POSS改性聚合物复合材料阻燃性及热稳定性研究进展

综述了近几年关于多面体低聚倍半硅氧烷(POSS)改性聚合物复合材料阻燃性及热稳定性方面的机理及POSS在聚合物改性中的应用,展望了今后的研究方向.     

POSS及其改性聚合物的研究进展

介绍了多面体倍半硅氧烷（POSS）的合成方法,综述了POSS改性聚合物的一些优异性能,总结了近3年国内的研究成果,展望了POSS改性聚合物的研究前景。     

POSS/GO复合接枝碳纤维/环氧树脂复合材料性能研究

在碳纤维表面逐层接枝多面体低聚倍半硅氧烷（POSS）和氧化石墨烯（GO）后,将其用于增强环氧树脂（CF/EP）制得复合材料,采用扫描电子显微镜、接触角测试和X射线光电子能谱等研究了POSS和GO复合接枝碳纤维对CF/EP复合材料力学性能的影响。结果表明,POSS和GO可以显著提高碳纤维的表面活性和比表面积,改善树脂与碳纤维的浸润性、反应性和机械啮合作用,从而提高复合材料的界面性能和力学强度。相比未改性碳纤维复合材料,POSS/GO复合接枝改性碳纤维复合材料的层间剪切强度（ILSS）提高了98.3%,弯曲强度提高了95.7%。     

POSS/聚合物复合材料的制备以及在尼龙中应用的研究进展

多面体低聚倍半硅氧烷(polyhedral oligomeric silsesquioxane,POSS)是一种具有独特中空刚性结构的纳米级材料,作为无机-有机的新型杂化材料,其可设计的分子杂化结构使得POSS能够在聚合物基体中达到分子水平或纳米级别的良好分散,有效提升材料的表面性能、热性能、介电性能和力学性能等,极大地拓宽了在聚合物中的应用领域。本文主要针对POSS的合成制备方法、功能化改性方法、POSS形貌与性能的关系、POSS/尼龙复合材料的制备方法等进行综述。主要介绍POSS的合成方法、官能化方法及POSS/尼龙复合材料的制备方法及结构与性能的关系。未来随着POSS官能化方法的改进必然能够将POSS引入更多的聚合物基体内并实现更好的分散,POSS在聚合物中的应用范围将不断扩大。     

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。     

聚合物/笼型倍半硅氧烷复合材料应用研究进展

综述了聚合物/笼型倍半硅氧烷（POSS）复合材料在阻燃材料、低介电材料和发光材料等方面的应用研究进展,展望了聚合物/POSS复合材料的发展前景并指出了其需研究解决的问题。     

多面体低聚倍半硅氧烷在涂料领域的研究进展

多面体低聚倍半硅氧烷(POSS)作为一种有机无机杂化纳米材料,由于其独特的结构特性及改善涂料综合性能的优势而备受关注。本文介绍了POSS的结构和特性,综述了POSS的合成方法,根据官能团数量的不同将合成方法分为3种;分析了POSS改性聚合物的方式以及其改性聚合物在涂料领域的研究进展,通过POSS的改性可以提高涂料的热稳定性、力学性能、阻燃性能等,并展望了其发展趋势。     

笼型倍半硅氧烷(POSS)的应用进展研究

综述了POSS近年来在复合材料方面的应用研究进展,介绍了POSS对常见聚合物的改性应用方式及结果,如在聚丙烯酸酯、环氧树脂、聚酰亚胺、聚烯烃、聚酯、聚氨酯、有机硅树脂以及其他类型的复合材料、功能材料如介电材料、发光材料方面的应用。     

笼状硅氧烷低聚物/聚合物复合材料的研究进展

介绍了笼状硅氧烷低聚物（POSS）的概念、分类及其合成工艺,综述了POSS／聚合物复合材料的制备方法及其在提高聚合物在热稳定性、阻燃性能、医学性能、光电性能、形状记忆及表面性能等方面的应用。     

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.     

多面体笼型倍半硅氧烷(POSS)结构与热降解性能研究进展

介绍了笼形倍半硅氧烷单体结构、制备方法及基本性能,详细介绍了笼形倍半硅氧烷的热降解及对聚合物热稳定和热降解的影响。通过比较发现：（1）对于POSS单体,不同的取代基对其的热性能影响很大;（2）POSS改性聚合物,能使热稳定性得到提高。     

Mechanical and structural characterization of POSS‐modified polyamide 6

This work investigated the mechanical behavior of POSS‐modified polyamide 6 (PA6), containing PA6 chains terminated at one end with aminopropyl‐heptaisobutyl POSS. Three systems with different POSS contents (5.4, 10.8, and 16.2 wt %), each characterized by a specific molecular mass, and the corresponding PA6 neat polymers were examined. The materials were first subjected to morphological and calorimetric analysis by wide‐angle X‐ray diffraction and differential scanning calorimetry, respectively. Tensile tests, performed on the samples in wet conditions, showed that stiffness, strength, and ductility were appreciably modified by the presence of POSS in the polymeric chains. The relationships among these effects and the microstructural characteristics of the systems also were analyzed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3409–3414, 2006     

POSS改性聚亚苯基硅氧烷的合成与表征

以α,ω-二羟基聚（四甲基对硅亚苯基）硅氧烷为起始原料,分别与1,4-双（甲基氯硅基）苯和甲基二氯硅烷反应,合成了两种带硅氢基的聚亚苯基硅氧烷P1和P2;然后,再与烯丙基七戊基低聚倍半硅氧烷（烯丙基七戊基POSS）进行硅氢加成反应,引入POSS侧基,合成了POSS-P1和POSS-P2。经^1H NMR和^29Si NMR分析证实得到了目标产物;GPC分析表明,两种聚合物经POSS改性后摩尔质量均增大,摩尔质量分布变宽;DSC和TGA分析表明,两种聚合物经POSS改性后熔点分别提高8.4℃和10.6℃,热质量损失率达到5%时的温度分别提高197℃和162℃,且均在400℃以上。     

Allylated novolac/4,4′‐bismaleimidodiphenylmethane resin containing polyhedral oligomeric silsesquioxane: Preparation,morphology and thermal stability

Allylated novolac/4,4′‐bismaleimidodiphenylmethane resin (AN/BDM) had been modified with well‐defined inorganic building blocks‐polyhedral oligomeric silsesquioxane (POSS). Octamaleimidophenyl polyhedral silsesquioxane (OMPS) was used as the cocuring reagent of the AN/BDM resin to prepare POSS‐modified AN/BDM resin, and POSS content was between 0 and 17.8 wt %. The curing reaction of the POSS‐modified AN/BDM resin was monitored by means of Fourier transform infrared spectroscopy (FTIR), and the results revealed that maleimide groups on OMPS molecule could undergothe curing reaction between allyl groups and maleimide groups. Therefore, the crosslinked network containing POSS was formed. Scanning electron microscopy (SEM) and X‐ray diffraction (XRD) were employed to study the morphology of the cured POSS‐modified AN/BDM resins. The homogeneous dispersion of POSS cages in AN/BDM matrices was evidenced. Thermogravimetric analysis (TGA) indicated that incorporation of POSS into AN/BDM crosslinked network led to enhanced thermal stability. The improved thermal stability could be ascribed to higher crosslink density and inorganic nature of POSS. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3903–3908, 2007     

Glass transition temperatures of poly(hydroxystyrene-co-vinylpyrrolidone-co-isobutylstyryl polyhedral oligosilsesquioxanes)

A series of poly(hydroxystyrene-co-vinylpyrrolidone-co-isobutylstyryl polyhedral oligosilsesquioxanes) (PHS-PVP-POSS) hybrid polymers with various POSS contents was prepared by free radical copolymerization of acetoxystyrene, vinylpyrrolidone with styrylisobutylpolyhedral oligosilsesquioxanes (POSS), followed by selective removal of the acetyl protective group. The POSS content of a hybrid polymer can be effectively controlled by varying the feed ratios of reactants. The T_g of the POSS hybrid increases with the POSS content of PHS-PVP-POSS hybrids. The mechanism of T_g enhancement in these PHS-PVP-POSS hybrids was investigated using DSC, FTIR and GPC. The formation of the physically cross-linked POSS in these hybrid polymers trends to restrict polymer chain motion and results in significant T_g increase.     

Poly(acetoxystyrene-co-isobutylstyryl POSS) Nanocomposites: Characterization and Molecular Interaction

The poly(acetoxystyrene-co-isobutyl styryl polyhedral oligomeric silsesquioxanes)s (PAS-POSS) were synthesized by free radical polymerization and characterized by FTIR, high resolution NMR, FTIR, GPC, and DSC. The results show that the POSS content can be controlled by varying the POSS feed ratios. The interactions between organic components and inorganic POSS core, and the effects of inorganic POSS core on the properties of the resulting hybrids were investigated by high resolution solid state ¹³C NMR, ²⁹Si NMR and FTIR spectra. The results provide detailed understandings of the effects of POSS moiety on properties of hybrid polymers.     

Hybrid networks based on epoxidized camelina oil

Lately, renewable resources received great attention in the macromolecular compounds area, regarding the design of the monomers and polymers with different applications. In this study the capacity of several modified vegetable oil-based monomers to build competitive hybrid networks was investigate, taking into account thermal and mechanical behavior of the designed materials. In order to synthesize such competitive nanocomposites, the selected renewable raw material, camelina oil, was employed due to the non-toxicity and biodegradability behavior. General properties of epoxidized camelina oil-based materials were improved by loading of different types of organic-inorganic hybrid compounds – polyhedral oligomeric silsesquioxane (POSS) bearing one (POSS1Ep) or eight (POSS8Ep) epoxy rings on the cages. In order to identify the chemical changes occurring after the thermal curing reactions, FT-IR spectrometry was employed. The new synthesized nanocomposites based on epoxidized camelina oil (ECO) were characterized by dynamic mechanical analyze and thermogravimetric analyze. The morphology of the ECO-based materials was investigate by scanning electron microscopy and supplementary information regarding the presence of the POSS compounds were establish by energy dispersive X-ray analysis and X-ray photoelectron spectroscopy. The smooth materials without any separation phase indicates a well dispersion of the Si–O–Si cages within the organic matrix and the incorporation of this hybrid compounds into the ECO network demonstrates to be a well strategy to improve the thermal and mechanical properties, simultaneously.     

Effect of nanostructured polyhedral oligomeric silsesquioxane on the physical properties of poly(vinyl alcohol)

An effective amphiphilic polyhedral oligomeric silsesquioxane (POSS) encapsulated poly(vinyl alcohol) (PVA) nanocomposite was successfully fabricated by solution blending method. Anionic octa(tetramethylammonium) (Octa‐TMA) and poly(ethylene glycol) (PEG) were used as cage side groups in POSS (Octa‐TMA‐POSS and PEG‐POSS) for the present study. Transmission electron microscopic analysis revealed the uniform dispersion of POSS in the PVA matrix. Crystallinity of PVA/POSS system was computed from differential scanning calorimetric studies. The effect of POSS on the mechanical, dynamic mechanical, and dielectric properties of PVA has been analyzed and discussed in detail with respect to the weight percentage of POSS. The incorporation of POSS in PVA matrix remarkably enhances the Young's modulus of the matrix. The viscoelastic properties such as storage modulus, loss modulus, damping behavior, and glass transition temperature of the membranes were evaluated. The relaxation corresponding to the crystal–crystal slippage characteristic of semicrystalline polymers were observed in storage modulus curves of PVA/POSS system, suggesting the crystalline nature of matrix even in the presence of POSS. Less polar, inert, and stiff inorganic center core of POSS contributes to the reduced energy dissipation and dielectric constant of PVA/POSS system. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45447.     

POSS/CE杂化复合材料的制备与介电性能研究

为制备介电常数(ε)低、介电损耗因子(tanδ)小的集成电路板用树脂基体,以笼型倍半硅氧烷(POSS)对双酚A型氰酸酯(CE)树脂进行改性,制备出一种POSS/CE无机-有机杂化复合材料。着重探讨了POSS用量和后处理工艺等对POSS/CE树脂体系介电性能的影响。结果表明:当w(POSS)=2%(相对于CE单体质量而言)、后处理工艺为240℃/3 h时,改性体系的介电性能相对最好,其测试频率为60 MHz时的ε(为2.9)和tanδ(为0.004 5)分别比纯CE树脂降低了9.4%和35.7%;该改性体系的表观活化能为51.9 kJ/mol。     

含POSS聚芴亚胺酮的合成、表征与性能研究

以9,9-双（4-氨基苯基）芴、4,4＇-二溴二苯甲酮及八氨基苯基笼型聚倍半硅氧烷（POSS）为反应单体,通过Buchwald-Hartwig交叉偶联反应,制得了一系列不同POSS含量的POSS基聚芴亚胺酮（PIKF）。通过红外、核磁共振、电子能谱、X射线衍射等对其结构进行了表征,采用热失重分析、紫外/可见光谱及荧光光谱测试了其性能。结果表明,随着POSS含量的提高,聚合物的起始热分解温度逐步升高（从497.62℃升高到508℃和541.61℃）;POSS的引入可有效降低聚集现象的发生,从而使其最大吸收波长红移（从385 nm移至412 nm）;而非共轭大体积POSS基的引入打断了链内共轭,使聚合物的最大发射波长蓝移（从518 nm至490 nm）。