反应性杂化纳米粒子的合成及其对不相容共混物的增容研究

采用八环氧多面体低聚倍半硅氧烷(POSS(epoxy)8)和端羧基聚甲基丙烯酸甲酯(PMMA-COOH)的开环反应,运用Graft-onto的方法合成了一种反应性杂化纳米粒子:四环氧多面体低聚倍半硅氧烷-接枝-四聚甲基丙烯酸甲酯(POSS(epoxy)4-g-PMMA4).通过傅里叶红外光谱仪(FTIR),示差扫描量热仪(DSC),热失重分析仪(TGA),核磁共振波谱仪(1H-NMR)等对反应性杂化纳米粒子的结构进行了表征,结果表明成功合成了POSS(epoxy)4-g-PMMA4.并将上述合成的反应性杂化纳米粒子应用于聚偏氟乙烯/聚乳酸(PVDF/PLLA)不相容体系的增容,运用万能材料试验机、扫描电子显微镜(SEM)和透射电子显微镜(TEM)对其增容原理和效果进行研究,结果表明POSS(epoxy)4-g-PMMA4可以作为PVDF/PLLA不相容体系的反应性增容剂.     

含氟聚酰亚胺接枝低聚倍半硅氧烷制备超低介电材料

含氟聚酰亚胺接枝低聚倍半硅氧烷制备超低介电材料;介电常数;纳米复合材料;低聚倍半硅氧烷;接枝共聚;含氟聚酰亚胺     

多面体低聚倍半硅氧烷的合成研究进展

多面体低聚倍半硅氧烷(POSS)由于具有规整的立体结构、纳米尺寸、优良的相容性和修饰性,使其成为分子结构设计和材料改性的最佳选择之一。因此,POSS的合成引起了人们广泛的关注,深入研究它的合成方法与反应机理具有十分重要的学术意义和应用价值。本论文综述了POSS的合成研究进展(包括水解缩合法、官能团衍生法、缺角闭环法等),重点介绍了全同取代(T8R8)、单官能团(T8R7R′)、多官能团(T8RnR′8-n)及半缩合POSS(T7)的制备方法与途径,并总结了POSS的合成经验及发展方向。     

低介电多孔薄膜的制备及形成机制研究

摘要利用硅烷偶联剂KH-570(γ-甲基丙烯酰氧基甲氧基硅烷)水解缩合生成的多面低聚倍半硅氧烷(POSS)溶胶为模板剂, 经热解制备低介电多孔薄膜材料. 使用FTIR对材料制备过程及形成机制进行动态研究, 通过 ²⁹Si NMR、 椭偏仪、 氮气吸脱附曲线和TEM等对材料的介电性质、 孔洞大小和分布情况进行表征. 制备的介电多孔薄膜材料孔洞分布均匀、 孔径约1 nm, 比表面积为384.1 m²/g, 介电常数为2.5的低.     

低聚倍半硅氧烷/聚酰亚胺复合薄膜的力学性能和疏水性能（英文）

具有优良的力学和疏水性能的复合薄膜在惯性约束物理实验中具有重要作用.在本文中,我们使用简单的溶液混合的方法合成了低聚倍半硅氧烷/聚酰亚胺(POSS/PI)复合薄膜.结果表明由于POSS的引入,力学性能和疏水性能显著增强.力学测试结果显示,当POSS质量分数为10%时,弹性模量和硬度分别达到29.29 GPa和29.29 MPa,相比纯的PI薄膜为14.9 GPa和0.64 MPa.同时,当POSS质量分数为20%,复合薄膜的接触角为83.59°,明显高于纯的PI薄膜(66°).因此,POSS/PI复合膜比纯PI薄膜显示了强大的生命力和极其广阔的应用前景在惯性约束聚变(ICF)物理实验中.     

带功能基的笼形倍半硅氧烷合成进展

笼形倍半硅氧烷(POSS)是基于化学键合作用而形成的分子内杂化体系,这种有着规整立体结构同时具有单纳米尺度的有机无机杂化分子引起了研究人员的广泛关注,独特的纳米笼形结构也为分子水平上改进高分子的科学研究提供了可能性.本文综述了多面体倍半硅氧烷(POSS)的结构、性能与合成方法,重点介绍了巯基POSS、金属杂化POSS、...     

含POSS光刻胶材料研究进展

光致抗蚀剂又称光刻胶,是微电子加工过程中的关键材料。多面体低聚倍半硅氧烷（POSS）是一种具有规则的笼型结构的聚合物增强材料,由POSS改性的聚合物实现了有机-无机纳米杂化,POSS刚性结构的引入阻碍了聚合物分子的运动,可以显著提高聚合物的玻璃化转变温度（T_g）,降低聚合物的介电常数,提高聚合物的力学性能,也提高了含POSS光致抗蚀剂的耐蚀刻性。基于这些优点,含POSS的光刻胶材料得到广泛关注。本文对含POSS光刻胶的研究进展作了简要介绍。     

POSS/聚氨酯复合材料结构与性能的研究进展

多面体低聚倍半硅氧烷(POSS)是新兴的有机/无机杂化材料,其特殊的笼状结构可以从纳米尺度上影响聚氨酯体系的结晶行为、微相分离程度、交联密度等结构特征。少量添加即可大幅提高聚氨酯的耐水性、热稳定性、力学性能,以及阻燃性能、黏结性能、韧性等。本文从POSS/聚氨酯复合材料的结构出发,介绍了化学合成POSS基聚氨酯及物理共混POSS/聚氨酯复合材料,总结分析了悬垂型、星型、串珠型以及物理混合POSS基聚氨酯复合材料的结构特点,以及POSS结构差异对其复合材料性能的影响与影响机理。     

反应性多面低聚倍半硅氧烷对聚烯烃的改性研究

带有可反应功能基团的多面低聚倍半硅氧烷(polyhedral oligomeric silsesquioxane,简称POSS),是一类极具应用前景的新型纳米增强剂。本文简要综述了该类纳米增强剂对聚乙烯、聚丙烯、聚苯乙烯、聚降冰片烯的改性研究进展。     

纳米增强聚(氨酯-酰亚胺)泡沫的研究

聚(氨酯-酰亚胺)(PUI)泡沫是一种兼具聚氨酯和聚酰亚胺优异性能的新型泡沫材料,而纳米增强方法是其增强改性的一种有效手段,这就使纳米增强PUI泡沫成为其纳米复合材料的一个重要发展方向。本文介绍了纳米增强PUI泡沫的研究概况,重点综述了纳米二氧化硅(纳米SiO2)/PUI、多面体低聚倍半硅氧烷(POSS)/PUI、碳纳米管/PUI、蒙脱土/PUI体系的复合泡沫研究进展,着重讨论了纳米SiO2/PUI和POSS/PUI复合泡沫的制备技术,并评述了碳纳米管/PUI复合泡沫、蒙脱土/PUI复合泡沫的主要进展。     

Liquid crystal alignment behaviours on poly(methyl methacrylate) having polyhedral oligomeric silsesquioxane groups

A series of poly(methyl methacrylate) derivatives containing polyhedral oligomeric silsesquioxane (POSS) groups (MCP#) were synthesised via free radical polymerisation (FRP) using methacryl isobutyl POSS (MA-POSS) and methyl methacrylate as monomers to investigate liquid crystal (LC) alignment property of these polymer films. The LC cells made from the films of the polymers having 100 mol% of MA-POSS units (MCP100) showed vertical LC alignment having a pretilt angle of about 90°. The vertical LC alignment behaviour on the MCP100 film was ascribed to the very hydrophobic MCP100 surface having the surface energy value smaller than about 23 mJ/m² generated by the nonpolar bulky POSS group. Good electro-optical characteristics, such as voltage holding ratio (VHR) and residual DC voltage (R-DC), were observed for the LC cells fabricated using MCP100 as a LC alignment layer.     

Structure and properties of low-dielectric-constant poly(acetoxystyrene-co- octavinyl-polyhedral oligomeric silsesquioxane) hybrid nanocomposite

<正>Low-dielectric-constant poly(acetoxystyrenezhi-co-octavinyl-polyhedral oligomeric silsesquioxane)(PAS-POSS) organicinorganic hybrid nanocomposite was successfully synthesized via one-step free radical polymerization and characterized by FTIR,high-resolution ~1H NMR,~(29)Si NMR,DSC,TGA,AFM,spectroscopic elhpsometry and dielectric constants measurements. The results show T_g and T_(dec) were elevated dramatically due to the incorporation of inorganic POSS cores.Spectroscopic ellipsometry and dielectric constants measurement display the incorporation of POSS into PAS homopolymer can apparently reduce the dielectric constant of materials due to the increase of relative porosity of the hybrid nanocomposites.     

Preparation and properties of polyhedral oligosilsequioxane tethered aromatic polyamide nanocomposites through Michael addition between maleimide‐containing polyamides and an amino‐functionalized polyhedral oligosilsequioxane

Polyhedral oligosilsequioxane (POSS) tethered aromatic polyamide nanocomposites with various POSS fractions were prepared through Michael addition between maleimide‐containing polyamides and amino‐functionalized POSS. The chemical structures of the polyamide–POSS nanocomposites were characterized with Fourier transform infrared and ¹H NMR. The polyamide–POSS nanocomposites exhibited good homogeneity in scanning electron microscopy and transmission electron microscopy observations. POSS modification increased the storage modulus and Young's modulus of the polyamides, slightly decreased their glass‐transition temperatures from 312 to 305 °C, and significantly lowered their dielectric constants from 4.45 to 3.35. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4632–4643, 2006     

Controllable porous fluorinated polyimide thin films for ultralow dielectric constant interlayer dielectric applications

In this paper, silica microspheres were used as template to prepare porous fluorinated polyimide (FPI) thin films from polyamic acid (PAA, precursor of FPI) and silica colloid solution. The strong hydrogen-bonding interaction between silica microspheres and PAA chains have improved the dispersion of silica microspheres in N,N-Dimethylformamide (DMF) solution, resulting in the high weight content of silica template in PAA/silica colloid solution, and thus giving rise to the formation of porous FPI films with maximum porosity of 35%. The interior microstructures of the resultant porous FPI thin films were investigated. It is found that the porous FPI thin films have interconnected “ink-bottle-type” porous structure, and the pore size, porosity could be precisely controlled by the diameter and weight content of silica microspheres, respectively. Although both the tensile strength and young modules declined with the increasing porosity, the high level void of the porous FPI films endowed the FPI ultralow dielectric constant of 1.84 when the porosity increased to 35%. Furthermore, the mechanical and dielectric properties of the porous FPI films were closely related to the microstructures and porosity, indicating the desired properties could be controlled to meet the application in the microelectronics.     

Morphological behavior of thin polyhedral oligomeric silsesquioxane films at the molecular scale

Synchrotron X-ray reflectivity (XRR) was used to study the structure of thin films of polyhedral oligomeric silsesquioxanes (POSS) with side organic chains of different flexibility and containing terminal epoxy groups. POSS films were deposited from volatile solvents on hydroxylated and hydrogen-passivated silicon surfaces. The XRR data show a variety of structural morphologies, including autophobic molecular monolayers and bilayers as well as uniform films. The role of conformational and energetic factors governing the development of different morphologies in a restricted geometry is discussed.     

Fluorinated polyimide/POSS hybrid polymers with high solubility and low dielectric constant

A series of fluorinated polyimide/POSS hybrid polymers(FPI-4-FPI-16) were prepared via a facile synthetic route using 2,2'-bis(trifluoromethyl)benzidine, 4,4'-oxydiphthalic dianhydride and monofunctional POSS as starting materials. The hybrid polymers showed excellent solubility and film formation ability. Flexible and robust hybrid films could be conveniently obtained via solution-casting. The hybrid films demonstrated low dielectric constants and high thermal stability. Their dielectric constants were in the range of 2.47–2.92 at 1 MHz measured for their capacitance, and were tunable and decreased with an increase of POSS content. Their 10% weight loss temperatures were in the range of 539-591 ℃ and the weight residual at 800 ℃ ranged from 48% to 53% in nitrogen atmosphere. These hybrid films also possessed good mechanical properties and hydrophobic characteristics. This work could provide a potential strategy for the preparation of fluorinated polyimide/POSS hybrid polymers.     

Synthesis and properties of low‐dielectric‐constant polyimides with introduced reactive fluorine polyhedral oligomeric silsesquioxanes

A high‐performance, low‐dielectric‐constant polyimide (PI) nanocomposite from poly(amic acid) (PAA) cured with a reactive fluorine polyhedral oligomeric silsesquioxane (POSS) isomer was successfully synthesized. The features of this reactive fluorine POSS isomer [octakis(dimethylsiloxyhexafluoropropylglycidyl ether)silsesquioxane (OFG)] provided two important approaches (containing fluorine or being porous in the polymer matrix) of reducing the dielectric constant of PI. This reactive POSS isomer had an average of four epoxy groups and four fluorine groups on the POSS cage, and the epoxy groups could be cured with PAA to form a network framework of a PI/POSS nanocomposite. The PI/OFG nanocomposite had a high crosslinking density, high porosity (24.3%), high hydrophobicity, and low polarizability. These properties enhanced the thermal (glass‐transition temperature ～ 362 °C) and dielectric (dielectric constant ～2.30) properties of PI more than other POSS derivatives introduced into the PI backbone. A large number of small POSS particles (<10 nm) were embedded inside the PI matrix when the OFG content was low, whereas interconnected POSS aggregation domains were observed when the OFG content was high. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5391–5402, 2006     

AFM,ellipsometry, XPS and TEM on ultra-thin oxide/polymer nanocomposite layers in organic thin film transistors

Here we report on the fabrication and characterization of ultra-thin nanocomposite layers used as gate dielectric in low-voltage and high-performance flexible organic thin film transistors (oTFTs). Reactive sputtered zirconia layers were deposited with low thermal exposure of the substrate and the resulting porous oxide films with high leakage currents were spin-coated with an additional layer of poly-α-methylstyrene (PαMS). After this treatment a strong improvement of the oTFT performance could be observed; leakage currents could be eliminated almost completely. In ellipsometric studies a higher refractive index of the ZrO₂/PαMS layers compared to the “as sputtered” zirconia films could be detected without a significant enhancement of the film thickness. Atomic force microscopy (AFM) measurements of the surface topography clearly showed a surface smoothing after the PαMS coating. Further studies with X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) also indicated that the polymer definitely did not form an extra layer. The polymer chains rather (self-)assemble in the nano-scaled interspaces of the porous oxide film giving an oxide–polymer “nanocomposite” with a high oxide filling grade resulting in high dielectric constants larger than 15. The dielectric strength of more than 1 MV cm⁻¹ is in good accordance with the polymer-filled interspaces.     

Architecture of brush-on-brush copolymers by photoinduced ATRP approach

We established a preparation method of brush-on-brush copolymers by grafting from photoinduced ATRP of multifunctional polystyrene having N,N-diethyldithiocarbamate (DC) pendant groups with stearyl methacrylate (STM). We studied the solution properties of brush-on-brush copolymers from the view point of crowding effect of PSTM brush side chains. It was speculated from angular dependence on dynamic light scattering (DLS) that the brush-on-brush copolymer (BB1:PSTM brushes were grafted at regular intervals of 1/4 styrene units on the backbone) with large aspect ratio took a geometrical anisotropic conformation such as a cylinder due to crowding of brush side chains. In fact, transmission electron microscopy (TEM) photograph of such brush-on-brush showed a rigid rod-like morphology.     

Immobilization of Au nanoparticles on poly(glycidyl methacrylate)-functionalized magnetic nanoparticles for enhanced catalytic application in the reduction of nitroarenes and Suzuki reaction

We report a novel strategy for the synthesis of magnetic nanocomposite for highly efficient catalysis. Poly(glycidyl methacrylate) (PGMA) chains were grafted to the surface of magnetic nanoparticles (MNPs) through surface-initiated reversible addition-fragmentation chain transfer polymerization. Then, the oxirane rings in the PGMA chains were opened with 2,6-diamino pyridine (DAP) molecules as ligands to prepare the solid support. Finally, this magnetic nanocomposite was used for the immobilization of gold nanoparticles. Fourier-transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, transmission electron microscopy, scanning electron microscopy, gel permeation chromatography, vibrating sample magnetometry, and atomic absorption spectroscopy were used for characterization of the catalyst. The loading of gold nanoparticles on the solid support was 0.52 mmol/g. The catalytic activity of the prepared catalyst (MNP@PGMA@DAP@Au) was evaluated for the reduction of nitro compounds and C–C coupling reaction in water. The catalyst can be easily recovered and reused seven times without significant loss of catalytic activity.