聚苯乙烯胶态晶体的合成

近年来 ,胶态晶体引起物理学家和化学家的共同关注 [1] .占据晶格点的纳米或微米级微粒自组装行为 [2 ] 在光学显微镜和扫描电子显微镜下可被清晰地观察到 ,因此能作为研究晶体相变的模型 [3 ] ,并有助于人们加深对晶体中点缺陷、晶界及位错等现象的了解 .胶态晶体所具有的周期性结构更使其在光学研究领域具有特殊意义 .与半导体中电子的能带结构类似 [4 ] ,胶态晶体中传播的光波色散曲线为不连续的带状结构 ,被称为“光子晶体”(photonic crystal) .在禁带区 (photonic band gap) ,光被禁止传播 ,而光散射加强 ,可将其应用于光电开关及光催…     

聚苯乙烯胶晶的组装

采用自然沉降法、离心法和垂直沉积法组装了聚苯乙烯胶晶。实验结果表明,所得胶晶都具有面心立方结构,结构有序性相当高。自然沉降法和离心法适用于块体胶晶的组装,自然沉降法适用于胶晶膜的组装。     

Effect of Hydrophilic Shells on the Formation of Colloidal Crystals by Monodisperse Core‐Shell Polymer Microspheres

We have found that a soft, hydrophilic shell is necessary in the formation of three‐dimensional colloidal crystals by polymeric microspheres prepared by surfactant‐free emulsion copolymerization. The core‐shell microspheres contain a hard, hydrophobic polystyrene core and a soft, hydrophilic shell made of polyacrylamide or poly(acrylic acid) (PAA). Dilution of the particles induced a red shift of the diffraction peak. We have found a pH switching effect for the formation of colloidal crystals by the microspheres with a PAA shell. When the carboxylic‐acid groups are protonated, the colloidal crystals lose their order. The same effect is observed when a poor solvent is added to the colloidal crystals formed by the microspheres with a polyacrylamide shell.

     

窄分散大粒径交联聚苯乙烯功能微球的合成研究

用分散聚合法，以聚乙烯吡咯烷酮（PVP）为稳定剂，偶氮二异丁腈（AIBN）为引发剂，乙二醇二甲基双丙烯酸酯（EGDMA）为交联剂，一次加料法在醇水介质中制备数个微米交联聚苯乙烯（PS）微球。研究了苯乙烯（St)、丙烯酸（AA）、EGDMA的用量对粒子大小，粒径分布的影响。测量了微球表面羧基的含量。     

改性聚苯乙烯微球的制备及其胶体晶体的组装

采用甲基丙烯酸改性的无皂乳液聚合方法制备了尺寸为210 nm、含羧基的聚苯乙烯(PS)微球，用红外光谱、透射电子显微镜和粒度分析仪对其形状和结构进行分析，结果表明，经甲基丙烯酸改性后得到了表面为高密度电荷的单分散性PS微球.用垂直沉积法快速制备出在较大范围(大于1 cm2)呈现很好有序性的密排结构聚苯乙烯胶体晶体薄膜，其在590 nm波长处存在光子带隙.在电子显微镜下，观察到这种胶体晶体是面心立方(fcc)密排结构.     

单分散聚苯乙烯交联微球可控制备的研究进展

单分散聚苯乙烯交联微球是一类具有高比表面积、吸附性强以及高表面活性的材料,以其优异的疏水性、优越的热稳定性和耐溶剂性能在生物医学、标准计量、电子信息、分析化学、色谱分离等领域具有十分广阔的应用前景,近年来有关交联聚合物微球的制备以及机理研究成为一大热点并且发展较快。本文重点介绍了交联剂存在下分散聚合的反应机理,探讨了单体、引发剂、交联剂、分散剂以及分散介质等对单分散聚苯乙烯交联微球可控制备的影响,展望了聚苯乙烯交联微球的发展趋势和应用前景。     

单分散交联聚苯乙烯微球HPLC固定相的合成

用分散聚合物合成了单分散聚苯乙烯微球种子，然后用种子聚合法合成了交联的聚苯乙烯向球，其粒径范围可控制在２μｍ～４μｍ，考察了反应条件对微球粒径和粒径分布的影响，确定了最佳合成条件，初步考察了交联微球的ＨＰＬＣ性能。     

无皂乳液聚合法合成阴离子PS微球及粒径控制

以苯乙烯(St)和丙烯酸(AA)为单体,过硫酸钾(KPS)为引发剂,采用无皂乳液聚合法合成了单分散阴离子聚苯乙烯(PS)微球,并对微球结构和影响单分散性的因素进行了研究。结果表明,AA单体也已共聚到聚合物链上,AA的加入使PS微球粒径减小,并赋予PS微球表面负电性;聚合反应的活化能为42.95kJ/mol,升高聚合温度提高了反应速率;随着KPS用量的增加,PS微球粒径减小,在用量为0.6%时呈现最好单分散性;随着反应介质中丙酮含量增加,聚合物在介质中溶解度增加,使PS微球粒径有所减小,但微球粒径分布有所变宽。     

无皂乳液聚合制备高浓度单分散聚(苯乙烯-甲基丙烯酸甲酯)胶体粒子

通过添加聚乙烯醇和丙酮，找到了一种无皂乳液聚合制备高浓度单分散苯乙烯－甲基丙烯酸甲酯共聚胶体粒子的新途径，粒子半径达纳米数量级，体系的固含量大于50％，研究了聚乙烯醇和丙酮对反应过程，胶乳粒子大小的影响，结果表明聚乙烯醇和丙酮对高浓度无皂纳米胶乳粒子的形成与稳定起重要作用。     

Tunable Self-Assembly of Diblock Copolymers into Colloidal Particles with Triply Periodic Minimal Surfaces

We herein report the tunable self-assembly of simple block copolymers, namely polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymers, into porous cubosomes with inverse or mesophases of controlled unit cell parameters as well as hexasomes with an inverse hexagonal (p6mm) structure, which have been rarely observed in polymer self-assembly. A new morphological phase diagram was constructed for the solution self-assembly of PS-b-PEO based on the volume fraction of the PS block against the initial copolymer concentration. The formation mechanisms of the cubosomes and hexasomes have also been revealed. This study not only affords a simple system for the controllable preparation and fundamental studies of ordered bicontinuous structures, but also opens up a new avenue towards porous architectures with highly ordered pores.     

Monodispersed Magnetic Polystyrene Beads with Excellent Colloidal Stability and Strong Magnetic Response

Monodispersed polystyrene beads incorporated with Fe₃O₄ nanoparticles are prepared via dispersion polymerization. The resultant magnetic beads present well‐defined composite structures, excellent colloidal stability, and strong magnetic response. The formation mechanism for the monodispersed composite beads, incorporated with preformed Fe₃O₄ nanocrystals, was investigated. The potential applications of the monodispersed magnetic beads in bacteria capturing were demonstrated. After being coated with anti‐Salmonella CSA‐1 antibody, the magnetic beads show capturing efficiencies of >99.4% in isolating Salmonella sp.

     

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     

Synthesis and Characterization of the Organic Surface Modifications of Monodisperse Colloidal Silica

Monodisperse colloidal silica spheres were prepared from tetraethylorthosilicate in mixtures of water, ammonia and ethanol. The surfaces of the spheres were successfully modified by chemical reaction with silane coupling agents. Several qualitative and quantitative methods were employed to analyse the organic surface modifications. As a result, the surface coverage of silica spheres with silane coupling agents could be calculated using different characterization methods.     

单分散聚苯乙烯微球的制备及影响因素研究

以聚乙烯吡咯烷酮为分散剂，无水乙醇为反应介质，偶氮二异丁腈为引发剂，采用分散聚合工艺，通过优化反应条件，制备出了粒径为5μm单分散（分散系数≤5％）聚苯乙烯微球。所制备的聚苯乙烯微球标准偏差δ＝0．16μm，分散系数ε＝0．02，且具有良好的球形度，表面非常光滑，无破损，无缺损。对影响单分散聚苯乙烯微球的因素进行了研究，结果表明：随着分散稳定剂用量的增加，聚苯乙烯微球的粒径减小；随着单体和引发剂用量的增加，聚苯乙烯微球的粒径增大。分散稳定剂和单体用量是影响聚苯乙烯微球粒径分布的两个主要因素。     

模板法制备聚苯乙烯/聚4-乙烯基吡啶功能微球

以工业化的聚苯乙烯中空微球为模板,利用种子乳液法合成了粒径均一的功能化中空聚苯乙烯/聚4-乙烯基吡啶(PS/P4VP)微球,改变制备条件可以控制功能基团4-乙烯基吡啶(4-VP)在聚苯乙烯微球表面的分布.合成的微球在水和有机溶剂如二氯甲烷、乙醇、乙腈等中有良好的分散性,并能促进油水体系混溶.     

TiO2掺杂调控聚苯乙烯微球折射率及胶体光子晶体结构色

胶体光子晶体由于其可调变的结构色在绿色印刷、印染等领域备受关注,而其光子带隙的宽度和位置由光子晶体的晶格参数(晶面间距,通常受胶体微球尺寸影响)和介质的折射率决定。现有人工胶体光子晶体主要基于SiO_2和高分子(如聚苯乙烯(PS)等)微球的组装制备,由于胶体微球材质种类有限,折射率调控受限,因而目前调控胶体光子晶体结构色主要靠改变胶体微球的尺寸来实现。本文首先制备高折射率(2.6)的TiO_2纳米晶,在乳液聚合制备单分散的PS(折射率1.6)微球过程中,将所制备的TiO_2纳米晶掺杂于PS微球中,通过TiO_2的掺杂量有效调控胶体微球的折射率,进而实现胶体光子晶体的结构色调控。以多色胶体光子晶体微球的水溶液为墨水,采用彩色喷墨打印技术打印了电脑设计的光子晶体彩画。本文发展的光子晶体结构色调控新技术拓展了胶体光子晶体的应用。     

Colorimetric Chemosensor for Chloramphenicol Based on Colloidal Magnetically Assembled Molecularly Imprinted Photonic Crystals

A novel colorimetric chemosensor with good sensitivity, specificity, and self‐reporting capability for chloramphenicol (CAP ) has been successfully constructed based on colloidal, magnetically assembled photonic crystals coupled with molecular imprinting. The colloidal, magnetically assembled, molecularly imprinted photonic crystals (CMA ‐MIPCs ) were prepared by assembling CAP in magnetic, molecularly imprinted nanohydrogels (MMIHs ) in a magnetic field. The magnetic assembly of photonic crystals and the sensing processes could be completed simultaneously when MMIHs were dispersed in CAP solutions and in a magnetic field, and the response time was less than 1 min. The CAP concentration could be visually determined from the color change of the CMA ‐MIPCs sensor. The diffraction color blue‐shifted from luminous yellow of the blank to purple in a 1.0 mg/mL CAP solution, with a determination limit of 1.0 × 10⁻³ mg/mL. It could provide a new strategy for qualitative or semiquantitative detection of CAP .     

Template‐Free Supracolloidal Self‐Assembly of Atomically Precise Gold Nanoclusters: From 2D Colloidal Crystals to Spherical Capsids

We report supracolloidal self‐assembly of atomically precise and strictly monodisperse gold nanoclusters involving p‐mercaptobenzoic acid ligands (Au₁₀₂‐pMBA₄₄) under aqueous conditions into hexagonally packed monolayer‐thick two‐dimensional facetted colloidal crystals (thickness 2.7 nm) and their bending to closed shells leading to spherical capsids (d ca. 200 nm), as controlled by solvent conditions. The 2D colloidal assembly is driven in template‐free manner by the spontaneous patchiness of the pMBA ligands around the Au₁₀₂‐pMBA₄₄ nanoclusters preferably towards equatorial plane, thus promoting inter‐nanocluster hydrogen bonds and high packing to planar sheets. More generally, the findings encourage to explore atomically precise nanoclusters towards highly controlled colloidal self‐assemblies.     

乳化剂对阳离子乳液聚合及乳胶粒性能的影响

以苯乙烯、丙烯酸丁酯为非离子单体,甲基丙烯酰氧乙基三甲基氯化铵（DMC）为阳离子单体,偶氮二异丁基脒盐酸盐（AIBA）为引发剂,十六烷基三甲基氯化铵（CTAC）和乙撑基双（十六烷基二甲基氯化铵）（G16—2—16）为乳化剂,采用半连续种子乳液聚合法进行阳离子乳液聚合。探讨了乳化剂的分子结构和用量对反应速率、单体转化率以及乳胶粒粒径、Zeta电位等的影响。结果表明：乳化剂的用量越大,反应速率越大,单体转化率越高,而乳胶粒粒径越小;使用G16—2—16作乳化剂时,单体转化率较高,乳胶粒粒径较大,Zeta电位较高。     

原子转移自由基聚合原位合成温敏性微球

以过硫酸钾为引发剂、丙酮-水[V(丙酮)∶V(水)＝4∶6]的混合溶剂为反应介质, 在少量二乙烯苯存在的条件下使苯乙烯(St)和对氯甲基苯乙烯(CMSt)进行无皂乳液共聚反应, 得到了粒径大小均匀的交联型聚苯乙烯(PSt)微球, 由X射线光电子能谱对表面组分测定发现: CMSt上的氯原子在聚合过程中富集于交联微球的表面. 以此交联型PSt微球为原子转移自由基聚合(ATRP)的引发剂, 在22 ℃下引发N-异丙基丙烯酰胺(NIPAAm)进行原位ATRP反应, 得到了表面原子转移自由基聚合接枝的交联聚苯乙烯(PNIPAAm-g-PSt)温敏性微球. 借助傅立叶变换红外光谱、差示扫描量热仪、扫描电子显微镜及激光光散射仪等对PNIPAAm-g-PSt的结构、相转变温度、形态及不同温度下的粒径变化进行了测定, 结果表明NIPAAm单体成功地原位ATRP接枝在交联PSt微球的表面, 接枝微球的球形更规整, 在水中的相转变温度约为32 ℃, 具有明显的温度敏感性.