Optically active core/shell nanoparticles prepared using self‐assembled polymer micelle as reactive nanoreactor

This article reports on optically active core/shell nanoparticles constituted by chiral helical polymers and prepared by a novel approach: using self‐assembled polymer micelles as reactive nanoreactors. Such core/shell nanoparticles were composed of optically active helical‐substituted polyacetylene as the core and thermosensitive poly(N‐isopropylacrylamide) as the shell. The synthetic procedure is divided into three major steps: (1) synthesis of amphiphilic diblock copolymer bearing polymerizable C[tbond]C bonds via atom transfer radical polymerization, followed by (2) self‐assembly of the diblock copolymer to form polymer micelles; and (3) catalytic emulsion polymerization of substituted acetylene monomer conducted using the polymer micelles as reactive nanoreactors leading to the core/shell nanoparticles. The core/shell nanoparticles simultaneously exhibited remarkable optical activity and thermosensitivity. The facile, versatile synthesis methodology opens new approach toward preparing novel multifunctional core/shell nanoparticles.© 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

交联核壳结构PBA/PS和PBA/PMMA纳米微球的制备与应用

考察了聚丙烯酸丁酯/聚苯乙烯(PBA/PS)以及聚丙烯酸丁酯/聚甲基丙烯酸甲酯(PBA/PMMA)交联核壳结构纳米高分子微球的制备方法,并对其在尼龙复合材料中的应用进行了初步研究.结果表明,通过交联剂的引入使粒子核层和壳层内部均形成了高度交联的结构,可以限制亲水性较小的聚苯乙烯(PS)壳层向粒子内部迁移的趋势;制备出的微球平均粒径为40~50 nm,粒径分布很窄.采用饥饿态加料方式加入第二单体不仅可以使微球具有较高的产率和凝胶率,而且可以使其具有更理想的核壳结构和更窄的粒径分布.此外,将合成出的PBA/PMMA核壳粒子对尼龙6基体进行复合的结果表明,由于该微球表面与尼龙6基体之间具有较强的界面相互作用且微球具有较大的形变能力,可以在基体中形成良好的分散,在保持材料强度的同时有效地提高了其刚性和韧性.     

Synthesis and characterization of poly(methyl methacrylate)/casein nanoparticles with a well‐defined core‐shell structure

Well‐defined, core‐shell poly(methyl methacrylate) (PMMA)/casein nanoparticles, ranging from 80 to 130 nm in diameter, were prepared via a direct graft copolymerization of methyl methacrylate (MMA) from casein. The polymerization was induced by a small amount of alkyl hydroperoxide (ROOH) in water at 80 °C. Free radicals on the amino groups of casein and alkoxy radicals were generated concurrently, which initiated the graft copolymerization and homopolymerization of MMA, respectively. The presence of casein micelles promoted the emulsion polymerization of the monomer and provided particle stability. The conversion and grafting efficiency of the monomer strongly depended on the type of radical initiator, ROOH concentration, casein to MMA ratio, and reaction temperature. The graft copolymers and homopolymer of PMMA were isolated and characterized with Fourier transform infrared spectroscopy and differential scanning calorimetry. The molecular weight determination of both the grafted and homopolymer of PMMA suggested that the graft copolymerization and homopolymerization of MMA proceeded at a similar rate. The transmission electron microscopic image of the nanoparticles clearly showed a well‐defined core‐shell morphology, where PMMA cores were coated with casein shells. The casein shells were further confirmed with a zeta‐potential measurement. Finally, this synthetic method allowed us to prepare PMMA/casein nanoparticles with a solid content of up to 31%. Thus, our new process is commercially viable. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3346–3353, 2003     

Chiral helical polyacetylene�Cvinyl polymer core/shell nanoparticles: preparation and application to optically active composite films

Optically active core/shell nanoparticles (NPs) were prepared by combining aqueous catalytic microemulsion polymerization of a monosubstituted N-propargylsulfamide monomer and free-radical polymerization of two vinyl monomers (MMA and BA) in one specific system. In such novel NPs, poly(N-propargylsulfamide) forming the cores took helical conformations of a predominant handedness, endowing the NPs with interesting optical activities. The use of two vinyl monomers simultaneously in one system led to NPs with desirable dispersity and morphology. From the NP emulsions, optically active composite films were prepared with poly(vinyl alcohol) as supporting material, attesting to the potential applications of the optically active core/shell NPs. Following the strategy, other novel core/shell NPs and advanced materials can be anticipated. The current investigations provide large possibilities to realize practical applications of highly interesting helical polyacetylenes.     

Preparation of SiO2/PMMA composite particles via conventional emulsion polymerization

A series of SiO₂/PMMA composite particles with different morphologies were prepared by conventional emulsion polymerization by the aid of acid–base interaction between the silanol groups of unmodified silica particles and the amino groups of 4‐vinylpyridine. In this approach, no surface treatment for nanosilica particles was required. The morphologies of composite particles, for example, multicore–shell, raspberry‐like, and conventional core–shell, could be controlled by modulating emulsifier content, monomer/silica ratio, silica size, and monomer feed method. The possible particle formation mechanisms were discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3807–3816, 2006     

Amphiphilic polymeric particles with core–shell nanostructures: emulsion-based syntheses and potential applications

The design and synthesis of amphiphilic nano- to micro-sized polymeric particles with core–shell nanostructures have attracted more and more attention because of their wide applicability in modern material science and their technological importance in the areas of colloid and interface science. Many synthetic strategies have been developed for the preparation of amphiphilic core–shell particles that consist of hydrophobic polymer cores and hydrophilic polymeric shells. In this review, we focus on emulsion-based approaches and properties of particles produced. These methods are: (1) grafting to functionalized particle that produces a corona-like particle, (2) grafting from reactive seed particle that produces a brush-like particle, (3) copolymerization of reactive macro-monomer with hydrophobic monomer that produces a corona-like particle, (4) emulsion polymerization in the presence of block or comb-like copolymer containing controlled free-radical moiety that produces a multi-layered particle, and (5) redox-initiated graft polymerization of vinyl monomer from a water-soluble polymer containing amino groups that produces a hairy-like particle. Potential applications of some of these particles in drug and gene deliveries, enzyme immobilization, colloidal nanocatalyst, chemical sensing, smart coating, and thermal laser imaging will be discussed.     

具有疏水核/亲水壳的双亲胶体粒子的制备

制备了具有疏水性聚苯乙烯核/亲水性聚丙烯酰胺壳的双亲粒子.疏水核通过超浓乳液聚合制备,亲水壳层通过过氧化羟基异丙苯和硫酸亚铁的界面引发制备.控制条件可得到网孔(半包覆)、褶皱(全包覆)两种形态的壳层.壳层孔的存在使得核层聚合物能够与外界接触.粒子的双亲性通过吸水吸油率进行表征.     

Immobilization of RAFT agents on silica nanoparticles utilizing an alternative functional group and subsequent surface‐initiated RAFT polymerization

Silica–polystyrene core‐shell particles were successfully prepared by surface‐mediated reversible addition fragmentation chain transfer (RAFT) polymerization of styrene monomer from the surfaces of the silica‐supported RAFT agents. Initially, macro‐RAFT agents were synthesized by RAFT polymerization of γ‐methacryloxypropyltrimethoxysilane (MPS) in the presence of chain transfer agents (CTAs). Immobilization of CTAs onto the silica surfaces was then performed by reacting silica with macro‐RAFT agents via a silane coupling. Grafting of polymer onto silica forms core‐shell nanostructures and shows a sharp contrast between silica core and polymer shell in the phase composition. The thickness of grafted‐polymer shell and the diameter of core‐shell particles increase with the increasing ratio of monomer to silica. A control experiment was carried out by conventional free radical emulsion copolymerization of MPS‐grafted silica and styrene under comparable conditions. The resulting data provide further insight into the chemical composition of grafted‐polymers that are grown from the silica surface through RAFT process. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 467–484, 2009     

A versatile surfactant‐mediated synthetic route to gold/polyaniline derivative core/shell nanocomposites

This article describes a versatile two‐step method for gold/polyaniline derivative core/shell nanocomposites with the aid of nonionic surfactant F127. First, F127 and monomer were introduced to gold colloids followed by the addition of oxidant to initiate the polymerization of monomer to afford a conducting polymer shell around each gold nanoparticle. Experimental parameters, such as kinds and concentrations of surfactant and monomer, gold core size and shape, reaction time, were systematically investigated to disclose the underground mechanisms involved in the formation of gold/polymer core/shell nanocomposites. Furthermore, Fourier transform infrared, ultraviolet–visible, X‐ray diffraction, and X‐ray photoelectron spectroscopy techniques were used to characterize the gold/polymer core/shell nanocomposites. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3903–3912, 2010     

Structured poly(divinylbenzene‐co‐chloromethylstyrene) microspheres by thermal imprinting precipitation polymerization

The formation of monodisperse, crosslinked, thermally inscribed core‐shell microspheres by free radical precipitation copolymerization of chloromethylstyrene and divinylbenzene in acetonitrile is reported. The radial density profiles of these microspheres match the thermal profiles used during copolymerization: stepping down the polymerization temperature from 75 °C to 65 °C several hours into the copolymerization led to core‐shell microspheres with porous cores and denser shells, while stepping up the polymerization temperature from 68 °C to 78 °C during the polymerization led to formation of microspheres with denser cores and more swellable shells. Microsphere size distributions and internal morphologies were studied using optical and transmission electron microscopy. The change in network swellability with temperature was compared with model studies of aggregation of corresponding nanogels, both in acetonitrile and in related solvent systems, as a function of temperature, indicating the theta‐temperature for this copolymer/solvent system to be around 30 °C. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1159–1166     

Fabrication of monodisperse luminescent nanoparticles with core/shell poly(styrene/thiophene) structure

Luminescent poly(styrene/thiophene) (PSt/PT) core/shell nanoparticles were prepared by oxidative polymerization in the presence of PSt seed particles. PSt seed particles with uniform size distribution were prepared with an anionic surfactant by an emulsion polymerization process, and were used as a template to prepare monodispersive PT‐coated nanoparticles. A luminescent Polythiophene (PT) layer was formed on the surface of PSt nanoparticles by oxidation polymerization with iron chloride (FeCl₃) and hydrogen peroxide (H₂O₂). The mechanism of core/shell formation was found to be the interface‐dominant polymerization induced by the electrostatic attraction between the sulfonate group of anionic surfactant and Fe³⁺ ions after the diffusion of thiophene monomer to the PSt nanoparticles. Field‐emission scanning electron microscopy and transmission electron microscopy (TEM) proved the core/shell structure, which provided key evidence that PT was incorporated onto the surface of PSt nanoparticles. In addition, the effect of the PT shell thickness on photoluminescent (PL) intensity was investigated by changing the shell thickness of PSt/PT nanoparticles. We observed that the PL intensity increased up to about 30 nm of PT shell thickness, and then decreased due to self‐absorption. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5968–5975, 2008     

Designed Synthesis of Well‐Defined Pd@Pt Core–Shell Nanoparticles with Controlled Shell Thickness as Efficient Oxygen Reduction Electrocatalysts

Improving the electrocatalytic activity and durability of Pt‐based catalysts with low Pt content toward the oxygen reduction reaction (ORR) is one of the main challenges in advancing the performance of polymer electrolyte membrane fuel cells (PEMFCs). Herein, a designed synthesis of well‐defined Pd@Pt core–shell nanoparticles (NPs) with a controlled Pt shell thickness of 0.4–1.2 nm by a facile wet chemical method and their electrocatalytic performances for ORR as a function of shell thickness are reported. Pd@Pt NPs with predetermined structural parameters were prepared by in situ heteroepitaxial growth of Pt on as‐synthesized 6 nm Pd NPs without any sacrificial layers and intermediate workup processes, and thus the synthetic procedure for the production of Pd@Pt NPs with well‐defined sizes and shell thicknesses is greatly simplified. The Pt shell thickness could be precisely controlled by adjusting the molar ratio of Pt to Pd. The ORR performance of the Pd@Pt NPs strongly depended on the thickness of their Pt shells. The Pd@Pt NPs with 0.94 nm Pt shells exhibited enhanced specific activity and higher durability compared to other Pd@Pt NPs and commercial Pt/C catalysts. Testing Pd@Pt NPs with 0.94 nm Pt shells in a membrane electrode assembly revealed a single‐cell performance comparable with that of the Pt/C catalyst despite their lower Pt content, that is the present NP catalysts can facilitate low‐cost and high‐efficient applications of PEMFCs.     

One‐stage synthesis of narrowly dispersed polymeric core‐shell microspheres

A method of one‐stage soap‐free emulsion polymerization to synthesize narrowly dispersed core‐shell microspheres is proposed. Following this method, core‐shell microspheres of poly(styrene‐co‐4‐vinylpyridine), poly(styrene‐co‐methyl acrylic acid), and poly[styrene‐co‐2‐(acetoacetoxy)ethyl methacrylate‐co‐methyl acrylic acid] are synthesized by one‐stage soap‐free emulsion polymerization of a mixture of one or two hydrophobic monomers and a suitable hydrophilic monomer in water. The effect of the molar ratio of the hydrophobic monomer to the hydrophilic one on the size, the core thickness, and the shell thickness of the core‐shell microspheres is discussed. The molar ratio of the hydrophobic and hydrophilic monomers and the hydrophilicity of the resultant oligomers of the hydrophilic monomer are optimized to synthesize narrowly dispersed core‐shell microspheres. A possible mechanism of one‐stage soap‐free emulsion polymerization to synthesize core‐shell microspheres is suggested and coagglutination of the oligomers of the hydrophilic monomers on the hydrophobic core is considered to be the key to form core‐shell microspheres. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1192–1202, 2008     

Synthesis of polymeric core–shell particles using surface‐initiated living free‐radical polymerization

An easy and novel approach to the synthesis of functionalized nanostructured polymeric particles is reported. The surfactant‐free emulsion polymerization of methyl methacrylate in the presence of the crosslinking reagent 2‐ethyl‐2‐(hydroxy methyl)‐1,3‐propanediol trimethacrylate was used to in situ crosslink colloid micelles to produce stable, crosslinked polymeric particles (diameter size ～ 100–300 nm). A functionalized methacrylate monomer, 2‐methacryloxyethyl‐2′‐bromoisobutyrate, containing a dormant atom transfer radical polymerization (ATRP) living free‐radical initiator, which is termed an inimer (initiator/monomer), was added to the solution during the polymerization to functionalize the surface of the particles with ATRP initiator groups. The surface‐initiated ATRP of different monomers was then carried out to produce core–shell‐type polymeric nanostructures. This versatile technique can be easily employed for the design of a wide variety of polymeric shells surrounding a crosslinked core while keeping good control over the sizes of the nanostructures. The particles were characterized with scanning electron microscopy, transmission electron microscopy, optical microscopy, dynamic light scattering, and Raman spectroscopy. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1575–1584, 2007     

Synthesis of Triple‐Layered Ag@Co@Ni Core–Shell Nanoparticles for the Catalytic Dehydrogenation of Ammonia Borane

Triple‐layered Ag@Co@Ni core–shell nanoparticles (NPs) containing a silver core, a cobalt inner shell, and a nickel outer shell were formed by an in situ chemical reduction method. The thickness of the double shells varied with different cobalt and nickel contents. Ag_0.04@Co_0.48@Ni_0.48 showed the most distinct core–shell structure. Compared with its bimetallic core–shell counterparts, this catalyst showed higher catalytic activity for the hydrolysis of NH₃BH₃ (AB). The synergetic interaction between Co and Ni in Ag_0.04@Co_0.48@Ni_0.48 NPs may play a critical role in the enhanced catalytic activity. Furthermore, cobalt–nickel double shells surrounding the silver core in the special triple‐layered core–shell structure provided increasing amounts of active sites on the surface to facilitate the catalytic reaction. These promising catalysts may lead to applications for AB in the field of fuel cells.     

Multicomponent latex IPN materials. I. Morphology control

A series of novel structured latex particles with interpenetrating polymer network (IPN) cores and glassy SAN shells were developed in an attempt to investigate the feasibility of these polymers as both toughening and damping agents in thermoplastics. The IPN cores were composed of one impact part (polybutadiene based) and one damping part (acrylic based, with T_g around +10°C). The particle morphologies of these polymers were determined by TEM. The glass transitions and mechanical behavior of the polymers were characterized from DMS. The effect of different components on the final core/shell particle morphologies and mechanical properties was studied. The mechanical behavior of core/shell particles with IPN cores was also compared with that of separate core/shell and multilayered core/shell particles. In addition, normal core/shell synthesis (rubbery part first then the glassy part) and inverted core/shell synthesis (glassy part first then the rubbery part) were performed to provide another access for morphology control. It was found that the core/shell latex particles with poly(butyl acrylate) based copolymers are more miscible than poly(ethylhexyl methacrylate)-based copolymers. The high grafting efficiency of poly(butyl acrylate) plays an important role in governing phase miscibility. The latex particles synthesized by the inverted core/shell mode showed higher miscibility than the normal synthesized ones. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2193–2206, 1997     

The preparation of amphiphilic core‐shell nanospheres by using water‐soluble macrophotoinitiator

The amphiphilic poly(AM‐co‐SA)‐ITXH macrophotoinitiator was synthesized by precipitation photopolymerization under UV irradiation with isopropylthioxanthone (ITX) as free radical photoinitiator. A novel method has been developed to prepare amphiphilic core‐shell polymer nanospheres via photopolymerization of methyl methacrylate (MMA) in aqueous media, with amphiphilic copolymer macrophotoinitiator poly(AM‐co‐SA)‐ITXH. During polymerization, the amphiphilic macroradicals underwent in situ self‐assembly to form polymeric micelles, which promoted the emulsion polymerization of the monomer. Thus, amphiphilic core‐shell nanospheres ranging from 70 to 140 nm in diameter were produced in the absence of surfactant. The conversion of the monomer, number average molecular weights (M_n), and particle size were found to be highly dependent on the macrophotoinitiator and monomer concentration. The macrophotoinitiator and amphiphilic particles were characterized by FTIR, UV‐vis, ¹H NMR, TEM, DSC, and contact angle measurements. The results showed the particles had well‐defined amphiphilic core‐shell structure. This new method is scientifically and technologically significant because it provides a commercially viable route to a wide variety of novel amphiphilic core‐shell nanospheres. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 936–942, 2010     

Hydroplasticization effect in structured latex particles film formation

Series of emulsion copolymers with structured particles were synthesized comprising copolymerized acrylic or methacrylic acid in the outer layer. All samples were based on particles, containing identical cores slightly crosslinked by allyl methacrylate and variable shells, weight ratio core/shell being constant 1/1. Each sample contained 10 wt% HEMA in the shell to achieve the film crosslinkability. In both series samples with different hardness and polarity (varible styrene/butyl acrylate ratio) of the shell layer were prepared. It was shown that the extent of particle swelling and hydroplasticization depends not only on the content of dissociated carboxylic groups, but also on the composition and crosslinking of the rest of polymer chain i.e. on its polarity and rigidity and on the origin of carboxylic groups. The effect of dissociated carboxylic groups on lowering the minimum film forming temperature was much more pronounced if the polymer chains were more polar.     

Controllable preparation of epoxy‐functionalized magnetic polymer latexes with different morphologies by modified miniemulsion polymerization

The synthesis of functional magnetic polymer latexes (MPLs) with epoxy groups introduced via a modified miniemulsion polymerization route was described. The epoxy group content on the surface could be controlled by seed emulsion followed and characterized by FTIR and zeta potential measurements. We also developed a novel approach to achieve manipulation of the morphology of the MPLs based on kinetic control of the polymerization system. MPLs with different morphologies were obtained ranging from core–shell microstructures, dispersed microstructures to asymmetric microstructure, which were characterized by TEM, DLS, and TGA. The mechanisms of the contribution of kinetic factors such as polymerization rate, reaction time, and temperature contributing to the formation of the different morphologies were also investigated. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2284–2293, 2010     

Preparation of Silica/Poly(tert‐butylmethacrylate) Core/Shell Nanocomposite Latex Particles

Nanocomposite latex particles, with a silica nanoparticle as core and crosslinked poly(tert‐butylmethacrylate) as shell, were prepared in this work. Silica nanoparticles were first synthesized by a sol‐gel process, and then modified by 3‐(trimethoxysilyl)propyl methacrylate (MPS) to graft C?C groups on their surfaces. The MPS‐modified silica nanoparticles were characterized by elemental analysis, FTIR, and ²⁹Si NMR and ¹³C‐NMR spectroscopy; the results showed that the C?C groups were successfully grafted on the surface of the silica nanoparticles and the grafted substance was mostly the oligomer formed by the hydrolysis and condensation reaction of MPS. Silica/poly(tert‐butylmethacrylate) core/shell nanocomposite latex particles were prepared via seed emulsion polymerization using the MPS‐modified silica nanoparticle as seed, tert‐butylmethacrylate as monomer and ethyleneglycol dimethacrylate as crosslinker. Their core/shell nanocomposite structure and chemical composition were characterized by means of TEM and FTIR, respectively, and the results indicated that silica/poly(tert‐butylmethacrylate) core/shell nanocomposite latex particles were obtained.