葡萄糖酸改性碱性钙基膨润土的制备及应用研究
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摘要
碱性钙基膨润土是近年开发出的第一种阴离子交换型膨润土,该膨润土层间钙离子带有活性氢氧根,为更多的有机物进入膨润土层间提供了可能,利用丰富的有机酸资源对碱性钙基膨润土进行有机改性可得到用途广泛的有机酸膨润土。葡萄糖酸是一种多羟基有机酸,用它改性碱性钙基膨润土后可得到一种多羟基有机膨润土,其亲水性好,与多羟基类高分子材料或大分子有着很好的相容性。
本文以葡萄糖酸改性碱性钙基膨润土为出发点,一方面在温和的反应条件下进行表面改性,在保持其层状结构的前提下,增加其表面的羟基数量,得到脱水能力强、稳定性良好的葡萄糖酸改性膨润土脱水材料;另一方面使葡萄糖酸分子充分进入层间与OH~-发生酸碱中和反应,因激烈放热致使膨润土层板发生剥离,层片达到纳米尺度,制得粒子剥离型葡萄糖酸纳米蒙脱石(P-EGAM)。葡萄糖酸纳米蒙脱石作为一种无机/有机复合纳米材料,可以对天然高分子或已经聚合的亲水性高分子材料实现膨润土高度分散改性。
本文通过单因素实验,分别探索出葡萄糖酸改性膨润土脱水材料和葡萄糖酸纳米蒙脱石制备的最佳工艺参数,并利用红外光谱、X射线衍射、差热分析和电子显微镜等手段对合成的产物进行结构表征。同时,对这两种材料的性能及应用作了初步研究。结构表征及应用结果表明,葡萄糖酸改性膨润土脱水材料仍保持碱性钙基膨润土的层状结构和层间距,表面粗糙多孔,热稳定性好,脱水再生温度低,在乙醇常压蒸汽脱水应用中,当乙醇进料质量浓度为95%时,每克吸附剂可生产99.5%乙醇0.706 g;表征结果表明葡萄糖酸纳米蒙脱石为葡萄糖酸表面修饰的蒙脱石粒子,热稳定性与葡萄糖酸钙相同,内部结构及形貌相对碱性钙基膨润土均已发生了明显的变化,粒子为厚度小于100 nm的纳米片。在淀粉糊添加P-EGAM制备P-EGAM/淀粉复合材料的应用实验中,P-EGAM能达到增粘的效果,并存在最佳添加量为2.5%。最后,综合对比两种材料的制备、表征、应用等结果,初步推测葡萄糖酸蒙脱石的剥离机理,并根据产品DSC的吸热焓变数据,定量计算了产品的剥离率。
葡萄糖酸改性碱性钙其膨润土的研究与开发,可以将膨润土和木薯淀粉两种资源的开发与利用有机地结合起来,拓宽膨润土在有机溶剂脱水、亲水性高分子复合材料方面的应用。
Alkaline Ca-bentonite is the first anion exchange bentonite which has been developed in recent years. Because calcium ion in the bentonite layer with activity hydroxide, it make possibility to more organics intercalate into the bentonite layer. Using organic acids which is rich in nature, alkaline Ca-bentonite can be modified by a wide range of organic acid bentonite. Gluconic acid is a polyhydroxy organic acid, and it can modify alkaline Ca-bentonite make a polyhydroxy bentonite which is good hydrophilicity and good compatibility for polyhydroxy polymer or macromolecular.
In this work, gluconic acid modified alkaline Ca-bentonite as the starting point, on the one hand, the bentonite modified reaction was carried on under mild conditions so as to maintain the layered structure, and the numbers of hydroxyl of bentonite surface were increased. Gluconic acid modified bentonite which is a good capacity and stability anhydrous material was prepared. On the other hand, let gluconic acid molecule fully enter the bentonite layer and occurre acid-base neutralization reaction with OH" in layer. Due to intense heat of the reaction, the bentonite layers were exfoliated into nano-piece. Then particle exfoliated gluconic acid nano-montmorillonite (P-EGAM) was prepared. As an inorganic/ organic composite nano-materials, gluconic acid nano-montmorillonite can modify the natural polymers or polymerized hydrophilicity macromolecular to a high degree decentralize.
In this paper, optimum preparation conditions of gluconic acid modified bentonite anhydrous material and paticle exfoliated gluconic acid montmorillonite were obtained through single-factor experiment. Using IRD, XRD, DSC and SEM, structure of the products were characterized. At the same time, both the properties and application of this two materials were preliminary studied. Results of characterization and application showed that the new anhydrous material remains the layered structure and the layer spacing of alkaline Ca-bentonite. It also indicates that the new anhydrous material has porous and roughness surface, and is good thermostability and regeneration of low temperature. Result of application in normal pressure ethanol vapor dehydration showed, when ethanol concentration in the feed was 95% (mass), production capacity was 0.706 gram product·(gram adsorbent)~(-1). Results of characterization and application showed that the particle exfoliated gluconic acid montmorillonite was a montmorillonite particle modified by gluconic acid. Its thermostability was similarly to calcium gluconate. Its interior structure and surface were changed apparently. It was a nano-piece which thickness was smaller than 100 nm. The application result in cassava starch modification showed that the P-EGAM could increase the viscosity of P-EGAM/ starch composites, and the optimal proportion of P-EGAM addition is 2.5%. Finally, exfoliated mechanism was preliminary speculated by comprehensive comparison of preparation, characterization and application of the two materials. From data of endothermic enthalpy change of DSC, exfoliated rate of gluconic acid montmorillonite was calculated.
Research and development of gluconic acid modified alkaline Ca-bentonite can combine organically with the development of bentonite and cassava starch. It also can broaden the application of bentonite in the field of dehydration of organic solvents and hydrophilic polymer composite material.
本文以葡萄糖酸改性碱性钙基膨润土为出发点,一方面在温和的反应条件下进行表面改性,在保持其层状结构的前提下,增加其表面的羟基数量,得到脱水能力强、稳定性良好的葡萄糖酸改性膨润土脱水材料;另一方面使葡萄糖酸分子充分进入层间与OH~-发生酸碱中和反应,因激烈放热致使膨润土层板发生剥离,层片达到纳米尺度,制得粒子剥离型葡萄糖酸纳米蒙脱石(P-EGAM)。葡萄糖酸纳米蒙脱石作为一种无机/有机复合纳米材料,可以对天然高分子或已经聚合的亲水性高分子材料实现膨润土高度分散改性。
本文通过单因素实验,分别探索出葡萄糖酸改性膨润土脱水材料和葡萄糖酸纳米蒙脱石制备的最佳工艺参数,并利用红外光谱、X射线衍射、差热分析和电子显微镜等手段对合成的产物进行结构表征。同时,对这两种材料的性能及应用作了初步研究。结构表征及应用结果表明,葡萄糖酸改性膨润土脱水材料仍保持碱性钙基膨润土的层状结构和层间距,表面粗糙多孔,热稳定性好,脱水再生温度低,在乙醇常压蒸汽脱水应用中,当乙醇进料质量浓度为95%时,每克吸附剂可生产99.5%乙醇0.706 g;表征结果表明葡萄糖酸纳米蒙脱石为葡萄糖酸表面修饰的蒙脱石粒子,热稳定性与葡萄糖酸钙相同,内部结构及形貌相对碱性钙基膨润土均已发生了明显的变化,粒子为厚度小于100 nm的纳米片。在淀粉糊添加P-EGAM制备P-EGAM/淀粉复合材料的应用实验中,P-EGAM能达到增粘的效果,并存在最佳添加量为2.5%。最后,综合对比两种材料的制备、表征、应用等结果,初步推测葡萄糖酸蒙脱石的剥离机理,并根据产品DSC的吸热焓变数据,定量计算了产品的剥离率。
葡萄糖酸改性碱性钙其膨润土的研究与开发,可以将膨润土和木薯淀粉两种资源的开发与利用有机地结合起来,拓宽膨润土在有机溶剂脱水、亲水性高分子复合材料方面的应用。
Alkaline Ca-bentonite is the first anion exchange bentonite which has been developed in recent years. Because calcium ion in the bentonite layer with activity hydroxide, it make possibility to more organics intercalate into the bentonite layer. Using organic acids which is rich in nature, alkaline Ca-bentonite can be modified by a wide range of organic acid bentonite. Gluconic acid is a polyhydroxy organic acid, and it can modify alkaline Ca-bentonite make a polyhydroxy bentonite which is good hydrophilicity and good compatibility for polyhydroxy polymer or macromolecular.
In this work, gluconic acid modified alkaline Ca-bentonite as the starting point, on the one hand, the bentonite modified reaction was carried on under mild conditions so as to maintain the layered structure, and the numbers of hydroxyl of bentonite surface were increased. Gluconic acid modified bentonite which is a good capacity and stability anhydrous material was prepared. On the other hand, let gluconic acid molecule fully enter the bentonite layer and occurre acid-base neutralization reaction with OH" in layer. Due to intense heat of the reaction, the bentonite layers were exfoliated into nano-piece. Then particle exfoliated gluconic acid nano-montmorillonite (P-EGAM) was prepared. As an inorganic/ organic composite nano-materials, gluconic acid nano-montmorillonite can modify the natural polymers or polymerized hydrophilicity macromolecular to a high degree decentralize.
In this paper, optimum preparation conditions of gluconic acid modified bentonite anhydrous material and paticle exfoliated gluconic acid montmorillonite were obtained through single-factor experiment. Using IRD, XRD, DSC and SEM, structure of the products were characterized. At the same time, both the properties and application of this two materials were preliminary studied. Results of characterization and application showed that the new anhydrous material remains the layered structure and the layer spacing of alkaline Ca-bentonite. It also indicates that the new anhydrous material has porous and roughness surface, and is good thermostability and regeneration of low temperature. Result of application in normal pressure ethanol vapor dehydration showed, when ethanol concentration in the feed was 95% (mass), production capacity was 0.706 gram product·(gram adsorbent)~(-1). Results of characterization and application showed that the particle exfoliated gluconic acid montmorillonite was a montmorillonite particle modified by gluconic acid. Its thermostability was similarly to calcium gluconate. Its interior structure and surface were changed apparently. It was a nano-piece which thickness was smaller than 100 nm. The application result in cassava starch modification showed that the P-EGAM could increase the viscosity of P-EGAM/ starch composites, and the optimal proportion of P-EGAM addition is 2.5%. Finally, exfoliated mechanism was preliminary speculated by comprehensive comparison of preparation, characterization and application of the two materials. From data of endothermic enthalpy change of DSC, exfoliated rate of gluconic acid montmorillonite was calculated.
Research and development of gluconic acid modified alkaline Ca-bentonite can combine organically with the development of bentonite and cassava starch. It also can broaden the application of bentonite in the field of dehydration of organic solvents and hydrophilic polymer composite material.
引文
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