含混合金属的羟基镍铝交联蒙托石的合成

用两种方法——取代法和共聚法合成了一系列羟基镍铝交联蒙托石(GNiAl-CLM和NiAl-CLM),首次利用两种方法,交联前和交联后高温老化处理,对交联蒙托石的热稳定性进行改进。结果表明:取代法合成的羟基镍铝交联蒙托石具有均一的(001)面衍射,底面间距d(001)值均为1.8nm左右,而共聚法合成的羟基镍铝交联蒙托石出现两个(001)面衍射,d(001)值分别为1.8nm和1.55nm;高温处理后,热稳定性得到明显改进,热稳定性可高达700℃以上。     

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     

有机硅改性水性阳离子聚氨酯的合成与性能研究

本研究合成了有机硅改性的阳离子聚氨酯乳液,有机硅的加入改善了漆膜的耐水性、漆膜光泽性和手感,随着有机硅的加入量的增加,漆膜的耐水性提高、吸水率下降,热重分析表明漆膜耐热性提高,FTIR表明乳液中不存在NCO。     

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%。     

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。     

PIPD/Cu2 纳米纤维气凝胶的制备及性能

以聚(2,5-二羟基-1,4-苯撑吡啶并二咪唑)(PIPD)为基体、三氟乙酸(TFA)和甲烷磺酸(MSA)为混酸,通过混酸剥离-去质子化诱导凝胶-冷冻干燥-惰性气氛高温处理制备出PIPD纳米纤维气凝胶.对PIPD纳米纤维气凝胶的形貌和结构进行表征,结果表明,混酸法制备PIPD纳米纤维气凝胶过程中,强质子酸破环了PIPD纤维的晶区和取向,PIPD主体的化学结构未发生明显变化.制得的PIPD纳米纤维气凝胶具有蜂窝孔结构、低密度(6.90～15.2 mg/cm3)和高孔隙率(99.1％～99.6％).当PIPD含量(以MSA和TFA总质量为基准,下同)不高于1％时,PIPD纳米纤维气凝胶无明显收缩.惰性氛围高温处理使PIPD纳米纤维气凝胶具有弹性.水平垂直燃烧、极限氧指数(LOI)、导热系数测试表明,PIPD含量为0.5％的纳米纤维气凝胶达到不可燃水平(UL-94,V-0级),LOI高达49.2％,100℃下低热传导性〔导热系数为0.052 W/(m·K)〕.此外,引入Cu2+配位交联网络提高PIPD纳米纤维气凝胶的压缩应力,增强后气凝胶的压缩应力是初始PIPD纳米纤维气凝胶的约16倍.     

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.