稳定性效果更佳，在油漆中推广应用具备显著的性能竞争优势。
The organic bentonite gel is a kind of thixotropic gel. It is mainly used as the thickener, viscosity regulator, thixotrope, agent for suspension, emulsion stabilizer and adsorbent in organic disperse system. It has been used extensively in oil-based drill slurry, paint, print ink, lubricant grease, household chemical industrial products and ointment, etc. In addition, it is a raw material for polymer/ montmorillonite nanometer compound material. In this paper, using Liaoning's Ca-bentonite as matrices, modifying with sodium compound at first, organically modifying with Octadecyl/Hexadecyl ammonium chloride as the cover agent, based on hydrothermal process, and dispersing the modified bentonite into the dimethyl benzene-methyl alcohol system fully, we synthesized the high-grade organic bentonite gel with stable quality and excellent characteristics. By some test and analyze methods as XRD, TEM etc., and by modern colloid chemistry theories, we investigated the structure and properties of the gel, the synthesized mechanism of the material, the gel characteristics, the nanometer characteristics, the thixotropy of the organic gel and its application in the epoxy-resin anti-rusting paint etc. The main contents and results of the paper are included as following:
1. The suitable modification and purification process and process parameters are selected by sodium modification and purification experiment based on studying systematically the physical properties, mineral and chemical compositions of the bentonite run-of mine. The results show that after the sodium purification, the physical and chemical properties are improved significantly; the impurity in the bentonite sample has obviously decreased; the montmorillonite content are raised to 90%; the sodium purification has a remarkable effect. The purification process uses the continuous dynamic centrifugal separation technique to guarantee the quality stability of sodium purified product, so it can provide the matrix with excellent properties and stable quality to the next organic modification and gel synthesis.
2. The organic bentonite gel with 5.0Pa·s and stable quality is synthesized using sodium purified bentonite as matrix, octadecyl/Hexadecyl ammonium chloride as the cover agent, dimethyl benzene-methyl alcohol as the organic dispersant, based on hydrothermal process, filtering, grinding and drying, gel synthesis process etc. The main influence elements on the gel properties are studied. The hydrothermal process uses the auto control system of the temperature in the reaction kettle. The grinding and drying process uses strong-power grinding and drying process. It makes grinding and drying carry out at the same time to promote the drying efficiency and avoid the excessive dry and reduce the product quality. The bentonite matrix selects the low layer charge bentonite. The optimum process conditions of organic modification are determined by the orthogonal tests with different cover agent dosages and pulp pH values and different reaction time and the single element optimization test. The influence of the moisture content of the organic bentonite product on the gel characteristics is studied, so the suitable range of the moisture content is determined. The quality stability and excellent properties of the organic bentonite gel can be guaranteed by the above-mentioned process optimization and process conditions experiment. The economic benefit is good if the organic bentonite product is industrial.
3. By some test and analyze methods as XRD, TEM etc., and by modern colloid chemistry theories, we investigated the structure and properties of the gel. The results show that the organic bentonite gel is an artificial space-truss-structure plastomer with large quantity of solution, which is formed by dispersed organic montmorillonite with end-to-end and end-to-face combination and it is a kind of elastic and jelly gel. The organic cover agent Octadecyl/Hexadecyl ammonium chloride configurated in montmorillonite interlayer with paraffin-type monolayer. The angle between the straight chain and the Si-0 layer is 25.9°. The influence of gel temperature on the gel properties is remarkable. By analyzing the TEM photos and observing the dispersed gel, the organic bentonite gel has favorable transparence and nanometer effect. It can be used in such high-new technical fields as high-grade paint, cosmetic and polymer/ montmorillonite nanometer compound material etc. The thixotropy of the organic bentonite gel is good and the thixotropy value is about 1.6.The dynamic theory models of the organic bentonite gel swelling can be described:
(1) the linear diffusion of the surface region swelling, the dynamic equation
(2) the swelling in the gel internal space-truss-structure is described withLi-Tanaka equation, the dynamic equation is
4. The application experiment in the epoxy-resin anti-rusting paint of the organic bentonite gel indicates: After the organic bentonite gel is used in the paint, it can make the dispersive and grinding effect of the paint better, make the paint not easy to sink to the bottom, make the main mechanical physical properties excellent, and it can improve the storage stability of the paint more effectively, so it would have a properties advantage if it would be used in the paint extensively.
引文
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