Exfoliation of Organically Modified Montmorillonite Driven by Molecular Diffusion in Maleated Polypropylene

This work is focused on the factors influencing the intercalation of maleated polypropylene (PPMA) into organically modified montmorillonite (OMMT). Two kinds of PPMA were used to explore the optimal candidate for effective intercalation into OMMT. The grafting degree of maleic anhydride and the viscosity of PPMA have effects on the diffusion of polymer molecules. Moreover, the loading level of surfactant was varied to optimize the modification of montmorillonite because the appropriate loading level can provide a balance between interlayer distance and steric hindrance. The kind of surfactant changes the interaction between OMMT and PPMA, and accordingly the intercalation of PPMA is different, resulting in the discrepancy of the intercalation of PPMA.

STRUCTURAL EVOLUTION AND COMPOSITION CHANGE IN THE SURFACE REGION OF POLYPROPYLENE/CLAY NANOCOMPOSITES ANNEALED AT HIGH TEMPERATURES

A model experiment was done to clear the formation mechanism of protective layers during combustion of polypropylene (PP)/organically modified montmorillonite (OMMT) nanocomposites. The investigation was focused on the effects of annealing temperature on the structural changes and protective layer formation. The decomposition of OMMT and degradation of PP/OMMT nanocomposites were characterized by means of thermogravimetric analysis (TGA). The structural evolution and composition change in the surface region of PP/OMMT nanocomposites during heating were monitored by means of X-ray photoelectron spectroscopy (XPS), ATR-FTIR and field emission scanning electron microscopy (FESEM).

An investigation on the dispersion of montmorillonite (MMT) primary particles in PP matrix

A novel path of preparing PP/o-MMT nanocomposites, which pay attention to the breaking up of MMT original agglomerates and dispersing of its primary particles, rather than the intercalation or exfoliation degree of o-MMT, was reported. The method of predispersing the o-MMT particles into a polar poly(vinyl alcohol) (PVA) matrix and then melt blending the pre-treated PVA/o-MMT hybrids with PP was studied. 3-isopropenyl-alpha,alpha-dimethylbenzene-isocyanate (TMI) was used as a modifier of PVA to improve the compatibility between PVA and PP matrix. Pre-disperse o-MMT with TMI modified PVA was proved to be an effective way to get a composite with fine o-MMT particles dispersion. But the method, which is pre-dispersing o-MMT with non modified PVA and then using TMI to modify such PVA/o-MMT hybrid, would largely reduce the reaction degree between TMI and PVA because of the relatively lower reaction temperature. Although the latter method also can obtain finer dispersion composites than that with using PP-g-MAH as compatibilizer, the relatively higher degradation degree of PP matrix in this method will limit the use of this nanocomposite.

Influences of catalysis and dispersion of organically modified montmorillonite on flame retardancy of polypropylene nanocomposites

The degradation and flame retardancy of polypropylene/organically modified montmorillonite (PP/OMMT) nanocomposite were studied by means of gas chromatography-mass spectrometry and cone calorimeter. The catalysis of hydrogen proton containing montmorillonite (H-MMT) derived from thermal decomposition of (alkyl) ammonium in the OMMT on degradation of PP strongly influence carbonization behavior of PP and then flame retardancy. Bronsted acid sites on the H-MMT could catalyze degradation reaction of PP via cationic mechanism, which leads to the formation of char during combustion of PP via hydride transfer reaction. A continuous carbonaceous MMT-rich char on the surface of the burned residues, which work as a protective barrier to heat and mass transfer, results from the homogeneous dispersion of OMMT in the PP matrix and appropriate char produced.

Synthesis and characterization of polypropylene/montmorillonite nanocomposites via an in-situ polymerization approach

Polypropylene/montmorillonite (PP/MMT) nanocomposites were prepared by in-situ polymerization using a MMT/MgCl2/TiCl4-EB Ziegler-Natta catalyst activated by trietbylaluminum (TEA). The enlarged layer spacing of MMT was confirmed by X-ray wide angle diffraction (WAXD), demonstrating that MMT were intercalated by the catalyst components. X-ray photoelectron spectrometry (XPS) analysis proved that TiCl4 was mainly supported on MgCl2 instead of on the surface of MMT The exfoliated structure of MMT layers in the PP matrix of PP/MMT composites was demonstrated by WAXD patterns and transmission electron microscopy (TEM) observation. The higher glass transition temperature and higher storage modulus of the PP/MMT composites in comparison with pure PP were revealed by dynamic mechanical analysis (DMA).

Preparation and optical properties of CdTe/CdO center dot nH(2)O core/shell nano-composites in aqueous solution

The deposition of CdO center dot nH(2)O On CdTe nanoparticles was studied in an aqueous phase. The CdTe nanocrystals (NCs) were prepared in aqueous solution through the reaction between Cd2+ and NaHTe in the presence of thioglycolic acid as a stabilizer. The molar ratio of the Cd2+ to Te2- in the precursory solution played an important role in the photoluminescence of the ultimate CdTe NCs. The strongest photoluminescence was obtained under 4.0 of [Cd2+]/[Te2-] at pH similar to 8.2. With the optimum dosage of Cd(II) hydrous oxide deposited on the CdTe NCs, the photoluminescence was enhanced greatly. The photoluminescence of these nanocomposites was kept constant in the pH range of 8.0-10.0, but dramatically decreased with an obvious blue-shifted peak while the pH was below 8.0. In addition, the photochemical oxidation of CdTe NCs with cadmium hydrous oxide deposition was markedly inhibited.

Transparent and Light-Emitting Epoxy Super-Nanocomposites Containing ZnO-QDs/SiO2 Nanocomposite Particles as Encapsulating Materials for Solid-State Lighting

In this article, the ZnO quantum dots-SiO2 (Z-S) nanocomposite particles were first synthesized. Transparent Z-S/epoxy super-nanocomposites were then prepared by introducing calcined Z-S nanocomposite particles with a proper ratio of ZnO to SiO2 into a transparent epoxy matrix in terms of the filler-matrix refractive index matching principle. It was shown that the epoxy super-nanocomposites displayed intense luminescence with broad emission spectra. Moreover, the epoxy super-nanocomposites showed the interesting afterglow phenomenon with a long phosphorescence lifetime that was not observed for ZnO-QDs/epoxy nanocomposites. Finally, the transparent and light-emitting Z-S/epoxy super-nanocomposites were successfully employed as encapsulating materials for synthesis of highly bright LED lamps.

增容PP／PA6合金的制备及形态结构、性能研究

本文以过氧化物为引发剂，采用反应挤出的方法，制备了用马来酸配官能化的聚丙烯。并对接枝反应的机理及提高接枝率的途径进行了深入的探讨。本工作还合成了低分子量，多端胺基或竣基的尼龙6，用反应共混的方法制备了PP/PP-g-MAHIPA6三元共混物。研究了该三元共混体系的形态结构、热性能、流变和染色性能等。用电喷雾质谱(ESI-MS)和GPC等手段，对接枝聚丙烯产物的二甲苯一丙酮抽提液进行了研究，并结合前人工作提出了以下聚丙烯熔融接枝马来酸配的反应机理：1、在聚丙烯熔融接枝马来酸配的反应条件下，马来酸配自由基只能发生歧化终止，因此在整个接枝体系中没有马来酸配的均聚物生成；2、过氧化物均裂产生的自由基在引发聚丙烯大分子的同时，也可以引发马来酸配单体，由于马来酸配自由基只能歧化终止，这一部分MAH单体将不能参加接枝反应；3,在接枝反应过程中，不是所有的聚丙烯大分子链上的三级自由基都发生p断链，也不是所有的二级自由基都发生偶合终止。只有没有参与接枝反应（即没有接枝上MAH )的三级（或二级）自由基才能发生β断链（或在链间形成交联结构）；4、在聚丙烯熔融接枝MAH时，加入适当的表面活性剂类的两性物质可以在保持产物的分子量的同时提高产物的接枝率。5、反应过程中的氧化作用对于产物的接枝率的影响可以忽略，但对最终产物的分子量有一定影响。该机理可以很好的解释所有实验结果。

用NMR、FT-IR、DSC和AFM的方法研究PP-b-PE的结构与性能

聚丙烯是一种优异的高分子材料，但其低温抗冲击性能欠佳，因而限制了其应用范围。采用PP与PE嵌段共聚来改善PP的抗冲击性能是世界上目前行之有效的方法，因而引起人们的重视。由于聚丙烯嵌段共聚物（PP-b-PE）是由多组分组成的复杂体系，对其组成和链的结构仍不十分清楚。因此，本工作选取国外（6组）和国内（5组）共计11组PP-b-PE样品，分别对其结构、性能及其影响因素进行了研究，为实际应用提供了依据。为了保证能将PP-b-PE中的橡胶成分抽提出来，先将PP-b-PE样品用二甲苯溶解，之后加入甲醇沉淀、过滤、干燥，最后用正庚烷抽提，使得PP-b-PE样品中正庚烷的不可溶物与可溶物完全分离。其中，可溶物即为橡胶，不可溶物为塑料。再利用高温核磁共振谱仪（NMR）、示差扫描量热仪（DSC）和傅立汗卜变换红外谱仪（FT-IR）等先进的分析技术手段进行结构分析，并用原子力显微镜（AFM）观察生产过程中样品的形貌。实验和分析结果表明：在正庚烷可溶物中含有低熔点的聚丙烯和嵌段长度不同且能结晶的聚乙烯；并且还含有属于乙丙无规共聚物橡胶部分的n值小于4的（-CH2-）n结构，以及嵌有结晶性的丙烯和乙烯链节。正庚烷的不可溶物主要为聚丙烯，及少量聚乙烯。对于不同物性的PP-b-PE而言，正庚烷不可溶物决定了其刚性，正庚烷可溶物决定了其韧性，并由其粘度比决定了橡胶在聚丙烯中的分布情况。用AFM来研究PP-b-PE中的橡胶颗粒的分布情况是非常好的分析方法。PP-b-PE样品中橡胶的含量及其组成成分将对PP-b-PE的性能产生很大的影响。国内用浆液法生产的PP-b-PE样品中橡胶含量相对于用液一气相法和气相法生产的要少，但在其正庚烷不可溶物中含有较多的乙烯。从而可以用控制乙烯的含量来改善其抗冲击性能，这是浆液法与液一气相法和气相法的最大区别。液一气相法和气相法生产的PP-b-PE样品中的正庚烷可溶物的含量和结构十分接近。结果表明，本文采用多种不同的先进的分析方法和实验手段对PP-b-PE的结构与性能的研究是一条有效可行的实验途径。

“PP-PE”聚合合金结构与性能的关系及PP/HDPE共混体系增容改性的新途径

试图澄清“PP-PE”结构与性能的关系，并以此为指导寻求增容改性PP/HDPE体系的新途径是本工作的主要内容。在本工作中，考虑到分子量、EPC组分和共混均匀性因素之后发现，“PP-PE”与相同条件下合成的均聚物样品构成的共混物之间在应力-应变行为、抗冲击性能和动态力学行为上并没有明显差别。在结合文献中有关现象详尽讨论了关于活性链寿命报导值和“（PP-PE）_(200)"的C~(13)NMR谱支持嵌段结构观点的可靠性之后，得到的结论是，现有实验现象不中以证明“PP-PE”具有嵌段结构，尽管四十年来这一观点已被普遍接受。通过TEM观察到，“PP-PE”与PP/HMWPE共混物结晶结构相同，“PP-PE”中的PE部分明显具有HMWPE的片晶特征，应力-应变和SEM实验的结果显示，“PP-PE”与HMWPE具有完全相同的增容PP/HDPE的作用。结合有关共混物结构和性能的实验结果，发现“PP-PE”主要是一个共混物，其中的HMWPE和EPC组分是决定其性能行为的主要因素。尽管在理论和实验上都已确认，分子量的增大不利于共混物组分间的相容，但通过应力-应变实验和形态结构的观察发现，虽然均聚物HMWPE的加入使PP/HDPE体系中PE组分平均分子量增大，但是体系中分散相尺寸却随HMWPE含量的增加大幅度减小，力学性能全面提高。HMWPE这种同接枝和嵌段共聚相似的增容作用既不能用“相似相容”，也不能用所谓“特殊相互作用”来阐明。为此，在本工作中提出了一个新的增容机制——“缠结作用”。应力-应变实验表明，PP/HMWPE体系的力学性能明显优于PP/HDPE体系。前者强度和断裂伸长率都高于后者，其差别尤以断裂伸长率为甚，而模量相差不大。SEM形态结构的观察发现，虽然PP/HDPE体系中的分散相尺寸随其量的增加而增大，并且界面清晰，但PP/HMWPE中的缠结作用使得组分间界面模糊，甚至消失。这种较强的组分间相互作用使得材料由脆性断裂转变为韧性断裂。PP/HMWPE的性能特点进一步证实了非理想换气条件下制备的“PP-PE”结构与性能的关系。