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。     

多面体低聚倍半硅氧烷合成的研究进展

介绍了多面体低聚倍半硅氧烷(POSS)的分类、结构和性能,POSS是基于化学键合作用而形成的一种分子水平上的纳米有机/无机杂化体,具有规整的立体结构、纳米尺度、优良的相容性和修饰性,其独特的纳米笼形结构使之成为分子结构设计和材料改性的最佳选择。综述了POSS的合成方法及研究进展,如三官能度硅烷或四官能度硅烷在酸、碱或有机盐催化下通过水解缩合反应合成POSS;以POSS为母体,通过封角闭环法和官能团转化衍生法合成POSS;点击化学法制备POSS等。比较了各种方法的优点和存在的问题,指出目前国内POSS的研究重点是合成带有高活性的POSS单体,改进合成路线及工艺,为其工艺化提供技术支持。     

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。     

笼型倍半硅氧烷基聚合物的制备和结构性能以及应用

笼型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,所以近年来被引入较为尖端的技术领域进行研究和应用。本文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说明。     

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及多面体低聚倍半硅氧烷-聚合物的研究进展

综述了多面体低聚倍半硅氧烷(POSS)的结构、性质与合成方法,重点介绍了单官能团、双官能团、多官能团3类POSS可以通过共聚、缩聚、接枝、共混等多种方式引进聚合物中,形成真正的有机/无机纳米杂化材料,最后指出了POSS的发展方向.     

多面体低聚倍半硅氧烷改性聚合物材料研究进展

介绍了多面体低聚倍半硅氧烷(POSS)的特性及POSS的3种基本制备方法,综述了POSS改性聚合物的最新研究进展(包括POSS改性聚烯烃、聚丙烯酸酯、聚酰亚胺、环氧树脂等)及POSS改性聚合物作为阻燃材料、耐热材料、光电材料、膜材料等的应用,指出了POSS材料的研究与应用前景.     

多面体低聚倍半硅氧烷的研究进展

介绍了多面体低聚倍半硅氧烷(POSS)的基本特性以及常用的5种制备方法。指出了POSS在多孔材料、高性能高分子材料、光固化树脂、电子材料以及航空与空间等领域的应用情况。对POSS在发展过程中存在的一些问题进行了分析并展望了其今后的发展趋势。     

氰酸酯-倍半硅氧烷杂化材料制备及其性能研究

采用分子中含有反应性环氧基团的环氧基倍半硅氧烷(SSQE)与氰酸酯(CE)共固化,形成了CE-SSQE杂化材料.采用红外光谱跟踪了体系的形成过程,表明SSQE也可以作为CE的固化刑而形成三嗪环.采用差示扫描量热法、热重分析法考察了杂化材料的热性能,表明该杂化材料具有较高的玻璃化转变温度及高的热解温度,作为耐高温烧蚀材料具有很好的发展前景.     

笼型单乙烯基倍半硅氧烷的合成及表征

用环戊基三氯硅烷合成不完全缩合三羟基硅氧烷［(C₅H₉)₇Si₇O₉(OH)₃］,再以乙烯基三氯硅烷和不完全缩合三羟基硅氧烷为原料,以四氢呋喃和三乙胺为混合溶剂,通过“顶角-戴帽”反应合成了笼型单乙烯基倍半硅氧烷,即1,3,5,7,9,11,13-七环戊基-15-乙烯基笼型倍半硅氧烷(VinylPOSS)。利用FTIR、¹H NMR、²⁹Si NMR、¹³C NMR、元素分析、WAXD和TGA表征了VinylPOSS的结构及热稳定性。研究结果表明VinylPOSS的产率随着反应时间的增加而提高,当反应时间为10 h时,产率高达90%;其在弱极性溶剂中具有较好的溶解性,5%失重温度为283℃,800℃残留率为56%,具有较高的热稳定性。研究了VinylPOSS和高含氢硅油(HHSF)的反应性,结果表明VinylPOSS能与含氢硅油发生α、β加成反应, 且以β加成为主。     

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。     

甲基笼型倍半硅氧烷/CE杂化复合材料的力学性能

以甲基笼型倍半硅氧烷(POSS)作为氰酸酯树脂(CE)的改性剂,制备出一种POSS/CE杂化复合材料。研究了杂化复合材料中POSS用量对CE结构及力学性能的影响,同时采用红外光谱(FT-IR)法对不同POSS/CE体系的反应性进行了研究。结果表明:POSS的加入对CE的反应性影响不大,有利于POSS/CE杂化体系固化工艺的制定;当杂化体系中w(POSS)=5%时,材料的冲击强度(9.7 kJ/m2)相对最大(提高了49%),弯曲强度(90 MPa)也相对较高,说明适量的POSS对CE具有明显的增韧、增强作用。     

Preparation of solid-state composite electrolytes based on organic/inorganic hybrid star-shaped polymer and PEG-functionalized POSS for all-solid-state lithium battery applications

A series of composite electrolytes (CEs) consisting of organic/inorganic hybrid star-shaped polymer (SPP13), plasticizer (PEG-functionalized POSS derivatives), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) were prepared to investigate the effects of the composite compositions and PEG chain length of PEs on the properties of CEs. SPP13 was prepared via ATRP from poly(ethylene glycol) methyl ether methacrylate (PEGMA) and methacryl-cyclohexyl-POSS (MA-POSS) using an octafunctional initiator, and the PEG-functionalized POSS derivatives were synthesized by the hydrosilylation reaction of octakis(dimethylsilyloxy)silsesquioxane (OHPS) and allyl-PEG. The CEs were found to be dimensionally-stable enough to separate the electrodes in batteries, but they still possessed high mobility of ion-conducting P(PEGMA) segments, as estimated by the low glass transition temperatures (T_g). The CEs having solid-state show quite high ionic conductivity (4.5 × 10⁻⁵ S cm⁻¹ at 30 °C) which is about three times of magnitude larger than that of the matrix polymer (SPP13) electrolyte (1.5 × 10⁻⁵ S cm⁻¹ at 30 °C). The CEs were electrochemically stable up to +4.2 V without the decomposition of electrolytes. An all-solid-state lithium battery prepared from the CEs exhibited larger discharge capacity than that prepared from the SPP13 electrolyte at 60 °C.     

Epoxy‐functionalized polyhedral oligomeric silsesquioxane/cyanate ester resin organic–inorganic hybrids with enhanced mechanical and thermal properties

A series of cyanate ester resin (CE) based organic–inorganic hybrids containing different contents (0, 5, 10, 15 and 20 wt%) of epoxy‐functionalized polyhedral oligomeric silsesquioxane (POSS‐Ep) were prepared by casting and curing. The hybrid resin systems were studied by the gel time test to evaluate the effect of POSS‐Ep on the curing reactivity of CE. The impact and flexural strengths of the hybrids were investigated. The micromorphological, dynamic mechanical and thermal properties of the hybrids were studied by SEM, dynamic mechanical analysis (DMA) and TGA, respectively. Results showed that POSS‐Ep prolonged the gel time of CE. CE10 containing 10 wt% POSS‐Ep displayed not only the optimum impact strength but the optimum flexural strength. SEM results revealed that the improvement of mechanical properties was attributed to the large amount of tough whirls and fiber‐like pull‐outs observed on the fracture surfaces of CE10. DMA results indicated that POSS‐CE tended to decrease E′ of the hybrids in the glassy state but to increase E′ of the hybrids in the rubbery state. TGA results showed that CE10 also possesses the best thermal stability. The initial temperature of decomposition (T_i) of CE10 is 426 °C, 44 °C higher than that of pristine CE. © 2013 Society of Chemical Industry     

一种星形大分子引发剂的合成与表征

本文以笼形八聚(二甲基硅烷基)倍半硅氧烷(Q8M8H)?烯丙醇??-溴代异丁酰溴为原料通过氢化硅烷化反应和酯化反应合成了八聚(2-溴-2-甲基异丁基硅氧基)倍半硅氧烷(OBPS)星形大分子引发剂,并通过FTIR、1H-NMR、29Si-NMR和GPC对其结构进行了表征,讨论了溶剂?温度和时间对产物结构和产率的影响?最佳反应条件为:以THF为溶剂,0℃反应3h,室温下反应20h,产率可达85.0%?该化合物可进一步做为原子转移自由基聚合的引发剂制备星形聚合物?     

Chemical Bonding between Phenolic Resins and Polyhedral Oligomeric Silsesquioxanes (POSS) in Inorganic–Organic Hybrid Nanocomposites

Three classes of inorganic–organic hybrid phenolic resin/polyhedral oligomeric silsesquioxane (POSS) nanocomposites were synthesized. Multifunctional dichloromethylsilylethylheptaisobutyl-POSS (POSS-1), trisilanolheptaphenyl-POSS (POSS-2), and poly(phenylsilsesquioxane) uncured POSS (POSS-3) were employed. Nonfunctional POSS-4 (octaisobuty1-POSS) was blended into the uncured phenolic resin and cured under the same conditions used for the other three nanocomposite classes. Weight ratios of 99/1, 97/3, 95/5 and 90/10 were prepared for the POSS-1, 2 and 4 series and 99/1, 97/3 and 95/5 ratios for the POSS-3 nanocomposites. POSS-1 incorporation into this phenolic resin network increases T _g and broadens the tan peak (DMTA) range. T _g and E′ values at T>T _g both increase with higher POSS-1 content. In contrast, incorporating 5 wt% of POSS-2 into the phenolic resin network lowers T _g to 193 from 213°C for the neat phenolic resin. All values of E′ for POSS-2 composites were higher, than those of the phenolic control in both glassy and rubbery regions. The T _g values of the 1 and 10% POSS-2 systems were higher. Incorporating 10 wt% of POSS-1 or POSS-2 improved the heat distorsion temperature and moduli (E′=123 and 201 GPa at 265°C, respectively, versus 56 GPa for the pure phenolic resin). Increases in E′ for T>T _g and T<T _g were also observed for all POSS-3 nanocomposites. However, the E′ at T>T _g and the T _g values of the POSS-4 composites were lower than those of the control resin. Octaisobutyl POSS-4 cannot form chemical bonds to the resin and could be extracted from its composites with THF. POSS derivatives were not present in residues extracted by THF from the phenolic resins containing POSS-1, 2 or 3, because each of these derivatives were chemically bound within the phenolic resin. Subsequent heating cycles produce much larger increases in T _g and E′ values in the rubbery region for the POSS-1, 2 and 3 composites than for the neat phenolic resin or for the POSS-4 systems. An erratum to this article can be found at     

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     

Synthesis and characterization of polyimide/polyhedral oligomeric silsesquioxane nanocomposites containing quinolyl moiety

A series of functional polyhedral oligomeric silsesquioxane (POSS)/polyimide (PI) nanocomposites were prepared using a two‐step approach. First, octa(aminophenyl)silsesquioxane (OAPS) was mixed with poly(amic acid) (PAA) prepared by reacting bis(4‐amino‐3,5‐dimethylphenyl)‐3‐quinolylmethane and 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride. Second, the resulting solution was subjected to thermal imidization. The well‐defined ‘hard particles’ (POSS) and the strong covalent bonds in the amide linkage between the carbon atom of the carboxyl side group in PAA and the nitrogen atom of the amino group in POSS lead to a significant improvement in the thermal and mechanical properties. Homogeneous dispersion of POSS cages in the PI is evident from scanning electron microscopy, which further confirms that the POSS molecule becomes an integral part of the organic‐inorganic inter‐crosslinked network system. Differential scanning calorimetry and dynamic mechanical analysis show that the glass transition temperatures of the POSS‐containing nanocomposites are higher than that of the corresponding neat PI system, owing to the significant increase of the crosslinking density in the PI/POSS nanocomposites. Increasing the concentration of OAPS in the PI networks decreases the dielectric constant. Pure PI and PI/POSS systems have good antimicrobial activity. Copyright © 2011 Society of Chemical Industry