聚合物/蒙脱土纳米复合材料的制备与结晶性能

本文综述了制备聚合物 /蒙脱土纳米复合材料的插层方法 ,并对有代表性的结晶性聚合物 /蒙脱土纳米复合材料的结晶性能进行了讨论。蒙脱土的加入对聚合物的结晶有两种作用 ,一方面是对聚合物有异相成核的作用 ,可以提高聚合物的结晶温度和结晶速率 ,降低结晶活化能 ;另一方面是对聚合物结晶生长有阻碍作用 ,导致结晶速率下降 ,结晶活化能提高     

Complex formation of montmorillonite clay with polymers. Part 2: The use of montmorillonite clay–vinyl monomer complex as a comonomer in the copolymerization reaction of styrene–acrylonitrile monomers

The bulk copolymerization of styrene–acrylonitrile monomers using styrene‐N⁺–montmorillonite complex as a comonomer in the polymerization was studied. The X‐ray diffraction (XRD) analysis showed that part of the styrene‐N⁺–montmorillonite complex remained non‐dispersed (immiscible) and the copolymer was excluded from the interlayer of the immiscible part of the clay. The successive chemical extraction process revealed that a reasonable amount of the styrene–acrylonitrile copolymer was directly attached to the styrene‐N⁺–montmorillonite complex and enveloped the clay. Highly exfoliated clay lamella and nanospheres (3–5 nm) were observed by transmission electron microscopy (TEM). The montmorillonite clay assume two different morphologies, immiscible and exfoliated, on the basis of the XRD and TEM data. A simple method of calculation of the ratio of the exfoliated/immiscible amounts of the clay indicated that the amount of the styrene‐N⁺–montmorillonite complex exfoliated into separate lamella was 40 % (w/w) of the amount of the clay samples containing 2 % of the (styrene‐N⁺–montmorillonite complex) clay. This amount of exfoliated clay decreases with the increase of the concentration of the clay. The presence of the styrene‐N⁺–montmorillonite clay in the copolymerization reaction had a minor effect on both the copolymer composition and the molecular weight. Modification of the clay with the derivatized styrene monomer can achieve a nanocomposite using a percentage no more than 4 % (w/w) of complex in the copolymer. Copyright © 2004 Society of Chemical Industry     

Properties of poly(ethylene terephthalate)–poly(ethylene naphthalene 2,6‐dicarboxylate) blends with montmorillonite clay

The production and properties of blends of poly(ethylene terephthalate) (PET) and poly(ethylene naphthalene 2,6‐dicarboxylate) (PEN) with three modified clays are reported. Octadecylammonium chloride and maleic anhydride (MAH) are used to modify the surface of the montmorillonite–Na⁺ clay particles (clay–Na⁺) to produce clay–C18 and clay–MAH, respectively, before they are mixed with the PET/PEN system. The transesterification degree, hydrophobicity and the effect of the clays on the mechanical, rheological and thermal properties are analysed. The PET–PEN/clay–C18 system does not show any improvements in the mechanical properties, which is attributed to poor exfoliation. On the other hand, in the PET–PEN/clay–MAH blends, the modified clay restricts crystallization of the matrix, as evidenced in the low value of the crystallization enthalpy. The process‐induced PET–PEN transesterification reaction is affected by the clay particles. Clay–C18 induces the largest proportion of naphthalate–ethylene–terephthalate (NET) blocks, as opposed to clay–Na⁺ which renders the lowest proportion. The clay readily incorporates in the bulk polymer, but receding contact‐angle measurements reveal a small influence of the particles on the surface properties of the sample. The clay–Na⁺ blend shows a predominant solid‐like behaviour, as evidenced by the magnitude of the storage modulus in the low‐frequency range, which reflects a high entanglement density and a substantial degree of polymer–particle interactions. Copyright © 2005 Society of Chemical Industry     

聚合物-蒙脱石纳米复合材料的制备、结构与性能

从结构与性能的观点出发,将聚合物-蒙脱石纳米复合材料划分为插层型、层离型和混合型(插层型+层离型),探讨了影响蒙脱石纳米化的因素,提出了蒙脱石纳米化中值得注意的几个问题.     

Maghnite‐H+, a solid catalyst for the cationic polymerization of α‐methylstyrene

The polymerization of α‐methylstyrene (AMS) catalyzed by Maghnite‐H⁺ (Mag‐H) was investigated. Mag‐H is a montmorillonite sheet silicate clay, exchanged with protons. It was found that the cationic polymerization of AMS is initiated by Mag‐H at ambient temperature in bulk and in solution. The effect of the amount of Mag‐H, the temperature, and the solvent was studied. The polymerization rate increased with increase in the temperature and the proportion of catalyst, and it was larger in nonpolar solvents. These results indicated the cationic nature of the polymerization. It may be suggested that the polymerization is initiated by proton addition to monomer from Mag‐H. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

蒙脱土-有机硅复合改性硅烷化聚氨酯密封胶

采用2,4-甲苯二异氰酸酯、聚醚多元醇、蒙脱土、有机硅(α,ω-二羟基聚二甲基硅氧烷)和硅烷偶联剂为原料,制备了有机蒙脱土/聚醚多元醇复合物(OMMT/330N)-有机硅复合改性的硅烷化聚氨酯(SPU)密封胶。通过广角X射线衍射、透射电子显微镜和傅里叶变换红外光谱手段表征了蒙脱土在复合材料中的分散情况,表征结果显示,有机蒙脱土以平均层间距不小于4.12nm的宽分布分散在SPU基体中。同时对密封胶的力学性能进行测试,测试结果表明,经OMMT/330N-有机硅复合改性的SPU密封胶具有性能互补效果,当添加质量分数为5%(基于330N)的OMMT和8%的有机硅时,复合改性的SPU密封胶的拉伸强度和断裂伸长率比纯SPU密封胶提高了65.8%和71.6%。     

硫掺杂ZnFe2O4/蒙脱石复合材料的铀酰吸附研究

为获得铀酰(UO2²⁺)吸附性能高的吸附剂,以蒙脱石(Montmorillonite,MMT)和铁酸盐(ZnFe₂O₄)为原材料与L-半胱氨酸通过水热反应制备了硫掺杂ZnFe₂O₄(S-ZnFe₂O₄)和ZnFe₂O₄/MMT(S-ZnFe₂O₄/MMT),采用XRD、FTIR和SEM对S-ZnFe₂O₄和S-ZnFe₂O₄/MMT进行了结构表征,研究了pH、接触时间和UO2²⁺初始质量浓度对UO2²⁺吸附效果的影响,结果表明:S-ZnFe₂O₄呈高分散的纳米颗粒状,并且均匀分布于蒙脱石片层结构表面;S-ZnFe₂O₄与蒙脱石复合后能明显提高其UO2²⁺吸附性能,最佳吸附pH为6.0;S-ZnFe₂O₄和S-ZnFe₂O₄/MMT复合材料对UO2²⁺的最大吸附量分别为51.44 mg/g和68.45 mg/g;吸附符合Langmuir等温吸附模型和伪二阶动力学模型,说明吸附过程属于表面单分子层化学吸附。     

阻燃OMMT/WPU纳米复合材料的制备及性能研究

采用端羟基聚丁二烯（HTPB）剥离层状有机蒙脱土（OMMT）为纳米片层,并与异佛尔酮二异氰酸酯（IPDI）、二羟甲基丙酸（DMPA）等单体通过原位聚合法制备了OMMT纳米片改性的水性聚氨酯（OWPU）纳米乳液及胶膜。利用小角XRD、TEM、DLS、EDS、TGA、LOI、CONE以及SEM对样品的结构和性能进行了表征。结果表明,HTPB剥离的OMMT纳米片的衬度均匀,完整性较好;改性后OWPU的乳液粒径增大,胶膜的弹性模量、热稳定性、抗熔滴性和阻燃性能均得到明显地改善,其中弹性模量可提高59.4%,热释放速率峰值可降低36.9%;燃烧炭渣表面形貌显示,瓦片状蒙脱土相互穿插形成了具有团簇结构的蒙脱土覆盖层。     

Synergistic Flame Retardant Effects of Carbon Nanotube-Based Multilayer Nanocoatings

In an effort to develop highly functionalized flame retardant materials, hybrid nanocoatings are prepared by alternately depositing a positively charged polyaniline (PANi) and negatively charged montmorillonite (MMT) using the layer-by-layer (LbL) assembly technique. Carbon nanotubes (CNTs) are employed in polymer nanocomposites as effective reinforcement, where nanotubes are stabilized in MMT aqueous solution. The 3D structure and high density of CNTs deposited in the PANi/CNTs-MMT multilayers produce thicker and heavier coatings in comparison to the LbL assemblies without CNTs. Vertical and horizontal flame testing show that the incorporation of CNTs improves fire resistance. Additionally, cone calorimetry reveals that stacking two nanomaterials (MMT and CNTs) in a single coating shows a significant reduction in peak heat release rate (up to 51%), total smoke release (up to 47%), and total heat release (up to 37%) for the polyurethane foam. The enhancement of flame retardancy is attributed to a synergistic effect; MMT serves as a physical barrier that retards the diffusion of heat and gas. The addition of CNTs strengthens the thermal stability and high char yield. These results, coupled with the simplicity with which the LbL deposition is applied, present a viable alternative to halogen-free flame retardant nanocoatings to natural and synthetic fibers.     

酪素/蒙脱土插层复合物制备及其耐水性能研究

在十六烷基季胺盐存在下进行蒙脱土插层得到[H4N(CH2)15CH3]+-蒙脱土插层物,酪素加热溶解后与[H4N(CH2)15CH]+-蒙脱土插层物混合,保温复合,然后沉淀分离,得到干酪素/蒙脱土纳米复合物。用XRD,TEM和TGA表征酪素纳米复合物的结构与性能。结果表明,插层复合物中蒙脱土晶片间距扩大,插层复合物耐热性能明显提高,与纯酪素相比,复合物拥有极好的耐水性能,特别适用于制备高速高性能啤酒生产线用贴标胶。