The synthesis and characterization of polystyrene/magnetic polyhedral oligomeric silsesquioxane (POSS) nanocomposites

Fc-CHCH-C₆H₆-(C₅H₉)₇Si₈O₁₂ (POSS1, Fc: ferrocene) which contain both metal and CC double bond was firstly synthesized by Wittig reaction. The chemical structure of POSS1 was characterized by FTIR, ¹H, ¹³C and ²⁹Si NMR, mass spectrometry and elemental analysis, and the magnetic property of POSS1 have also been studied. Polystyrene composites containing inorganic-organic hybrid polyhedral oligomeric silsesquioxane (POSS1) were prepared by bulk free radical polymerization. XRD and TEM studies indicate that POSS1 is completely dispersed at molecular level in PS matrix when 1 wt% POSS1 is introduced, while some POSS1-rich nanoparticals are present when content of POSS1 is beyond 3 wt%. GPC results show that molecular weight of the PS/POSS1 nanocomposites are increased with addition of POSS1. TGA and TMA data show the thermal stabilities of PS/POSS1 nanocomposites have been improved compared to neat PS. The PS/POSS1 nanocomposites also display higher glass transition temperatures (T_g) in comparison with neat PS. Viscoelastic properties of PS/POSS1 nanocomposites were investigated by DMTA. The results show the storage modulus (E′) values (temperature>T_g) and the loss factor peak values of the PS/POSS1 nanocomposites are higher than that of neat PS. Mechanical properties of the PS/POSS1 nanocomposites are improved compared to the neat PS.     

Epoxy nanocomposites with octa(propylglycidyl ether) polyhedral oligomeric silsesquioxane

The POSS-containing nanocomposites of epoxy resin were prepared via the co-curing reaction between octa(propylglycidyl ether) polyhedral oligomeric silsesquioxane (OpePOSS) and the precursors of epoxy resin. The curing reactions were started from the initially homogeneous ternary solution of diglycidyl ether of bisphenol A (DGEBA), 4,4′-Diaminodiphenylmethane (DDM) and OpePOSS. The nanocomposites containing up to 40 wt% of POSS were obtained. The homogeneous dispersion of POSS cages in the epoxy matrices was evidenced by scanning electronic microscopy (SEM), transmission electronic microscopy (TEM) and atomic force microscopy (AFM). Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) showed that at the lower POSS concentrations (<30 wt%) the glass transition temperatures (T_gs) of the nanocomposites almost remained invariant whereas the nanocomposites containing POSS more than 40 wt% displayed the lower T_gs than the control epoxy. The DMA results show that the moduli of the nanocomposites in glass and rubbery states are significantly higher than those of the control epoxy, indicating the nanoreinforcement effect of POSS cages. Thermogravimetric analysis (TGA) indicates that the thermal stability of the polymer matrix was not sacrificed by introducing a small amount of POSS, whereas the properties of oxidation resistance of the materials were significantly enhanced. The improved thermal stability could be ascribed to the nanoscaled dispersion of POSS cages and the formation of tether structure of POSS cages with epoxy matrix.     

Epoxy nanocomposites containing mercaptopropyl polyhedral oligomeric silsesquioxane: Morphology,thermal properties,and toughening mechanism

A novel polyhedral oligomeric silsesquioxane (POSS) containing a mercaptopropyl group [mercaptopropyl polyhedral oligomeric silsesquioxane (MPOSS)] was synthesized via the hydrolytic condensation of γ-mercaptopropyl triethoxysilane in an ethanol solution catalyzed by concentrated hydrochloric acid and was used to modify epoxy–amine networks by a cocuring reaction with diglycidyl ether of bisphenol A (DGEBA). The structure, morphology, and thermal and mechanical properties of these MPOSS/DGEBA epoxy nanocomposites were studied and investigated with thermogravimetric analysis/differential thermal analysis (TGA–DTA), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR). From SEM analysis, we observed that the miscibility between epoxy and POSS occurred at a relatively high POSS content, which characterized this mixture as a polymer nanocomposite system. The impact test showed that MPOSS reinforced the epoxy effectively, and the SEM study of the impact fracture surface showed that the fibrous yielding phenomenon observed was an indication of the transition of the brittle stage to a ductile stage and correlated well with the large increases in the impact strength; this was in agreement with the in situ reinforcing and toughening mechanism. The TGA–DTA analysis indicated that the MPOSS/DGEBA epoxy hybrids exhibited lower thermostability at a lower temperature but higher thermostability and higher efficiency in char formation at an elevated temperature. Differential scanning calorimetry showed that the glass transition temperature (T_g) of the MPOSS/epoxy hybrids were lower than that of the neat epoxy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

笼型倍半硅氧烷改性UPR的固化性能与热性能

采用示差扫描量热仪(DSC),热重分析仪(TGA)及动态力学分析仪(DMA)研究了甲基丙烯酰氧丙基笼型倍半硅氧烷(MAP-POSS)与一缩二乙二醇型UPR、苯乙烯的等温共固化反应及动力学,测试了固化物的热性能和动态力学性能。结果表明,固化过程符合自催化反应机理,当体系中MAP-POSS质量分数为5%时,5%热失重温度和残留量5%时的温度较未加体系分别提高7℃和31℃,玻璃化转变温度降低4.2℃,热降解动力学符合1级反应。     

笼型倍半硅氧烷（POSS）的功能化改性 及应用研究进展

有机/无机杂化材料的改性及应用是目前材料科学中最富有活力的研究领域之一。其中笼型倍半硅氧烷（Polyhedral oligomeric silsesquioxane,POSS）在分子水平上实现了有机组分与无机组分的结合,结构呈硅氧骨架连接的立体笼型,具有优异的反应活性、耐热阻燃性、多孔性和纳米尺寸效应等特性,通过化学改性可将其应用在多个领域。本文主要从官能团改性、聚合改性和配位改性三个方面阐述了POSS的改性方法,综述了POSS在耐热材料、阻燃材料、增强材料和多孔材料等领域的应用研究进展,并对POSS今后的研究方向提出了展望。可从POSS的构效关系、改性方法以及安全性等方面进行更加深入和系统的研究,以促进POSS材料更广泛的应用。     

Polymer/polyhedral oligomeric silsesquioxane (POSS) nanocomposites: An overview of fire retardance

A review is presented of the recent developments concerning the use of polyhedral oligomeric silsesquioxane (POSS) for designing polymer nanocomposites endowed with enhanced fire retardancy. Emphasis is placed on the scientific and technological advances in the use of POSS as fire retardants, as well as on the achievements and challenges associated to the exploitation of POSS either alone or in combination with conventional fire retardants to provide the required fire retardancy to polymer materials. Polymer/POSS nanocomposites show a great potential to provide materials characterized by improved fire retardancy together with superior physical properties and environmental neutrality. Achievements obtained with POSS in fire retardancy are presented for the different types of polymer materials and critically discussed, especially in terms of the modes of fire retardant action, in the attempt to reveal attractive strategies for successful development of the next generation of polymer/POSS materials and applications.     

笼型倍半硅氧烷(POSS)/环氧杂化树脂体系固化反应动力学及性能研究

为了提高环氧树脂的耐热性,采用笼型倍半硅氧烷(POSS)改性双酚A型环氧树脂E51,得到有机无机杂化树脂。采用Ozawa和Kissinger两种方法研究了杂化树脂/4,4′-二氨基苯砜(DDS)体系的固化反应动力学。TGA分析表明,POSS的加入提高了E51/DDS固化树脂体系的热性能。     

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。     

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