烯丙基异丁基多面体低聚倍半硅氧烷/聚丁二烯遥爪型纳米杂化材料的制备及表征

采用负离子聚合法,以单官能团笼型烯丙基异丁基多面体低聚倍半硅氧烷(POSS)和丁二烯为单体、正丁基锂为引发剂、环己烷为溶剂及乙基四氢糠基醚为调节剂,制备了烯丙基异丁基POSS/聚丁二烯遥爪型纳米杂化材料,对其结构进行了表征.结果表明,POSS与丁二烯发生了共聚合,实现了活性负离子引发聚合制备POSS/聚丁二烯遥爪型纳米...     

聚丁二烯/烯丙基异丁基多面体低聚倍半硅氧烷纳米杂化材料的形貌及性能

对采用活性负离子聚合法制得的聚丁二烯( PB)/烯丙基异丁基多面体低聚倍半硅氧烷(A - POSS)纳米杂化材料进行硫化,采用X射线衍射仪、扫描电子显微镜、差示扫描量热法、热重分析、动态力学性能分析等手段,研究了A - POSS含量对硫化PB/A -POSS纳米杂化材料的微观形貌、耐热性能和动态力学性能的影响.结果表明...     

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。     

多面体低聚倍半硅氧烷研究的最新进展

多面体低聚倍半硅氧烷（POSS）是目前研究相当活跃的一类有机—无机杂化结构的纳米粒子。通过官能化POSS直接聚合或利用化学反应将POSS结合到聚合物中以及作为纳米添加剂与其他材料共混,可制备多种多样的聚合物/POSS纳米复合材料。POSS的引入能有效降低材料的介电常数,改善材料的热性能、机械性能、耐火性、防水防油性、加工性能、牢固度和透明度等;因此,POSS被认为是一种优良的纳米构筑材料。本文对POSS研究的近况进行了简要概述。     

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。     

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.     

疏水性聚倍半硅氧烷纳米杂化材料的合成及性能

以甲基三乙氧基硅烷（MTES）和十二烷基三甲氧基硅烷（DTMS）为前驱体,以NaOH为催化剂,在乙醇-水体系中进行水解-缩合反应,制得了一种疏水性聚十二烷基/甲基倍半硅氧烷纳米杂化材料（PDMSQ NPs）。通过FTIR和XPS对PDMSQ NPs的化学结构进行了表征;用DLS、FE-SEM及 TGA等对PDMSQ NPs的平均粒径、微观形貌和耐热稳定性进行了考察,对其合成工艺条件进行了优化。结果表明,PDMSQ NPs表面C元素含量高达41.73 %,电子结合能103.04 eV处归属为聚倍半硅氧烷中Si 2p的特征峰,PDMSQ NPs为表面含十二烷基和甲基且以Si—O键为骨架的纳米球结构。PDMSQ NPs失重5 %时温度为351 ℃,表明PDMSQ NPs热稳定性优良。FE-SEM分析可知,当反应温度为60℃,n(MTES)∶n(DTMS)=10∶1.0~10∶1.4时,制得的PDMSQ NPs表面光滑、呈单分散性规整球形,水静态接触角最高达168°。提出了PDMSQ NPs的形成机理。     

多面体低聚倍半硅氧烷在聚合物中的应用

多面体低聚倍半硅氧烷(POSS)具有特殊的纳米级笼形结构,与聚合物有良好的结合性和相容性,采用POSS改性聚合物可制备分子级分散的纳米复合材料。介绍了POSS的结构及特性,并综述了POSS在聚合物中的应用及研究进展。     

离子型聚合反应机理制备聚合物/POSS纳米杂化材料的研究进展

多面体低聚倍半硅氧烷（POSS,Polyhedral Oligomeric Silsesquioxane）作为一种特殊的有机/无机杂化纳米粒子备受关注。本文综述了国内外通过离子型反应机理制备聚合物/POSS纳米杂化材料的一些进展,着重介绍反应机理、特点,并对这一领域的前景进行了展望。     

Highly soluble polyamide–polyhedral oligomeric silsesquioxane hybrid nanocomposites: Synthesis and characterization

A method of preparing linear polyamide‐polyhedral oligomeric silsesquioxane (PA‐POSS) hybrid nanocomposites in a reactor using thionyl chloride/triethylamine (TEA) as the activating agent was investigated. Soluble polyamic acid (PAA) having carboxylic acid end groups were first synthesized by condensation reaction of 2,2‐ bis(3,4‐dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and 2,2‐bis[4‐(4‐aminophenoxy)phenyl]‐1,1,1,3,3,3‐hexafluoropropane, (6FODA). The PAA was acylated by SOCl₂/TEA and followed by the addition of different mole percentages of aminopropyl heptacyclopentyl POSS (AP‐POSS) and 3‐(trifluoromethyl) aniline to get the PA‐POSS hybrid nanocomposites. The chemical structure of PA‐POSS hybrid nanocomposites were investigated by ATR‐FTIR and NMR spectroscopic techniques. Thermal and morphological properties of PA‐POSS were influenced by changing the percentage of POSS and investigated by thermogravimetric analysis, differential scanning calorimetry, scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. Wide angle X‐ray diffraction and contact angle measurements. The PA‐POSS with hexafluoroisopropylidene and POSS groups have higher bulk density resulting in higher free volume and then increasing the solubility property. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Synthesis and characterization of polyhedral oligomeric silsesquioxane-based waterborne polyurethane nanocomposites

A series of aqueous polyurethane nanocomposites were prepared using various amounts (0.3-4.6 wt%) of a diol functionalized polyhedral oligomeric silsesquioxane (POSS) by the prepolymer mixing method. N,N-bis(2-hydroxy ethyl-2-amino ethane sulfonic acid sodium salt (BES sodium salt) was used as the anionic internal emulsifier and ionic center. The molecular structure of the samples was characterized by ATR-FTIR spectroscopy. We investigated the effect of the POSS contents on the properties of the specimens by particle size and viscosity measurements, X-ray diffractometry, mechanical behavior assessment, dynamic mechanical thermal analysis (DMTA), thermogravimetric analysis and morphological studies. The results showed that with increasing the POSS contents, particle size, viscosity, tensile strength, modulus, T _g , and thermal stability of the synthesized samples were improved. Also, SEM and TEM images indicated that a homogeneous morphology was obtained in the 1.2 wt% POSS-based sample. AFM results showed that the surface roughness increased as the POSS amounts increased.     

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     

Synthesis and characterization of amorphous octakis-functionalized polyhedral oligomeric silsesquioxanes for polymer nanocomposites

We have synthesized the polyhedral oligomeric silsesquioxane (POSS) derivatives OS-POSS and OA-POSS through the hydrosilylation of styrene and 4-acetoxystyrene, respectively, with octakis(dimethylsiloxy)silsesquioxane (Q₈M₈^H). We then prepared OP-POSS through acetoxyl hydrazinolysis of OA-POSS with hydrazine monohydrate. The chemical structures of these POSS derivatives were characterized using FTIR and ¹H NMR spectroscopy and MALDI-TOF mass spectrometry. Unlike Q₈M₈^H, which is crystalline, these three hydrosilylated POSS derivatives are liquids at 25 °C. Through DSC and XRD analyses, we found that they exhibit polymer-like glass transitions and amorphous halos. These octakis-functionalized POSS derivatives can be regarded as amorphous glasses possessing low glass transition temperatures, the values of which depend on the intermolecular interactions of their outer organic groups. To investigate the dispersion of these POSS derivatives in polymer nanocomposites, we blended OS-POSS, OA-POSS, and OP-POSS with polystyrene, poly(4-acetoxystyrene), and poly(4-vinylpyridine), respectively, and investigated the effects of the resulting intermolecular aromatic hydrophobic, dipole-dipole, and hydrogen-bonding interactions, respectively. Dipole-dipole interactions provided the best dispersion of OA-POSS in poly(4-acetoxystyrene), in which the POSS-polymer intermolecular interactions were of similar strength to the POSS-POSS interactions.     

Synthesis and characterization of poly(trimethylene terephthalate)/polyhedral oligomeric silsesquixanes nanocomposites

This article reports the preparation of poly(trimethylene terephthalate) (PTT)– polyhedral oligomeric silsesquioxanes (POSS) nanocomposites through in situ polymerization. The chemical structure of the PTT–POSS nanocomposites was characterized with Fourier‐transform infrared and nuclear magnetic resonance spectroscopies and the presence of POSS was further confirmed by the elemental analysis. The crystal structures as well as the position of POSS in the nanocomposites were ascertained by the X‐ray diffraction (XRD) studies. Thermal characterization studies showed the gradual decrease in the glass transition and melt crystallization temperatures. Though the thermal stability of the PTT was not affected by the incorporation of POSS, the amount of residues obtained from thermal degradation process was increased with an increase in the content of POSS. The tensile studies showed that the values of initial modulus and breaking strength were dramatically decreased with an increase in the content of POSS. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Synthesis and characterization of differently substituted phenyl hepta isobutyl‐polyhedral oligomeric silsesquioxane/polystyrene nanocomposites

Variously substituted polyhedral oligomeric silsesquioxanes (POSSs)/polystyrene (PS) nanocomposites of general formula R₇R′(SiO_1.5)₈/PS (where R = isobutyl and R′ = 4‐methoxyphenyl, 4‐methylphenyl, 3,5‐dimethylphenyl, 4‐fluorophenyl, 2,4‐difluorophenyl, 4‐chlorophenyl) were prepared by in situ polymerization of styrene in the presence of 5% w/w of POSS. The actual filler concentration in the obtained nanocomposites was checked by ¹H NMR spectroscopy. Scanning electron microscopy and FTIR spectroscopy evidenced the presence of filler‐polymer interactions. Inherent viscosity (η_inh) determinations indicated that the average molar mass of polymer in halogenated derivatives was lower than neat PS, and were in agreement with calorimetric glass transition temperature (T_g) measurements. Finally, a comparative study concerning the thermal stability of synthesized nanocomposites was carried out in both inert (flowing nitrogen) and oxidative (static air) atmospheres into a thermobalance, in the scanning mode, at 10°C min⁻¹, and the temperatures at 5% mass loss (T_5%), of various compounds were determined. The results were discussed and interpreted. POLYM. COMPOS., 35:151–157, 2014. © 2013 Society of Plastics Engineers     

八乙烯基多面体低聚倍半硅氧烷的合成与表征

采用水解缩合法,在浓HCl为催化剂的条件下,以乙烯基三甲氧基硅烷为原料合成了八乙烯基多面体低聚倍半硅氧烷,并对合成产物进行了表征;研究了反应温度、反应物的投料比对产物收率的影响.结果表明,在25 ℃,反应物水解缩合21 d,乙烯基三甲氧硅烷、HCl、CH3OH三者的体积比为9∶ 12∶ 200,乙烯基三甲氧基硅烷、HCl的体积分数分别为3.90%、5.43%时,产物的收率达到最高,为26.3%.     

Synthesis and characterization of polybenzoxazine networks nanocomposites containing multifunctional polyhedral oligomeric silsesquioxane (POSS)

A new class of polybenzoxazine/POSS nanocomposites with network structure is prepared by reacting multifunctional benzoxazine POSS (MBZ-POSS) with benzoxazine monomers (Pa and Ba) at various compositional ratios. Octafunctional cubic silsesquioxane (MBZ-POSS) is used as a curing agent, which is synthesized from eight organic benzoxazine tethers through hydrosilylation of vinyl-terminated benzoxazine monomer (VP-a) with octakis(dimethylsiloxy)silsesquioxane () using a platinum complex catalyst (Pt-dvs). Incorporation of the silsesquioxane core into polybenzoxazine matrix could significantly hinder the mobility of polymer chains and enhance the thermal stability of these hybrid materials. For these nanocomposites, increasing the POSS content in the hybrids is expected to improve its thermal properties with respect to the neat polybenzoxazine. The morphology feature is useful to explain the thermal property changes (T_g and T_d) and AFM images show that the presence of POSS aggregation in larger scales occurs at higher POSS contents. The reason of the heterogeneous phase separation may be from the less compatibility of the inorganic silsesquioxane core with organic benzoxazine species and the homopolymerization of MBZ-POSS. In the course of the formation of the polybenzoxazine/POSS hybrids, POSS particles were separated from the polybenzoxazine rich region, leading to POSS rich domains in the range of 50-1000 nm.