磺化聚苯乙烯胶体晶的红外光谱分析

单分散乳胶体系可以通过自组装形成有序的胶体晶结构,在窄波段光过滤器[1]、生物医学传感器[2]、智能化学传感器[3] 等领域具有重要的应用价值.最近,人们以此有序结构作为模板,制备了有序孔材料[4～7] .另外,此有序结构在仿生学如模拟蛋白石等有序结构等方面也具有重要意义[8].但是,一般的单分散体系如聚苯乙烯体系所形成的有序结构都属于硬性材料,缺乏对外场的响应特性.此外,微球表面没有功能性基团,很难与其它物质兼容,这使得其作为模板合成其它复合材料的潜力大大降低. ANALYSIS OF FT-IR SPECTRA OF THE SULFONATED POLYSTYRENE COLLOIDAL CRYSTALS     

胶体晶体中的两种排列方式及堆积模式

由单分散的有机或无机粒子制备三维有序的胶体晶体越来越受到人们的关注 [1～ 3 ] ,单分散颗粒如何排布和堆积是形成三维有序胶体晶体的关键 .自然界中的蛋白石 (Opal)是由单分散 Si O2 粒子的三维有序堆积中渗入水溶性的硅酸盐固化而成的 .仿照自然界的模式由单分散的有机或无机粒子制备三维有序的胶体晶体是对当今科学技术的一个挑战 [4 ] .以胶体晶体为模板制备有机、无机、金属和陶瓷等的多孔材料在催化、吸附以及光子晶体等方面具有重要的应用前景 [5～ 9] .本文研究了以单分散的聚苯乙烯 -甲基丙烯酸甲酯 -丙烯酸 [P(St- MMA- AA)…     

单分散聚苯乙烯乳胶有序膜在二氧化硅多孔材料制备中的模板作用

自然界中许多物质经千万年发展进化,具有特殊结构,决定了它们具有奇异特性.人们对此过程非常关注,试图了解其结构性能关系,从而实现人工合成,仿生学应此而产生.比如天然蛋白石能呈现出鲜艳颜色,其原因在于单分散二氧化硅微球与具有选择性吸收光的某些金属氧化物微粒形成了有序的超晶格结构[1].为了模拟此过程,人们以单分散二氧化硅或聚苯乙烯微粒形成的胶体晶作为模板,实现蛋白石的人工合成[2].可以说,模板合成技术是制备有序材料的有效手段.本文以单分散聚苯乙烯乳胶室温形成的有序膜为模板,采用快速溶胶凝胶方法,制备了聚苯乙烯/二氧化硅…     

微凝胶胶体晶体研究进展

Poly(N-isopropylacrylamide)(PNIPAM)微凝胶粒子是一种软的胶体粒子.和单分散的SiO_2、PS、PMMA等硬的胶体粒子一样,单分散的PNIPAM微凝胶粒子也可以自组装成为高度有序的胶体晶体.微凝胶粒子软物质的特性及其对外部刺激的响应性赋予其不同于硬球的组装行为.微凝胶胶体晶体的高度有序结构及其刺激响应性使其在诸多领域有重要用途.本文分别介绍了三维及二维微凝胶胶体晶体组装的研究进展,并对已开发的基于微凝胶胶体晶体的应用进行了总结.     

二氧化硅胶体晶模板技术制备间规聚苯乙烯有序孔材料

结晶高分子在受限空间中的聚合行为及聚集态均与本体的有着显著的差异 ,因而呈现不同的性能[1] .受限空间是指介观有序的分子筛 .间规聚苯乙烯具有熔点高、结晶速度快、弹性模量高、绝缘及抗溶剂性能优良等特点 ,具有广阔的应用前景 .自从 Ishihara等 [2～ 5]首次报道苯乙烯间规聚合以来 ,国内外对间规聚苯乙烯的均聚和共聚反应进行了大量研究 .苯乙烯在二氧化硅胶体晶中通过自由基聚合得到三维有序聚苯乙烯孔材料 ,实验表明 ,即使在亚微米的受限空间内 ,聚苯乙烯的生成和性质也会发生明显变化 [6] .本文以有序二氧化硅胶体晶为模板 ,在其…     

表面富含羧基的单分散交联聚合物微球的快速自组装制备胶体晶的研究

在20～70℃范围内,用垂直沉积的方法可使表面富含羧基的单分散交联聚合物微球在不同的基底上快速自组装成三维有序的胶体晶.不同粒径的微球形成的胶体晶其光禁带峰位不同,因此可调控不同波长的光在胶体晶中的传播.利用紫外-可见光谱研究了胶体晶的光禁带峰位与组成其微球粒径之间的关系.结果表明,随着构成胶体晶微球粒径的增大,胶体晶光禁带峰位发生了红移,而随着入射光角度的增大,胶体晶的光禁带峰位发生了蓝移.利用原子力显微镜和扫描电子显微镜研究了其它条件对聚合物微球有序排列的影响,发现聚合物微球在pH值为3.0～13.0范围内可以形成三维有序自组装胶体晶.这是由于在不同的pH值下,聚合物微球表面发生羧基化及去羧基化反应,导致在自组装过程中微球之间和微球与介质之间作用力的变化     

磺化聚苯乙烯有序孔水凝胶的制备及其模板效应

有序大孔聚苯乙烯材料通过胶体晶模板技术合成, 再经过磺化处理制备得到有序大孔水凝胶体系. 研究了其化学组成和形态. 以溶胶/凝胶制备有序无机材料如二氧化钛对凝胶进行复型, 证明了有序大孔凝胶的形态特征, 同时显示了有序大孔水凝胶作为新型模板制备形态可控的介观尺度有序无机材料的潜力.     

憎水性单分散粒径小于10 nm复合金属量子点的制备

0引言粒径小于10nm的量子点,具有特殊的物理化学性质。如低电子转换性能、高氧化还原电位,高矫顽力,高催化性能等,金量子点还具有生物识别、生物传感器等性能[1]。纳米颗粒的合成与应用已经引起人们的广泛兴趣[2￣4],二维、三维量子点阵长程有序排布对将来的纳米电子器件及超功能性材料具有重要意义[5,6]。然而,二维、三维量子点阵长程有序排布需要单分散量子点。这就需要人们利用各种方法制备单分散量子点。直接合成法,如Lianos等[7,8],利用反胶束法合成出粒径为5nm量子点,但是单分散性不佳。目前,获得单分散纳米颗粒主要有3种方法,种子增…     

胶体分散体系与有序分子组合体的小角X射线散射研究

小角X射线散射(SAXS)是当前化学、物理、生物等学科前沿交叉领域--软凝聚态物质的一个强有力研究工具.本文评述了SAXS方法自身的优势及其在胶体分散体系与有序分子组合体研究中的广泛应用,重点论述了对粒子尺寸或孔径大小分布、胶体体系分散状态、长程有序结构以及混合体系之间相互作用的测量与表征等.     

利用二氧化硅欧泊模板合成三维多孔金属镍

金属镍在高效催化剂、传感器、导电浆料、高密度磁记录材料、高性能电极材料等领域具有广阔的应用前景,在材料科学和凝聚态物理领域引起了广泛的研究兴趣。多孔金属镍结构由金属镍骨架及孔隙所组成,与致密块体镍相比,其内部具有大量的孔隙,因而具有诸多优异的特性,如密度小、比表面积大、光学性能优异等。多孔金属镍可用来制作过滤器、催化剂及催化剂载体、多孔电极等[1]。1987年Yablonovitch[2]和John[3]几乎同时提出了光子晶体这一新概念和新材料。构成三维模板的途径之一是在液体中自组装成具有光波量级的单分散胶体微球——胶体晶体,这…     

纳米图案化高分子凝胶的制备

A new method was proposed to prepare binary composite colloidal crystal hydrogels by interlocking the as-prepared polystyrene/sulfonated polystyrene core/shell colloidal crystal hydrogel with a second responsive gel. The shell thickness thus the core size were synchronously controlled by altering the sulfonation time and temperature. The proper monomers were radically polymerized forming the second gel within the first gel network. The composition and structure were confirmed. Nanopatterued hydrogel including porous bulk hydrogels and surface patterned hydrogels were derived by properly treating the binary composite hydrogels. Specially, some typical patterns such as arrays of “nano-bowls” ,arrays of “nano-ribbons” and “nano-mask” were achieved by changing the treatment method such as by immersion in the solvent, after solvent evaporation from the sample surface during high rate rotation. This work provides a method to prepare nanopatterued hydrogels.     

杂萘联苯共聚醚砜的非均相磺化

以杂萘联苯共聚醚砜(PPHES)为原料,氯仿为溶剂,浓硫酸为磺化试剂,采用非均相磺化法对PPHES进行了磺化改性,得到了一系列不同磺化度的磺化杂萘联苯共聚醚砜(SPPHES).考察了浓硫酸浓度、磺化反应温度和时间等工艺条件对产物磺化度的影响.利用FT-IR、1H-NMR对SPPHES进行了表征.结果表明,磺酸基已成功引...     

Influence of the bisphenol structure on the direct synthesis of sulfonated poly(arylene ether) copolymers. I

New sulfonated poly(arylene ether sulfone) copolymers with high molecular weights were successfully synthesized with controlled degrees of disulfonation of up to 70 mol % via the direct copolymerization of sulfonated aromatic dihalides, aromatic dihalides, and one of four structurally distinct bisphenols. The disodium salts of the 3,3′‐disulfonated‐4,4′‐dichlorodiphenyl sulfone and 3,3′‐disulfonated‐4,4′‐difluorodiphenyl sulfone comonomers were synthesized via the sulfonation of 4,4′‐dichlorodiphenyl sulfone or 4,4′‐difluorodiphenyl sulfone with 30% fuming sulfuric acid at 110 °C. Four bisphenols (4,4′‐bisphenol A, 4,4′‐bisphenol AF, 4,4′‐biphenol, and hydroquinone) were investigated for the syntheses of novel copolymers with controlled degrees of sulfonation. The composition and incorporation of the sulfonated repeat unit into the copolymers were confirmed by ¹H NMR and Fourier transform infrared spectroscopy. Solubility tests on the sulfonated copolymers confirmed that no crosslinking and probably no branching occurred during the copolymerizations. Tough, ductile films were solvent‐cast that exhibited increased water absorption with increasing degrees of sulfonation. These copolymers are promising candidates for high temperature proton‐exchange membranes in fuel cells, which will be reported separately in part II of this series. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2264–2276, 2003     

Sulfonation of polystyrene: Toward the “ideal” polyelectrolyte

Sulfonation of narrow polydispersity polystyrene, PS, standards remains the method of choice for generating polystyrene sulfonate, PSS, samples with defined composition. Although a variety of sulfonation techniques have been described, relatively little is reported on the material obtained, which is used for so many studies on the fundamental behavior of polyelectrolytes. Here, we show that powdered polystyrene treated with concentrated sulfuric acid (96%) at 90 °C without catalyst yields fully sulfonated PSS. Extensive characterization with ¹H and ¹³C NMR as well as size exclusion chromatography coupled with static and dynamic light scattering shows no evidence of sulfone crosslinking or chain degradation under the conditions used. Though mono‐sulfonated as soon as it dissolves in the acid, the PSS contains about 6% meta substitution. Sulfonation kinetics for this heterogeneous reaction depend strongly on particle size, sulfuric acid content and temperature. For preparing perdeuterated PSS from the corresponding PS it is essential to employ D₂SO₄, as about half of the aromatic units undergo H/D exchange during sulfonation. The remaining ortho H/D may be exchanged with extended exposure to the concentrated sulfuric acid, but the meta site is deactivated. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2416–2624     

Controlled sulfonation of poly(arylene ether sulfone)s and poly(arylene ether ketone)s with different molecular structures for polymer electrolyte membranes

Poly(arylene ether sulfone) copolymers derived from 9,9-bis(4-hydroxyphenyl)fluorene, bisphenol S and 4,4′-difluorodiphenylsulfone and poly(arylene ether ketone) copolymers derived from 4-phenoxybiphenyl, diphenyl ether and isophthaloyl chloride were prepared as precursor polymers for sulfonation reaction in which sulfonic groups are introduced quantitatively into specified positions. Sulfonation reaction for these two series of copolymers by concentrated sulfuric acid was successfully carried out to give sulfonated polymers with controlled positions and degree of sulfonation. Thermal stability, moisture absorption and proton conductivity for these two series of copolymers were measured and the results were compared to those of perfluorosulfonic acid polymers.     

Formation of microstructured silicon surfaces by electrochemical etching using colloidal crystal as mask

Silicon disk arrays and silicon pillar arrays with a close-packed configuration having an ordered periodicity were fabricated by the electrochemical etching of a silicon substrate through colloidal crystals used as a mask. The colloidal crystals were directly prepared by the self-assembly of polystyrene particles on a silicon substrate. The transfer of a two-dimensional hexagonal array of colloidal crystals to the silicon substrate could be achieved by the selective electrochemical etching of the exposed silicon surfaces, which were located in interspaces among adjacent particles. The diameter of the tip of the silicon pillars could be controlled easily by changing the anodization conditions, such as current density and period of electrochemical etching.     

Fabrication of spherical colloidal crystals using electrospray

We demonstrated the use of electrohydrodynamic atomization to prepare uniform-sized emulsion droplets in which equal spheres of silica or polystyrene were dispersed. The size of the emulsion droplets was easily controlled by the electric field strength and the flow rate, independently of the diameter of the nozzles. During the evaporation of solvent in the droplets, spherical colloidal crystals were formed by self-assembly of the monodisperse colloidal spheres. The diameter of the spherical colloidal crystals was in the range of 10-40 microm. Depending on the stability of colloidal particles, the morphology of the self-assembled structure was varied. In particular, silica spheres in ethanol droplets were self-assembled into compactly packed silica colloidal crystals in spherical shapes, whereas polystyrene latex spheres in toluene droplets self-assembled into spherical colloidal crystal shells with hollow cores. The silica colloidal assemblies reflected diffraction colors according to the three-dimensionally ordered arrangement of silica spheres.     

Superhydrophobic bionic surfaces with hierarchical microsphere/SWCNT composite arrays

Superhydrophobic bionic surfaces with hierarchical micro/nano structures were synthesized by decorating single-walled or multiwalled carbon nanotubes (CNTs) on monolayer polystyrene colloidal crystals using a wet chemical self-assembly technique and subsequent surface treatment with a low surface-energy material of fluoroalkylsilane. The bionic surfaces are based on the regularly ordered colloidal crystals, and thus the surfaces have a uniform superhydrophobic property on the whole surface. Moreover, the wettability of the bionic surface can be well controlled by changing the distribution density of CNTs or the size of polystyrene microspheres. The morphologies of the synthesized bionic surfaces bear much resemblance to natural lotus leaves, and the wettability exhibited remarkable superhydrophobicity with a water contact angle of about 165 degrees and a sliding angle of 5 degrees.     

聚(苯乙烯-co-甲基丙烯酸)胶体晶体原位反转制备孔阵列研究

利用甲苯浸泡法,将聚(苯乙烯-co-甲基丙烯酸)(P(Sc-o-MAA))胶体晶体转变成孔阵列,利用扫描电镜和原子力显微镜详细研究了胶体球在向孔转变过程中结构的变化细节,同时利用表面元素分析法检测其反转前后元素含量的变化.结果表明,在选择性溶剂作用下,胶体球经历了溶胀—粘连—破裂—溶解—成孔—扩张等一系列变化,处于内核的聚苯乙烯被溶出胶体球后不仅填充到球与球之间的空隙中而且扩散到了溶剂中,而胶体球表面富集的聚甲基丙烯酸链段与溶出的聚苯乙烯混合物则主要对孔结构起固定和支撑作用,但长时间的甲苯浸泡最终会破坏孔的结构和阵列的完整性.