新型无机/有机复合柱撑粘土材料的合成与表征

以无机TiCl4／HCl制成的钛基柱撑液和十六烷基三甲基溴化胺(CTAB)为有机改性液,通过控制两种柱撑液的加入顺序以及相对含量,利用蒙脱石粘土矿物层间域的特殊化学反应场所的特性,合成得到三类复合柱撑蒙脱石材料．X射线衍射结果表明,d001晶面由于CTAB与钛基水合离子的相互作用形成粒度不同的柱撑空间而表现为两个峰值．与FT-IR光谱相比,FT-Raman光谱能够更加有效地表征和鉴定复合柱撑粘土的结构差别．采用原土无机柱撑后再有机柱撑,可以合成层间距更大的复合柱撑粘土材料．经热处理后得到锐钛型氧化钛的改性粘土材料,并且可以重新合成得到无机／有机复合柱撑的新型改性粘土材料．这些合成手段为制备新型改性粘土材料应用于环保以及化工等方面提供了借鉴．     

热塑性弹性体/蒙脱土纳米复合材料的制备及性能

热塑性弹性体;蒙脱土;纳米复合材料;动态硫化     

The influence of interlayer cations on the photo‐oxidative degradation of polyethylene/montmorillonite composites

The photo‐oxidative degradation of polyethylene/montmorillonite (PE/MMT) nanocomposite and microcomposite has been investigated. It has been found that the rate of photo‐oxidative degradation of PE/MMT nanocomposite and PE/Mⁿ⁺MMT (where Mⁿ⁺ stands for multivalent transition metal cation) microcomposites is much faster than that of pure PE. For the PE/MMT nanocomposite, the acceleration of photo‐oxidative degradation is due to the influence of MMT and ammonium ion, in which the influence of ammonium is primary. The decomposition of ammonium ion may create acidic sites on layered silicates; meanwhile, the complex crystallographic structure and habit of clay minerals could also result in some active sites. The reversible photo‐redox reaction of transition metal cations has a catalytic effect in the degradation of the polymer matrix. All these catalytic active sites can accept single electrons from donor molecules of polymer matrix and induce the formation of free radical upon UV irradiation. The generation of free radical leads to the oxidization and break of molecular chain. Thus, the materials suffer degradation and their mechanical strength decreases. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3006–3012, 2004     

Crystallization kinetics and crystallization behavior of syndiotactic polystyrene/clay nanocomposites

We investigated the effects of montmorillonite (clay) on the crystallization kinetics of syndiotactic polystyrene (sPS) with isothermal differential scanning calorimetry analyses. The clay was dispersed into the sPS matrix via melt blending on a scale of 1–2 nm or up to about 100 nm, depending on the surfactant treatment. For a crystallization temperature of 240 °C, the isothermal crystallization data were fitted well with the Avrami crystallization equation. Crystallization data on the kinetic parameters (i.e., the crystallization rate constant, Avrami exponent, clay content, and clay/surfactant cation‐exchange ratio) were also investigated. Experimental results indicated that the crystallization rate constant of the sPS nanocomposite increased with increasing clay content. The clay played a vital role in facilitating the formation on the thermodynamically more favorable all‐β‐form crystal when the sPS was melt‐crystallized. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2097–2107, 2001     

Synthesis and characterization of polycyanurate/montmorillonite nanocomposites

The advantages of cyanate esters (CEs) versus competitor systems such as epoxies and polyimides, as well as the great reinforcing potential of organoclays properly dispersed into a polymeric matrix, have been examined in a series of polycyanurate (PCN)/montmorillonite (MMT) nanocomposites prepared under appropriate polymerization conditions. The curing schedule applied resulted in gradual propagation of polymerization. Through this procedure, the intragallery curing rate becomes comparable to the extragallery one, allowing intercalation before gelation. Systems with clay loadings from 1 to 3% per weight were synthesized, and their morphology and mechanical properties were studied by means of scanning electron microscopy (SEM), atomic force microscopy (AFM), wide angle X‐ray scattering (WAXS), dynamic mechanical analysis (DMA), and tensile tests. Microscopy investigations revealed better dispersion for the 3 wt % system compared to smaller concentrations, in which aggregation and, in some cases, agglomeration were the conspicuous features. Roughness and area analyses revealed more homogeneous dispersion for this nanocomposite. Topology and 3D‐phase images further suggested considerable reduction of the average particle diameters. WAXS analysis showed that the interlayer spacing of nanocomposites was increased compared to pristine MMT, indicating the formation of intercalated structures. On the other hand, tensile strength and elongation at break values displayed abrupt diminution with MMT addition, while Young's modulus exhibited a slight but systematic increment with MMT content. The decreasing glass transition tendency observed for small clay loadings was reversed in the case of 3 wt %, while secondary transitions were practically unaffected by the presence of MMT. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1036–1049, 2008     

Effect of anisometry of a platelike nanofiller on the elastic constants of a transversely isotropic composite

Analysis results for the elastic properties of a composite with a small amount of coplanarly arranged platelike filler particles are presented. The geometrical form of the particles is described by an oblate ellipsoid of revolution. The calculations are performed by formulas obtained by using the Eshelby approach for media with a low concentration of inclusions. The effect of anisometry of the ellipsoidal particles and of the ratio between the elastic moduli of the filler and matrix on the effective elastic constants of the composite is discussed. Calculation results are compared with experimental data for the elastic moduli of a nanocomposite containing completely exfoliated particles of an unmodified montmorillonite. __________ Translated from Mekhanika Kompozitnykh Materialov, Vol. 44, No. 4, pp. 493–504, July–August, 2008.     

质子交换MgO:LiNbO3波导的双层结构

本文报导MgO:LiN_bO₃质子交换波导X射线双晶衍射和红外吸收的实验结果。这些结果表明质子交换波导由浅表面层和深表面层构成。浅表面层是一个连续应变层,有着大量随机排列的O—H—O形式的缔合OH^-基团。深表面层是一个均匀应变层,其内H⁺以自由OH^-基团形式出现。质子交换波导折射串不稳定性与双层结构中的结构驰豫密切相关。通过对质子交换过程的分析,提出两条避免双层结构的途径,其一为降低交换剂中的H⁺浓度,另一条是采用有限源工艺。     

Unprecedented alkylation of silicon enolates with alcohols via carbenium ion formations catalyzed by tin hydroxide-embedded montmorillonite

The solid acid, tin hydroxide-embedded montmorillonite, catalyzes the unprecedented alkylation of various silicon enolates with primary, secondary and tertiary benzylic alcohols as well as secondary allylic alcohols. The acid catalysis of Sn-Mont was not only higher than that of the other ion-exchanged montmorillonites (M-Mont; M = H, Ti, Fe and Al), but also higher than that of the typical homogeneous acid catalysts such as BF₃·OEt₂, TMSOTf and TfOH.     

阿司匹林-蒙脱土-壳聚糖缓释微球的制备及其体外释放性能

利用溶液法预先制备壳聚糖(Cs)-蒙脱土(MMT)复合材料(Cs-MMT),以Cs-MMT、Cs为原料,采用反相悬浮聚合法制得一种新型药物缓释体系阿司匹林-蒙脱土-壳聚糖载药微球(Asp-MMT-Cs)。采用FT-IR、SEM表征了Cs-MMT和Asp-MMT-Cs载药微球的结构及形态;设计正交实验优化了Asp-MMT-Cs载药微球的制备工艺;通过体外释放实验探讨了载药微球在不同模拟释放液中的释药规律。结果表明:所得微球球形度好,粒径分布较均匀;最优工艺制得的载药微球平均粒径为81.20μm,载药量为9.61%,包封率为76.78%。该缓释体系具有pH敏感性,更倾向于在pH较高的磷酸盐缓冲溶液中释放。