Synthesis and characterization of novel Ag-polypyrrole@poly(styrene-co-methacrylic acid) nanocomposite particles

Novel raspberry-like Ag-polypyrrole/poly(styrene-co-methacrylic acid) (Ag-PPy/P(St-co-MAA)) colloidal nanocomposite particles were prepared by aqueous oxidative polymerization of pyrrole using AgNO₃ as the oxidant. The polymerization was carried out in the pre-synthesized polymer-emulsion of P(St-co-MAA) with emulsifier-free P(St-co-MAA) latex particles serving as both the templates and the stabilizers. Without any extra surfactants or polymer stabilizers, the polymerization proceeded steadily with the in-situ produced Ag-PPy nanocomposites depositing on the surface of the template particles. The obtained product is typical of raspberry-like morphology, whose nanostructures and compositions were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), powder X-ray diffraction (XRD) and electron dispersive X-ray spectrometer (EDS), respectively. The results confirmed that the surface of the P(St-co-MAA) latex was coated by Ag-PPy nanocomposite particles with a size range from 2 nm to 50 nm. Most of Ag nanoparticles are encapsulated by the PPy sheath or dispersed in the PPy layer.     

Synthesis of SiO2-coated Bi2S3/poly(styrene) nanocomposites by in-situ polymerization

New nanocomposites containing silica-coated Bi2S3 nanofibers were synthesised by in situ polymerization using two distinct synthetic strategies: emulsion and suspension polymerization. Transmission and scanning electron microscopy of the nanocomposite particles showed that in both cases the Bi2S3/SiO2 nanoparticles were densely coated with poly(styrene). In situ emulsion polymerization afforded nanocomposites in which the nanofibers were coated with polymer spheres whilst suspension polymerization gives rise to a homogeneous polymer layer coat. The morphology of the poly(styrene) coating observed is discussed considering the surface modification of the nanofibers and the polymerization technique involved.     

Nonspherical dented poly(methyl methacrylate)/poly(styrene-co-divinylbenzene) particles formed in seeded soap-free emulsion copolymerization

In this study, nonspherical poly(methyl methacrylate)/poly(styrene-co-divinylbenzene) [PMMA/P(St-co-DVB)] particles having multiple dents on the surface were prepared by seeded soap-free emulsion copolymerization of St and DVB (used as a crosslinker) on spherical linear PMMA seed particles. The effect of various polymerization parameters on particle morphology, as well as polymerization kinetics and morphological evolution, were investigated in detail. It was found that, to prepare this kind of nonspherical particles, it was necessary to conduct the polymerization at a relatively low temperature, using batch monomer addition mode and PMMA seed of relatively high molecular weight. The formation of the nonspherical particles was attributed to the phase separation between the second-stage monomers and the crosslinked P(St-co-DVB) network being formed during polymerization.     

Polybutylacrylate/poly(methyl methacrylate) Core-Shell Elastic Particles as Epoxy Resin Toughener:Part Ⅰ Design and Preparation

Polybutylacrylate (PBA)/poly(methyl methacrylate) (PM MA) core-shell elastic particles (CSEP), whose rubbery core diameterranged from 0.08 μm to 1.38 μm, were synthesized by using conventional emulsion polymerization, multi-step emulsion polymerization, and soapless polymerization. Allyl methacylate (ALMA) and ethylene glycol dimethacrylate (EGDMA) were selected as crosslinking reagents for core polymerization. Methacrylic acid (MAA) was used as functional co-monomer with methyl methacrylate as shell component. The content of vinyl groups in PBA rubbery core increased with the amount of crosslinking reagents. The core-shell ratio affected great on the morphology of the complex particles. Furthermore, the amounts of carboxyl on the surface of core-shell particles, copolymerized with acrylic acid, were determined by potentiometric titration. Results showed that methylacrylic acid was distributed mostly on the surface of particles.     

Polybutylacrylate/poly(methyl methacrylate) Core-Shell Elastic Particles as Epoxy Resin Toughener: Part I Design and Preparation

Polybutylacrylate (PBA)/poly(methyl methacrylate) (PMMA) core-shell elastic particles (CSEP), whose rubbery core diameter ranged from 0.08 μm to 1.38μm, were synthesized by using conventional emulsion polymerization, multi-step emulsion polymerization, and soapless polymerization. Allyl methacylate (ALMA) and ethylene glycol dimethacrylate (EGDMA) were selected as crosslinking reagents for core polymerization. Methacrylic acid (MAA) was used as functional co-monomer with methyl methacrylate as shell component. The content of vinyl groups in PBA rubbery core increased with the amount of crosslinking reagents. The core-shell ratio affected great on the morphology of the complex particles. Furthermore, the amounts of carboxyl on the surface of core-shell particles, copolymerized with acrylic acid, were determined by potentiometric titration. Results showed that methylacrylic acid was distributed mostly on the surface of particles.     

Preparation of multilayered organic-inorganic hybrid core-shell particles by stepwise surface formation

This paper introduces a stepwise formation method for micro-sized, multilayered core-shell particles comprising an inorganic core, organic inner shell, and inorganic outer shell. A silica core was coated with a polystyrene seed layer, followed by surface seed polymerization with styrene, to afford the inner shell. These particles were then coated with a silica outer shell by a surface sol-gel reaction with tetraethoxysilane. The versatility of this combined surface seed polymerization and sol-gel method is emphasized by the precise control achieved over particle diameter as well as shell thickness and count. Moreover, the organic inner shell can be readily eliminated to afford a single-core-containing micro-capsular structure.     

微胶囊制作技术及其在电子纸中的应用

电泳显示、LCD等信息显示技术,应用于电子纸产品,存在性能不稳、产品寿命短等问题．本文综述了复凝聚、原位聚合等微胶囊合成方法及其改进技术,包括使用阻聚剂提高胶囊平滑度、加入抗冲击剂改善胶囊分散状态以及无机颜料、有机颜料和纳米SiO2等电泳颗粒的微胶囊改性技术,展示了电泳墨水微胶囊技术的新进展．微胶囊技术应用于电泳显示、LCD以及双色球和磁性电子纸等,改善了电子纸显示器性能,促进了电子纸及其应用技术产业化发展。     

Morphology and growing of nanometric multilayered films formed by alternated layers of poly(3,4-ethylenedioxythiophene) and poly(N-methylpyrrole)

Multilayered nanometric films formed by alternated layers of conducting poly(3,4-ethylenedioxythiophene) and poly(N-methylpyrrole) doped with perchlorate anions (ml-PEDOT/PNMPy) have been prepared using a layer-by-layer electrodeposition technique combined with a very small polymerization time. The mechanisms of formation and growth of the resulting multilayered systems have been investigated using Atomic Force Microscopy (AFM), and compared with those obtained for the corresponding homopolymers, which were prepared using identical experimental conditions. Furthermore, the local conductivity, electroactivity and electrostability have been also examined. Analyses of the morphology, topography and roughness of the surfaces indicate that the formation and growth of the multilayered films strongly depend on the number of layers as well as on the chemical nature of the conducting polymer. Interestingly, AFM reflects that the formation and growth of the ml-PEDOT/PNMPy films are significantly different from those of PEDOT and PNMPy homopolymers. The electrical and electrochemical properties of the systems under study are fully consistent with the proposed mechanisms. Results evidenced that multilayered systems formed by two conducting polymers are more advantageous from a technological point of view than the corresponding copolymers.     

Preparation of an ion-exchange chromatographic support by a "grafting from" strategy based on atom transfer radical polymerization

A new "grafting from" strategy based on surface-initiated atom transfer radical polymerization (ATRP) was first used for the preparation of a polymer-based ion-exchange support for HPLC. The most important property of the proposed method is to be applicable for the synthesis of any type of ion exchanger in both the strong and the weak forms. Monodisperse, porous poly(glycidyl methacrylate-co-ethylene dimethacrylate), poly(GMA-co-EDM) particles 5.8 mum in size were synthesized by "modified seeded polymerization". Poly(dihydroxypropyl methacrylate-co-ethylene dimethacrylate), poly(DHPM-co-EDM) particles were then obtained by the acidic hydrolysis of poly(GMA-co-EDM) particles. The ATRP initiator, 3-(2-bromoisobutyramido)propyl(triethoxy)silane was covalently attached onto poly(DHPM-co-EDM) particles via the reaction between triethoxysilane and diol groups. In the next stage, the selected monomer carrying strong cation exchanger groups, 3-sulfopropyl methacrylate (SPM), was polymerized on the initiator-immobilized particles via surface-initiated ATRP. The degree of polymerization of SPM (i.e., length of polyionic ligand) on the particles was precisely controlled by adjusting ATRP conditions. Poly(SPM)-grafted poly(DHPM-co-EDM) particles obtained with different ATRP formulations were tried as chromatographic packing in the separation of proteins by ion-exchange chromatography. The proteins were successfully separated with higher column yields with respect to the previously proposed materials. The plate heights between 100 and 150 mum were achieved with the column packed with the particles carrying the shortest poly(SPM) chains. The plate height showed no significant increase with increasing flow rate in the range of 0.5-16 cm/min.     

Preparation and characterization of antifouling thermosensitive magnetic nanoparticles for applications in biomedicine

Copolymer brushes grafting onto magnetic nanoparticles (MNPs) were prepared via surface free radical polymerization to improve antifouling properties of thermosensitive MNPs. A chain transfer agent was firstly attached to MNPs by silanization. Copolymerization of poly(ethylene glycol) monomethacrylate and N-isopropylacrylamide was then conducted to graft polymer brushes on the particles surface via surface free radical polymerization. The lower critical solution temperature of the obtained thermosensitive MNPs is 43 °C, which is higher than that of homopolymer poly(N-isopropylacrylamide). Nonspecific adsorption of protein was resisted at room temperature and 45 °C. The result suggested that poly(ethylene glycol) monomethacrylate segments decrease nonspecific adsorption of protein above LCST.     

Synthesis of graphite incorporated core–shell composite of styrene-methylacrylate/polyaniline by surfactant free mini-emulsion polymerization and evaluation of their electrical property

A series of core–shell particles (SMAP/G) having polystyrene-methylacrylate copolymer (styrene-methyl acrylate) as the core and graphite incorporated polyaniline as the shell were prepared by surfactant free mini-emulsion polymerization. Here poly (SMA) copolymer latex particles were first dispersed in water and then coated with polyaniline (PA) by in situ polymerization of aniline in presence of different percentage (0.25, 0.50 and 1.0%) of graphite. The composite particles were characterized by FTIR, XRD and TGA. TEM and SEM analysis confirms the core–shell morphology of the composite particles. DC electrical conductivity values of all the samples were measured by using a standard four-probe method. The effect of temperature and the amount of graphite incorporated into the PA shell on the dc electrical conductivity of the core–shell composites was investigated. The electro chemical behaviour of the core–shell composites was studied by using a cyclic voltammeter. Electro chemical data shows that the core–shell composites are sufficiently stable under redox potential of 50 mV/s to find applications in various electronic devices.     

Fumed silica/polymer hybrid nanoparticles prepared by redox-initiated graft polymerization in emulsions

Hybrid particles comprising aggregated fumed silica nanoparticles as the core and hydrophobic polymers existing around the nanoparticles were prepared by ‘grafting from’ polymerization in emulsions. The emulsion polymerization employed cetyltrimethylammonium bromide (CTAB) as a cationic surfactant and sodium dodecyl sulfate (SDS) as an anionic surfactant, respectively, to stabilize the emulsion polymerization. The polymerization was initiated by the redox reaction between ceric ion Ce(IV) and the amine groups on the surfaces of aminated fumed silica nanoparticles that were modified by 3-aminopropyltriethoxysilane. Infrared spectroscopy and thermogravimetric analysis demonstrated that both poly(methyl methacrylate) (PMMA) and polystyrene (PS) were successfully grafted onto the fumed silica surface. The type of surfactant greatly affected the grafting ratio, monomer-to-polymer conversion, and morphology of the product. When CTAB was used as the surfactant, both the grafting ratio and monomer-to-polymer conversion were lower than when SDS was used, but transmission electron microscopy and light scattering analysis indicated that most of the resultant particles were sub-100 nm hybrid nanoparticles with a non-spherical shape and particles sizes of 75–90 and 57–85 nm for PMMA and PS-grafted fumed silica, respectively. Whereas, when SDS was used as the surfactant, the particles agglomerated to form large irregular clusters or even networks, possibly due to the electrostatic attractions between SDS and Ce(IV) and/or the aminated fumed silica nanoparticles in aqueous solution.     

Preparation and Compaction Behaviour of Poly(methyl methacrylate) Coated Iron Microparticles

The poly(methyl methacrylate)(PMMA) coatings onto surface of iron particles were electrochemically prepared and the effect on both surface structure and internal structure of the resulted material after compaction was carried out.The electrochemical polymerization treatment was performed in a fluidized bed electrolyzer using sulphuric acid solution containing potassium persulphate and methyl methacrylate(MMA).The surface topography and the microstructure of the samples were observed by scanning electron mic...     

含氟丙烯酸酯核壳乳液的合成与性能

采用三阶段种子半连续乳液聚合,制得了以BA(丙烯酸丁酯)-MMA(甲基丙烯酸甲酯)共聚物为核,BA-MMA-TFEA(甲基丙烯酸三氟乙酯)共聚物为壳的核壳型含氟丙烯酸酯乳液.对乳液聚合过程中单体转化率的变化,特别是乳胶粒子的增长及分布的演变进行了测试和分析,证实了乳胶粒子核壳结构的形成.乳液聚合物膜的性能测试结果表明,与相同含氟单体用量的常规孔液相比,含氟聚合物富集于壳层的核壳形态有利于含氟结构单元在聚合物膜表面的分布,使用少量的含氟单体即可显著降低聚合物膜的表面能,提高其耐水性.     

多孔高分子微球的制备研究

以苯乙烯、二乙烯苯为单体,引入混合溶剂作为致孔剂,采用悬浮聚合的方法制备了多孔交联聚苯乙烯微球,并通过有机萃取等方法带出致孔剂,形成永久性大孔.分析了搅拌速度、分散剂用量、致孔剂等因素对微球粒径分布和孔比表面积的影响,研究了不同工艺条件下的微球形态.结果表明,转速在180r/min左右,分散剂质量分数在0.15%左右时,可以制得粒径范围为0.2～0.8mm的聚苯乙烯微球,且微球具有良好的粒径分布.采用石蜡/甲苯、石蜡/乙酸乙酯为致孔剂时,可以形成纳米级小孔,且当石蜡/甲苯用量为86%时,孔比表面积可达到33.07m2/g,并随着交联剂用量的增加而增大.     

Growth of different shape Cu2O micro structures using PEDOT coated ITO electrode

Crystalline cuprous oxide (Cu2O) particles were successfully deposited on poly(3,4-ethylenedioxythiophene) [PEDOT] coated indium tin oxide (ITO) glass. PEDOT film was first prepared on ITO glass by electrochemical polymerization. Crystalline Cu2O particles were then deposited on the PEDOT film by applying various electrochemical synthesis methods using a copper sulfate precursor. The effects of applied electrochemical methods on the compositions, grain sizes and shapes, and surface morphologies of the electrodeposited films were investigated. The micro structures of Cu2O particles were confirmed by scanning electron microscopy (SEM) and X-ray diffraction (XRD). When the cyclic voltammetry (CV) and chronoamperometry (CA) were applied, fine Cu2O particles of cubic and pyramidal phase were formed, respectively. However, bare ITO electrode was used, metallic copper particle was obtained. It shall be assumed that PEDOT might act as a buffer layer in electrochemical reduction of cuprous ion. The details of PEDOT behavior will be the topic of future studies.     

Proton-transfer lasers from solid polymeric chains with covalently bound 2-(2'-hydroxyphenyl) benzimidazole groups

The lasing properties of a number of newly synthesized 2-(2'-hydroxyphenyl) benzimidazole derivatives copolymerized with methyl methacrylate or dissolved in poly (methyl methacrylate) and pumped with an N(2) laser are reported. The radiation mechanism is based on the intramolecular proton-transfer in the electronic excited state. Both the lasing efficiency and the dye photostability increase significantly when the proton-transfer chromophore is covalently bound to the polymeric chain, and energy-conversion efficiencies comparable to those obtained in liquid solution are demonstrated.     

Toward transparent nanocomposites based on polystyrene matrix and PMMA-grafted CeO2 nanoparticles

The association of transparent polymer and nanosized pigment particles offers attractive optical materials for various potential and existing applications. However, the particles embedded into polymers scatter light due to refractive index (RI) mismatch and reduce transparency of the resulting composite material. In this study, optical composites based on polystyrene (PS) matrix and poly(methyl methacrylate) (PMMA)-grafted CeO(2) hybrid particles were prepared. CeO(2) nanoparticles with an average diameter of 18 ± 8 nm were precipitated by treating Ce(NO(3))·6H(2)O with urea in the presence of a polymerizable surfactant, 3-methacyloxypropyltrimethoxy silane. PMMA chains were grafted on the surface of the nanoparticles upon free radical in situ solution polymerization. While blending of unmodified CeO(2) particles with PS resulted in opaque films, the transparency of the composite films was remarkably enhanced when prepared by PMMA-grafted CeO(2) hybrid particles, particularly those having a PMMA thickness of 9 nm. The improvement in transparency is presumably due to the reduction in RI mismatch between CeO(2) particles and the PS matrix when using PMMA chains at the interface.     

Synthesis of crosslinked poly(styrene-<Emphasis Type="Italic">co</Emphasis>-divinylbenzene-<Emphasis Type="Italic">co</Emphasis>-sulfopropyl methacrylate) nanoparticles by emulsion polymerization: Tuning the particle size and surface charge density

We have synthesized highly charged, crosslinked poly (styrene-co-divinylbenzene-co-sulfopropyl methacrylate) copolymer colloidal particles using emulsion polymerization. The effects of concentration of the emulsifier and the initiator on the particle size and the charge density of the colloidal particles are studied. Colloidal particle size is highly dependent upon the concentration of the emulsifier and the initiator. The colloidal particle diameter decreases with increasing concentration of the emulsifier and increases with increasing concentration of the initiator in the polymerization mixture. Number of particles, surface charge density and charges per particle are also functions of both the emulsifier and the initiator concentration. The surface charge density and the number of charges per sphere increase with increasing particle diameter. These copolymer colloid particles self assemble readily and diffract visible light. Polymer hydrogel imbibed with these colloids shows the light diffraction.     

Optimizing hydrogen-bonding miscible binary polymer blends made by concentrated emulsion polymerization

Polystyrene/poly (n-butyl methacrylate) blends were prepared by concentrated emulsion polymerization using (2-hydroxy ethyl) methacrylate and n-butyl methacrylate as hydrogen-bond donor and acceptor respectively. Two concentrated emulsions of styrene/(2-hydroxy ethyl) methacrylate and n-butyl methacrylate monomers were prepared separately, and mixed mechanically after partial polymerization. The products thus obtained consisted of compact particles. The specific formation of hydrogen bond between poly [styrene-co- (2-hydroxy ethyl) methacrylate] with poly (n-butyl methacrylate) were studied by transmission electron microscope and dynamic mechanical thermal analysis. The results showed that the miscibility is induced via hydrogen bonding between the hydroxyl group and the carbonyl groups and that hydrogen bonding plays an important role in the compatibilization of the PS/PBMA blends. The TEM micrographs also showed that the PS/PBMA blends are partially inhomogeneous on a scale of 50 nm, and only a single glass transition temperature was found by DMTA for the PS/PBMA blends containing more than 3.0 ml of (2-hydroxy) methacrylate /100 ml styrene.