笼型倍半硅氧烷基聚合物的制备和结构性能及应用

笼型聚倍半硅氧烷基聚合物是一种典型的多面体有机/无机分子复合物材料,因其具有优异的光、电、热、磁、声、力学和化学相容性等性能,所以近年来被极力的引入较为尖端的技术领域进行研究和应用。本文详尽归纳总结了笼型倍半硅氧烷基聚合物的现行制备方法,讨论了笼型倍半硅氧烷结构对材料性能的影响。最后,对笼型倍半硅氧烷基聚合物材料的应用领域和发展趋势进行了详细说明。     

笼型倍半硅氧烷基聚合物的制备和结构性能以及应用

笼型聚倍半硅氧烷基聚合物是一种典型的多面体有机/无机分子复合物材料,因其具有优异的光、电、热、磁、声、力学和化学相容性等性能,所以近年来被极力的引入较为尖端的技术领域进行研究和应用。本文详尽归纳总结了笼型倍半硅氧烷基聚合物的现行制备方法,讨论了笼型倍半硅氧烷结构对材料性能的影响。最后,对笼型倍半硅氧烷基聚合物材料的应用领域和发展趋势进行了详细说明。     

笼型倍半硅氧烷改性树脂的性能分析

笼型倍半硅氧烷是一类具有特殊分子结构的有机硅化合物。其分子的无机硅氧骨架核心为材料提供良好的耐热性,外围有机基团可增强与聚合物基体间的相容性,以它为前驱体可以得到硅氧骨架为核心的分子级有机/无机纳米杂化材料。笼型倍半硅氧烷通过共价键或共混接入聚合物中会限制分子链的运动,使高分子链的柔性降低,导致了聚合物玻璃化转变温度升高。笼型倍半硅氧烷最显著的特性是提高聚合物的热性能及阻燃性。     

硅倍半氧烷-环氧杂化材料的研究

将环己基硅倍半氧烷硅三醇与环氧树脂E-51在环烷酸钴催化下进行反应,制成硅倍半氧烷-环氧杂化材料.通过傅立叶红外光谱、差热分析证实,反应具有较低的活化能,只是笼型结构外围的Si-OH与环氧基团进行反应,反应对笼型结构无影响;动态力学性能与热稳定性的分析表明,与4,4′-二氨基二苯砜固化的环氧固化物相比,硅倍半氧烷-环氧杂化材料具有较高的玻璃化转变温度、储能模量及热分解温度和热残余量.     

有机-无机杂化纳米结构体——多面体低聚硅倍半氧烷研究进展

多面体低聚硅倍半氧烷是基于化学键合作用形成的分子内杂化体系,其改性后的材料是一类具有广泛潜在应用价值的新型有机-无机杂化材料。介绍了多面体低聚硅倍半氧烷单体的结构、性能、单体及其衍生物的合成,以及其改性聚合物材料在航空、航天、生物、电子等高科技领域内的应用前景。针对国内的研究现状,指出低聚硅倍半氧烷-聚合物杂化体系研究所存在的问题。     

多面体低聚倍半硅氧烷基多孔材料的研究进展

综述了多面体低聚倍半硅氧烷基多孔材料的制备方法,包括硅氢化反应、自由基反应、偶联反应、Friedel-Crafts反应等,并对其发展趋势进行了展望。     

硅系阻燃剂研究进展

综述了近年来有关硅系阻燃剂的结构与性能以及阻燃改性等方面的研究进展。介绍了无机硅系阻燃剂 (包括聚合物/层状硅酸盐以及聚合物/二氧化硅纳米复合材料)的热稳定性和阻燃性能。侧重论述了有机硅系阻燃剂(包括本质阻燃聚合物、笼状倍半硅氧烷及其改性聚合物)的热稳定性、阻燃性能和阻燃机理。     

倍半硅氧烷基电致发光材料的研究进展

有机电致发光器件(OLED)作为一种新型显示器件,其结构简单、易于制造、成本更低、性能更好,未来在各领域将有很大的应用潜力。其中电致发光材料是OLED的核心材料,是OLED能否工业化生产的关键因素,但目前发光材料仍存在一些不足。多面体倍半硅氧烷(POSS)作为一种笼状无机材料,由于具有良好的耐热性、力学强度、稀释效应,经常与咔唑、芴等有机物杂化,从而有效地改善光电和物理性能,被用作OLED电致发光材料,已得到当前电致发光研发领域的极大关注。本文主要介绍了倍半硅氧烷基电致发光材料的研究进展。     

含活性氢基的八聚笼型倍半硅氧烷的合成与表征

笼形倍半硅氧烷具有较低的介电常数。采用正硅酸乙酯和季铵碱为原材料,合成了八聚四甲基铵基笼型倍半硅氧烷,并采用二甲基氯硅烷对其进行烷基取代,得到了含活性氢基的八聚笼型倍半硅氧烷。采用核磁共振29Si、13C、1H谱和凝胶渗透色谱GPC对其结构进行了表征和确认。     

乙丙共聚物相对分子质量分布的研究

以三氯氧钒-混合烷基铝、改性三氯氧钒-倍半烷基铝、三氯氧钒-倍半烷基铝、三乙酰丙酮钒-三异丁基铝为催化体系,以己烷为溶剂、氢气为相对分子质量调节剂,研究了不同催化体系对聚合物相对分子质量分布的影响。对主催化剂的加入量、助催化剂与主催化剂的比例、氢气的体积分数对聚合物相对分子质量分布的影响进行了较详细的研究。结果表明,采用不同的催化体系,得到的聚合物相对分子质量分布不同,n(Al)/n(V)对聚合物相对分子质量分布无影响。     

Electrical properties of poly(arylene ether nitrile)/graphene nanocomposites prepared by in situ thermal reduction route

A series of functional metallo-supramolecular materials based on polyhedral oligomeric silsesquioxane (POSS) and phenanthroline ligand were prepared using a two-step approach. Firstly, using a phenanthroline ligand, an amino-functionalized transition metal complex was prepared by tin(II) chloride. In the second step, this metal complex was subsequently reacted with the octakis(3-chloropropyl)octasilsesquioxane, resulting for the metallosupramolecular polymers bearing POSS structure. All the synthesized compounds were fully characterized by spectroscopic analysis, thermal and electron microscopy techniques. Stimuli responsible properties of metallo-supramolecular materials were also investigated the reversibility upon external factors, such as electrochemical or the addition of competitive complexing ligands by electroanalytic techniques and UV–Vis spectroscopy. The electro- and chemo-responsive properties of the metallo-supramolecular materials were also improved. As a result, prepared phenanthroline-functionalized polyhedral silsesquioxane are good candidates for electronic, opto-electronic, and photovoltaic applications as a smart stimuli-responsive material.     

Metallo‐supramolecular materials based on terpyridine‐functionalized polyhedral silsesquioxane

In this study, novel metallo‐supramolecular materials based on terpyridine‐functionalized polyhedral silsesquioxane were synthesized from 4′‐chloro‐2,2′:6′,2″‐terpyridine and amino‐group‐functionalized polyhedral oligomeric silsesquioxane. The obtained terpyridine‐functionalized polyhedral silsesquioxanes were converted to metallo‐supramolecular hybrid materials by coordination polycondensation reaction with Co(II) or Cu(II) ions. The supramolecular polymers created were characterized by means of structure, morphology and stimuli‐responsive performance employing scanning electron microscopy, amperometric techniques and UV–visible and Fourier transform IR spectroscopy. UV?visible and cyclic voltammetry studies showed that both the optical and electrochemical properties of metallo‐supramolecular materials are affected by the substituent at the pyridine periphery. The supramolecular polymers obtained exhibited electrochromism during the oxidation processes of cyclic voltammogram studies. As a result, these terpyridine‐functionalized polyhedral silsesquioxanes are good candidates for electronic, opto‐electronic and photovoltaic applications as smart stimuli‐responsive materials. © 2013 Society of Chemical Industry     

Investigation of the thermal,mechanical and morphological properties of poly(vinyl chloride)/polyhedral oligomeric silsesquioxane nanocomposites

Research into organic–inorganic nanocomposites has recently become popular, particularly the development of new polymer nanocomposites. Compared to pristine polymers or conventional composites, these nanocomposites exhibit improved properties. The storage modulus of a poly(vinyl chloride) (PVC)/polyhedral oligomeric silsesquioxane (POSS) nanocomposite slightly decreased with POSS content, but had a higher modulus from 50 to 100 °C. Some of the material appeared to be aggregated with 1 wt% POSS in the polymeric matrix. Conversely, with a POSS content of 5 wt%, a better dispersion of the nanoparticles was observed. The presence of POSS in the plasticised PVC compound had little influence on the final properties of the nanocomposites, showing weaker interactions between the POSS and the plasticised PVC compound. Copyright © 2010 Society of Chemical Industry     

State-of-the-Art Overview on Polymer/POSS Nanocomposite

Research into polymer containing polyhedral oligomeric silsesquioxane has been expanded during the past years, enlightening new categories of polymer/polyhedral oligomeric silsesquioxane nanocomposite and unanticipated applications. These hybrids own superior structural and functional properties (strength, thermal stability, optical features, low toxicity, biocompatibility) due to nanometer size of polyhedral oligomeric silsesquioxane. The state of polyhedral oligomeric silsesquioxane-reinforced polymeric [poly(methyl methacrylate, poly(vinyl chloride), polyurethane, polyamide, epoxy, and poly(ethylene glycol)] systems are reviewed in this article. Physical blending, covalent bonding, and chemical cross-linking have been used to provide excellent reinforcement. A comprehensive coverage of various appliances of polymer/polyhedral oligomeric silsesquioxane nanocomposite has been given particularly aerospace, semiconducting material, biomedical, and textile industry.     

POSS related polymer nanocomposites

This review describes the syntheses of polyhedral oligomeric silsesquioxane (T₈-POSS) compounds, the miscibility of POSS derivatives and polymers, the preparation of both multifunctional and monofunctional monomers and polymers containing POSS including styryl-POSS, methacrylate-POSS, norbornyl-POSS, vinyl-POSS, epoxy-POSS, phenolic-POSS, benzoxazine-POSS, amine-POSS, and hydroxyl-POSS. The thermal, dynamic mechanical, electrical, and surface properties of POSS-related polymeric nanocomposites prepared from both monofunctional and multifunctional POSS monomers are discussed. In addition, we describe the applications of several high-performance POSS nanocomposites in such systems as light emitting diodes, liquid crystals, photo-resist materials, low-dielectric constant materials, self-assembled block copolymers, and nanoparticles.     

POSS/聚合物有机-无机杂化材料的研究进展

介绍了笼型倍半硅氧烷(POSS)的特点。综述了POSS/聚合物杂化材料近年来的研究进展(包括POSS/环氧树脂杂化材料、POSS/聚酰亚胺杂化材料、POSS/有机硅杂化材料、POSS/聚乙烯杂化材料、POSS/聚丙烯杂化材料和其他类型含POSS的杂化材料等),并对其应用前景进行了展望。     

Soluble network polymers based on trifluoropropyl-substituted open-cage silsesquioxane: Synthesis,properties, and application for surface modifiers

Fluorinated completely condensed polyhedral oligomeric silsesquioxanes (F-CC-POSSs) are widely utilized as surface modifiers for polymeric materials because of their polyhedral and fluorine-rich structures, which generate polymers with lower surface energies under molecular-level control. In contrast, their derivatives, fluorinated incompletely condensed or open-cage POSSs (F-IC-POSSs), have similarly intriguing structures, but their utilization for polymer synthesis remains undeveloped. Herein, fluorinated network polymers were prepared based on a 3,3,3-trifluoropropyl-substituted IC-POSSs via hydrosilylation polymerization with isobutyl- and phenyl-substituted IC-POSS under optimized conditions. In addition to their good thermal stability and tunable refractive indices, these polymers exhibited solution processability and their casting films showed excellent optical transparency, indicating their potential for constructing fluorinated polymers. Their utilization as surface modifiers was examined by addition to poly(methylmethacrylate) (PMMA) films. Intriguingly, modified PMMA films with 2.0 and 0.5 wt% addition showed similar hydrophobicity and surface energies to the films prepared with only fluorinated network polymers.