【作者】 李学强；

【导师】 夏华；

【作者基本信息】 中国地质大学 ， 分析化学， 2003， 硕士

【摘要】 在过去十几年中，聚合物／层状硅酸盐(简称PLS)纳米复合材料已成为一个极为活跃的研究领域，吸引着众多研究者。不同于传统的复合材料，这种复合材料其微区通常为纳米尺度，在其内部各组分的协同作用下会产生一些母体所不具备的特异性质。近几年来，PLS纳米复合材料的制备是探索高性能复合材料的一条重要途径，是材料科学领域研究的一个热点，已引起人们的广泛关注。有关这方面的研究主要集中在聚合物／蒙脱土纳米复合材料。 高岭土与蒙脱土同属于层状硅酸盐，两者都具有典型的层状结构，是用插层复合法制备聚合物／层状硅酸盐纳米复合材料理想的主体矿物。在高分子材料领域，高岭土是性能较蒙脱土更加优异的无机填料。与蒙脱土相比，其层状结构更为完美，杂质更少。可以预料，如果能够制备出聚合物／高岭土纳米复合材料，那么它将可能会展现出更加诱人的优异性能。近年来，高岭土／聚合物纳米复合物研究已经开始成为一个研究热点。 目前，国内外对聚合物／高岭土纳米复合材料的研究，基本上还只是停留在制备高岭土／有机插层复合物阶段，真正制备出来的高岭土／聚合物纳米复合物只有少数几种，还没有将其用于材料工业生产的报导。 国内外高岭土／有机插层复合物研究的重点，主要集中在挑选通用插层剂、改进插层方法、缩短插层反应时间、提高插层率、探索插层复合物的结构和性能等几个方面。这些都是为将来聚合物／高岭土纳米复合材料的广泛应用所做的基础性工作。 本文在查阅大量文献基础上，综述了近年来国内外有机／无机纳米复合材料，特别是聚合物／层状硅酸盐纳米复合材料的研究现状。插层复合法是制备聚合物／层状硅酸盐纳米复合材料的主要方法。文中着重阐述了聚合物／层状硅酸盐纳米复合材料的结构、分类、制备方法以及材料的性能和应用。 本文研究了高岭土／乙酸盐插层复合物的制备和表征方法。这种制备方法是对以前的制备方法的重要改进。通过本法制备出的高岭土／乙酸盐插层复合物，可以直接用作高岭土／聚合物纳米复合物的中间体。研究发现，在水的参与下，乙酸钾可以直接插入高岭土层间，形成高岭土／乙酸钾插层复合物。反应体系中，高岭土、乙酸钾和水的量都必须严格控制，才能获得比较满意的插层率。实验发现，当高岭土、乙酸钾与水的比例为7：3：1时，只需24小时，就基本达到最大插层率(插层率超过80％)。傅立叶变换红外光谱显示，水和乙酸钾一同插入到高岭土的层间，并与高岭土的内表面羟基形成了氢键。用无水乙醇作洗涤液可以将吸附在高岭土颗粒表面的乙酸钾洗脱除去，而已经插入高岭土层间的乙酸钾则不受影响。在严格控制pH的条件下，乙酸铵也可以直接插入高岭土层间，但插层率很低。与乙酸钾不同，乙酸铵与高岭土的插层作用在pH=9的缓冲溶液中，比在近干态下进行的完全。当乙酸铵的浓度为10mol／L时，乙酸铵与高岭土的插层作用进行的更快、更充分。并且此时在X射线粉晶衍射图谱中，会出现d值为3.13nm的衍射峰。钾离子的存在，可能对乙酸盐的插层有很大的促进作用。 本文探讨了以高岭土/毗淀插层复合物的制备与表征方法。实验中以高岭土旧MSO插层复合物作为前驱体，将甲醇引入高岭土层间，制得高岭土/甲醇插层复合物。然后以高岭土/甲醇插层复合物为中间体，将毗睫引入高岭土层间，从而制得高岭土邓比睫插层复合物。在实验过程中，用XRD、Ff-IR和TG一DSC等方法对制备的各插层复合物进行了表征。研究发现，在大量甲醇存在，并每天更换新鲜甲醇的情况下，甲醇可以置换高岭土旧MSO插层复合物中的DMSO，而插入高岭土层间，得到高岭土/甲醇插层复合物。毗淀可以置换高岭土/甲醇插层复合物中的甲醇，使高岭土层间距进一步增大，得到高岭土/毗咤插层复合物。IR谱图表明，甲醇、毗睫与高岭土层间的内表面轻基形成了氢键。文中对毗陡分子在高岭土层间的形态进行了分析，判断毗淀在高岭土层间是立着的。砒咤分子中的氮原子正对着高岭土层面。高岭土/甲醇插层复合物和高岭土/毗淀插层复合物，都不很稳定，在常温下放置就会导致有机分子在层间的排列方式变化，甚至脱嵌。 本文还初步尝试了高岭土/聚丙烯睛纳米复合物的制备方法。实验中，以高岭土/乙酸钾插层复合物为中间体，用插层取代的方法，将丙烯睛单体引入高岭土层间，通过引发剂引发，单体原位聚合，制备高岭土/聚丙烯睛纳米复合物。XRD图谱显示，在所得产品中，高岭土己经非晶态化，各衍射峰已变得很弱，几乎被削平了，这说明聚丙烯睛己经与高岭土达到了纳米尺度的均匀复合。更多还原

【Abstract】 In the past more than ten years, polymer/layered silicate nanocomposites(abbr. PLS) have become a quite active research field, which attract numerous researchers. Different from the traditional composites, the disperse phase in PLS is usually in nanometer scale. Under the synergjstic action among components in nanometer scale, PLS show some specificity that parent materials do not possess. In recent years, the preparation of PLS is an important way to probe high-performance composites, a research focus of material science, which has caused people’s extensive concern. The research now mainly concentrate on polymer/montmorillonite nanocomposites.Having typical layered structure, kaolinite and montmorillonite are all ideal host minerals for preparing polymer/layered silicate nanocomposites by intercalation composite method. In the field of high polymer material, kaolinite is the inorganic filler with more excellent performance than montmorillonite. Comparing with montmorillonite, the layer structure of kaolinite is more perfect, less impurity. It is expected that polymer/kaolinite nanocomposites may show more captivating excellent performance. In recent years, the reseach on kaolinite/organic intercalation composites has already become a research focus.At present, in domestic and international, the study on polymer/kaolinite nanocomposites remains in the stage of preparing kaolininite/organic intercalation composites. Only several kind kaolinite/polymer nanocomposites was prepared and characterized. There is no report on industrial production of this kind yet.In domestic and international, the research on kaolinite/organic intercalation composites focus on selecting universal intercalation reagents, improving intercalation method, shortening intercalation reaction time, increasing intercalation rate, and exploring structure and performance of intercalation composites. These are all fundamental research for the widespread application of polymer/kaolinite nanocomposites for future.Based on a large number of documents, this dissertation presentes a literature review on organic/inorganic nanocomposites in domestic and international in recent years, especially on polymer/layered silicate nanocomposites. Intercalation composite method is the main means for preparation of polymer/layered silicate nanocomposites. The review emphasis on structure, classification and preparation methods of polymer/layered silicates nanocomposites as well as their performance and application.In this dissertation, kaolinite/acetate intercalation composites was prepared and characterized. The preparation method is important improvement of existed means. The kaolinite/acetate intercalation composites prepared by means mentioned in this paper can use as the intermedia for preparation of kaolinite/polymer nanocomposites directly. Research show that potassium acetate can directly insert between the inner layer of kaolinite under the participation of water, formingkaolinite/potassium acetate intercalation composites. The relative mass ratio of potassium acetate and water in the chemical reaction system must be controlled strictly for high intercalation rate. It only takes 24 hours to reach the maximum intercalation rate(beyond 80%) when the relative mass ratio of kaolinite, potassium acetate and water is 7:3:1. FT-IR spectrum show that water insert between the inner layer of kaolinite with potassium acetate, which form hydrogen bond with the inner surface hydroxyl of kaolinite. Potassium acetate adsorbed on the surface of kaolinite particle can be eluted by absolute ethyl alcohol, while that intercalated between the inner layer of kaolinite may not be affected. Ammonium acetate can also directly insert between the inner layer of kaolinite by controlling pH strictly, but the intercalation rate is very low. Different from potassium acetate, ammonium acetate intercalated into the inner layer of kaolinite more completely in buffer solution(pH=9) than under near dry condition. When the concentration of ammonium acetate is lOmol/L, in更多还原