摘要
本文从在PP／MMT和PVC／MMT纳米复合材料制备过程中出现的两个难题着手进行研究：一是由于PP的非极性，难以直接用有机蒙脱土(OMMT)熔融插层法制备PP／MMT纳米复合材料；二是利用熔融插层法制备PVC／MMT纳米复合材料过程中，OMMT导致的PVC热降解问题。本文具体研究了蒙脱土纳米母料的制备以及利用这种母料通过熔融插层法制备聚丙烯、聚氯乙烯／蒙脱土纳米复合材料，并且对这些纳米复合材料进行了结构表征和性能测试。
在蒙脱土纳米母料制备部分，通过熔融插层法成功制备了OMMT／MPP和OMMT／MPP／EP两种蒙脱土纳米母料，OMMT含量达60wt％。通过XRD分析结果得知，OMMT／MPP／EP为完全插层型纳米母料，蒙脱土层间距达到了3.33nm；而OMMT／MPP则属于部分插层型纳米母料。另外，还在OMMT高含量(60wt％)条件下，通过单体插层原位聚合法制得了OMMT／PMMA无序插层型纳米母料，蒙脱土的层间距达到了3.65nm。
在PP／MMT复合体系部分，采用OMMT／MPP(MMT_(OM))和OMMT／MPP／EP(MMT_(OME))两种蒙脱土纳米母料成功制得了PP／MMT纳米复合材料，另外还直接利用OMMT制得PP／OMMT纳米复合材料。通过XRD分析比较这三种PP／MMT纳米复合材料微观结构得到，PP／MMT_(OME)属于完全插层，PP／MMT_(OM)与PP／OMMT的插层程度相近，但是PP／MMT_(OM)相对较好；通过对纯PP和三种PP／MMT纳米复合材料的结晶性能研究发现，蒙脱土纳米片层对PP结晶产生明显的异相成核作用，结晶能力增强，使PP的结晶温度和结晶速率提高，结晶度增加，球晶晶粒细化，但是没有改变PP的结晶形态，三种PP／MMT纳米复合材料的结晶形态都属于α晶；通过对PP／MMT纳米复合材料的力学性能测试得知，蒙脱土的加入全面提高了PP的力学性能，缺口冲击强度、拉伸强度和弯曲性能都有一定程度的提高，
浙江{_业大学硕十学位论文
摘要
但是提高幅度都不是很大，不过OMMT、MMToM和MMTc)ME三种蒙脱土对PP
力学性能有着不同的改性作用，其中pp/MMToM最好，pp月边MTO崛次之，PP/oMMT
最低，这种情况主要是由蒙脱土对PP结晶性能的影响和蒙脱土的纳米改性作用造
成的。
在硬质PVC/MMT复合体系部分，采用OMMT/MPP/EP蒙脱土纳米母料成功
制备了硬质PVC/MMToME剥离型纳米复合材料，解决了OMMT造成的PVC热降
解问题。通过力学性能测试发现，在蒙脱土含量为7Phr时，硬质PvC的缺口冲击
强度最大提高了108%，弯曲模量也有所提高。但是，硬质PVC/Na一MMT复合体
系的缺口冲击强度只提高了29%，蒙脱土层间距还是1.29nm，属于普通填充型复
合材料。
在软质PVC八叭MT复合体系中，由于增塑剂DOP对PVC有一定的热稳定作
用，可以直接利用OMMT制备软质PVC/MMT插层型纳米复合材料，蒙脱上层间
距为3.73nm。通过对软质PVC薄膜的增塑剂DOP挥发损失率测试发现，OMMT
的加入明显提高了软质PVC的抗增塑剂迁移性能，这也同时说明了纳米化的蒙脱
土片层分散在PVC基体中可以提高阻隔性能。
This paper found two problems during the preparation processes of polypropylene /organophilic montmoriUonite (PP/OMMT) nanocomposite and poly(vinyl chloride) /organophilic montmorillonite(PVC/OMMT) nanocomposite: One was that PP/MMT nanocomposite was difficultly prepared by melt intercalation as a result of PP is non-polarity polymer; Other was that OMMT resulted in PVC degraded in preparation of PVC/MMT nanocomposite by melt intercalation. In this paper, MMT nano-masterbatches were prepared and characterization; PP/MMT and PVC/MMT nanocomposites were prepared with MMT nano-masterbatches by melt intercalation, and the structure and properties of these two nanocomposites were characterized.
Preparation of MMT nano-masterbatch. Two sorts of MMT nano-masterbatches of organo-montmorillonite/polypropylene-g-maleic anhydride/epoxy resin(OMMT/MPP /EP) and organo-montmorillonite/polypropylene-g-maleic anhydride (OMMT/MPP) were successfully prepared by melt intercalation. In these masterbatches, MMT content reached 60wt%. The results from X-ray diffraction showed that OMMT/MPP/EP was a fully intercalated nano-masterbatch, the space of the layers increased from 1.95nm up to about 3.33nm; But OMMT/MPP was just partly intercalated nano-masterbatch. In addition, in the condition of high content of OMMT, poly(methyl methacrylate)/organophilic montmorillonite(OMMT/PMMA) prepared by in-situ polymerization was orderlessly intercalated nano-masterbatch, the space of the layers reached 3.65nm.
PP/MMT nanocomposites. PP/MMT nanocomposites were successfully prepared with OMMT/MPP/EP(MMTOme) and OMMT/MPP(MMTOm) by melt intercalation, PP/OMMT nanocomposite was prepared with OMMT also. The results from X-ray diffraction demonstrated that PP/ MMTome was a fully intercalated nanocomposite, PP/ MMTom and PP/OMMT were partly intercalated nanocomposites, but the intercalation effect of PP/ MMTom nanocomposite was better; The crystallization characteristics of pure PP and PP/MMT nanocomposites were investigated by DSC, WAXD and POM. The result of these testing showed that MMT nano-layers acted as nucleating agents for the crystallization of PP, the addition of MMT had effect on the crystallization process, leading the increasing of crystallization temperature crystallization rate and crystallinity, but also the dimension of spherulite reduced. But the formation of PP crystal didn't change, the formation of PP crystal in three PP/MMT nanocomposites and pure PP were a-form on the whole; Influences of three sorts of MMT on mechanical properties of PP/MMT nanocomposites were studied, as a result, the addition of MMT comprehensively improved mechanical properties of PP: notched impact strength, tensile strength and flexural properties were all increasing, but the extent of increasing weren't large. Additionally, three sorts of MMT had different effect on the mechanical properties of PP: PP/MMTOm was best, PP/MMTOme was better and OMMT was last. Analyzed these results, the paper considered there were two causes: the influence of MMT on crystallization of PP and nano-function of MMT nano-layers.
Hard PVC/MMT(HPVC/MMT) nanocomposite. PVC/MMT exfoliated nanocomposite were successfully prepared with MMTome by melt intercalation. The problem that OMMT resulted in PVC degraded was settled. But Na-MMT in PVC/Na-MMT composite was simply common filler, the space of the layers was 1.29nm. The mechanical properties of system of HPVC/MMT composites showed, the notched impact strength of HPVC/MMTOme nanocomposite was 1.08 times of that of pure HPVC, but the notched impact strength of PVC/Na-MMT composite increased only 29%.
Soft PVC/MMT(SPVC/MMT) nanocomposite. OMMT can been directly used for the preparation of SPVC/MMT nanocomposite because dioctyl phthalate(DOP)
plasticizer can improve the heat stabilization of PVC in some sort. The space of the layers of MMT in SPVC/MMT nanocomposite reached 3.73nm. The volatilization rate into air of SPVC composites were examined, the result showed that the addition of OMMT could significantly improv
引文
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