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水滑石/PA6纳米复合材料的制备、结构与性能

Preparation, Structure and Proterties of Hydrotalcite/PA6Nanocomposites

【作者】 李宏林

【导师】 吴玉程;

【作者基本信息】 合肥工业大学 , 材料学, 2014, 博士

【摘要】 本论文采用原位聚合方法的不同工艺制备了水滑石/PA6纳米复合材料、类水滑石/PA6纳米复合材料、水滑石/PA6/PS三元复合体系、类水滑石/PA6/PS三元复合体系及PA6紫外吸收功能微球,并对所得样品形貌、性能进行表征和讨论。具体研究内容如下:1)采用己内酰胺水解开环原位聚合方法制备的MgAl-LDHs/PA6和MgAl-THlcs/PA6纳米复合材料,MgAl-LDHs和MgAl-THlcs在复合材料中均达到均匀分散,MgAl-LDHs含量为0.3wt%的复合材料CP-0.3出现了部分片层剥离的水滑石,MgAl-THlcs含量为0.3wt%的复合材料CPH-0.3出现了部分片层剥离的类水滑石;部分片层剥离的水滑石或类水滑石的存在明显促进复合材料中PA6γ晶型的生成;水滑石或类水滑石的加入在PA6结晶的过程中起到了很好的异相成核剂的作用,提高了PA6的结晶能力;低含量MgAl-LDHs和MgAl-THlcs对PA6的热稳定性影响不显著;少量均匀分散的MgAl-THlcs使复合材料对近紫外波长为320~380nm的紫外线吸收效果明显,MgAl-THlcs对紫外线的吸收在其复合材料中发生了红移。2)采用静态浇注己内酰胺阴离子开环原位聚合方法制备的MgAl-LDHs/PA6纳米复合材料,TEM显示MgAl-LDHs在复合材料中团聚较严重;另外,MgAl-LDHs的加入对复合材料中PA6的晶型、结晶能力和热稳定性均无明显影响。3)采用反应挤出己内酰胺阴离子开环原位聚合得到了MgAl-THlcs在复合材料中呈纳米级均匀分散的MgAl-THlcs/PA6纳米复合材料RCPHs,在MgAl-THlcs含量为1wt%时出现了部分片层剥离型水滑石;MgAl-THlcs的加入使复合材料对近紫外波长为320~380nm的紫外线吸收效果明显;少量均匀分散的MgAl-THlcs起到了很好的异相成核剂的作用,不仅提高了PA6的结晶温度,而且也增加了其结晶度。但在反应挤出工艺中,MgAl-THlcs的加入对复合材料PA6晶型结构影响不大;部分片层剥离MgAl-THlcs的存在明显提高了复合材料的热稳定性。4)采用连续双原位聚合方法合成了MgAl-LDHs/PA6/PS和MgAl-THlcs/PA6/PS三元复合材料。当加入MgAl-LDHs时,复合材料是完全不相容的PA6微球分散相/PS连续相的结构,而当加入MgAl-THlcs复合材料的形貌由PA6微球分散相/PS连续相逐渐变为PA6连续相/PS分散相的结构;TEM表明添加MgAl-LDHs或低含量MgAl-THlcs时,水滑石分散在PA6微球中;另外MgAl-LDHs和MgAl-THlcs的加入对复合材料中PA6晶型和结晶能力均无太大影响。5)利用连续双原位聚合和MgAl-THlcs的选择性分布成功制备了PA6紫外吸收功能微球。PA6紫外吸收功能微球的粒径分布较窄,平均粒径43μm,并且表面有丰富的活性基团;在波长330~400nm范围内,PA6紫外吸收功能微球的紫外吸收能力比PA6微球明显提高;与PA6微球相比,PA6紫外吸收功能微球具有较好的热稳定性。

【Abstract】 In this dissertation, the LDHs/PA6nanocomposites, THlcs/PA6nanocomposites,LDHs/PA6/PS ternary composites, THlcs/PA6/PS ternary composites and PA6UVabsorbance microspheres were prepared via in situ polymerization based on differenttechniques. Various characterization such as the morphological structure, crystallizationand thermal properties, and so on of the samples were investigated and discussed. Themain contents are as follows:1) MgAl-LDHs/PA6and MgAl-THlcs/PA6nanocomposites were prepared byhydrolyzed ring opening in-situ polymerization. The part nanodispersion of exfoliatedMgAl-LDH layers and MgAl-THlc layers in nanocomposites CP-0.3and CPH-0.3hadbeen verified by the observation of TEM image. The XRD results showed that partexfoliated MgAl-LDHs and MgAl-THlcs favored the formation of the γ-crystalline ofPA6form. DSC data showed that the exfoliated MgAl-LDH layers and MgAl-THlclayers played the role of nucleating agents with strong heterogeneous nucleation effecton the crystallization of PA6. But TAG results showed the thermal stability ofMgAl-LDHs/PA6and MgAl-THlcs/PA6nanocomposites were worse than that of PA6.The composites containing small uniformly dispersed MgAl-THlcs absorbed theultraviolet about the wavelength320~380nm obviously.2) MgAl-LDHs/PA6nanocomposites had been prepared by static casting anionic ringopening in-situ polymerization. TEM showed that MgAl-LDHs in the compositesreunited more serious. In addition, There were no much effect about MgAl-LDHs oncomposites crystal form, crystallization ability and thermal stability.3) MgAl-THlcs/PA6nanocomposites had been prepared by reactive extrusionanionic ring opening in-situ polymerization. The nanodispersion of exfoliatedMgAl-THlc layers in nanocomposites RCPH-1.0had been verified by the observationof TEM image. The composites containing MgAl-THlcs absorbed the ultraviolet aboutthe wavelength320-380nm obviously. The small uniformly dispersed MgAl-THlcsplayed the role of nucleating agents with strong heterogeneous nucleation effect on thecrystallization of PA6. But there were no effect about MgAl-THlcs on compositescrystal form and crystallization ability here. In additional, the thermal stability of thecomposites had been improved because the composites contained part exfoliatedMgAl-THlcs. 4) LDHs/PA6/PS ternary composites and THlcs/PA6/PS ternary composites wereprepared via successive in-situ polymerization. The effects of MgAl-LDHs andMgAl-THlcs on the morpholugies and properties of the ternary composites had beenstudied. The structure of the ternary composites with MgAl-LDHs and littleMgAl-THlcs were incompatible PA6microspheres dispersed/PS continuous phasecompletely, and the structure of the ternary composites with more MgAl-THlcs were thePA6microspheres dispersed/PS continuous phase gradually became PA6continuousphase/PS dispersed phase. Hydrotalcite dispersed in PA6microspheres when the ternarycomposites with MgAl-LDHs and little MgAl-THlcs. There were no much effect aboutMgAl-LDHs and MgAl-THlcs on composites crystal form, crystallization ability andthermal stability.5) PA6UV absorbance microspheres were prepared via successive in-situpolymerization. The PA6UV absorbance microspheres had narrow particle sizedistribution and rich surface active groups. The average particle size of the PA6UVabsorbance microspheres is43μm. The PA6UV absorbance microspheres absorbed theultraviolet about the wavelength330~400nm obviously. Compared with PA6microspheres, PA6UV absorbance microspheres have better thermal stability.

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