Preparation of Bowl-Like Polymer Particles via Multi-Step Emulsion Polymerization and Alkali Post-Treatment

Summary : Monodisperse P(BA-MMA-MAA-EGDMA)/P(St-MAA-DVB) core/shell latex particles were first synthesized by a four-step emulsion polymerization, and a new kind of latex particles with “bowl-like” morphology were obtained by post-treating the resultant core/shell particles under alkali condition. Results indicated that the feeding rates of the monomer mixture and initiator aqueous solution were the key parameters to obtain monodisperse core/shell latex particles in the emulsion polymerization process, and the latex particles with “bowl-like” morphology could be generated only when the treatment temperature was equal or higher than 70 °C.     

SiO2/聚合物核壳型杂化粒子及其空心结构的制备

SiO2/聚合物核壳型杂化粒子及其空心结构以其独特的形貌在药物控制释放、催化剂载体、生物医药等领域应用前景广阔,引起了人们的广泛关注。本文着重从乳液聚合法、仿生矿化法等制备方法角度阐述了SiO2/聚合物核壳型杂化粒子及其空心结构的研究进展。乳液聚合制备SiO2/聚合物核壳型杂化粒子简单易行,一般需要预先合成SiO2纳米粒子,其合成过程通常需要一些非理想的条件,如高温高压、极端pH、昂贵或有毒的有机试剂等,而且预先合成的SiO2粒子无法与聚合物实现100%匹配,即总有纯的聚合物粒子存在。相比之下,原位仿生矿化法制备SiO2杂化粒子不仅在环境条件下可进行,而且能够精确控制其纳米尺度的形态及分级有序结构。目前对材料科学家来讲,要使人工合成SiO2/聚合物杂化粒子实现像自然生物硅那样优异的性能,仍然是很大的挑战。     

浓乳液双相聚合方法制备异形聚合物粒子

采用浓乳液双相聚合方法,成功制备了聚丙烯酸丁酯(PBA)的异形粒子,通过在连续相中引入聚合物隔层,大大提高了浓乳液聚合过程中的稳定性,探讨了隔层种类对浓乳液稳定性的影响,并研究了浓乳液分散相体积分数和交联剂用量对PBA粒子异形程度的影响,并结果表明,浓乳液双相聚合过程中,分散相体积分数越高,交联剂用量越高,PBA粒子的异形程度越大。     

Preparation of Responsive Micrometer‐Sized Microgel Particles with a Highly Functionalized Shell

We describe a facile approach for the synthesis of micrometer‐sized (∼3.5 μm), pH‐responsive microgel particles, which have functional carboxylic acid groups concentrated in the shell. The large size offers the possibility to directly study the interactions between individual, isolated microgel particles with active ingredients by optical microscopy. Our results show that the synthesized microgel particles can load and release active ingredients via changing pH values. The complexation of Ca²⁺ with the ‐COOH functional groups located at the microgel surfaces not only regulates the active ingredient's uptake efficiency, but also provides a novel way to reveal the spatial distribution of the functional groups inside the microgel particles.     

聚合物中空微球的合成策略（英文）

在过去的20年中,聚合物中空微球由于其独特的结构和优异的性质受到了广泛的关注.它们表现出低密度、高比表面积和高负载力的特性,在催化、药物递送及能量存储等领域中展现出巨大的应用前景.本文综合评述了聚合物中空微球的合成策略,主要包括模板法、乳液聚合法、自组装与及微流控等,并详细阐述和讨论了这些合成策略的原理、典型过程以及优缺点.同时,还指出了现有合成策略面临的挑战以及聚合物中空微球存在的不足,并对聚合物中空微球的制备和应用前景进行了展望.     

Synthesis and Characterization of Large Dimension PBA-P(MMA-ITA) Latex Particles with Core-Shell Morphology

In this paper, a novel large dimension poly(n-butyl acrylate)-poly(methyl methacrylate-itaconic acid) (PBA-P(MMA-ITA)) core-shell latex particles (CSR) with diameter of 200 nm～300 nm were successfully synthesized via pre-emulsion and semi-continuous seeded emulsion polymerization process. The analysis on the surface tension and coagulation rate of polymeric system, size and distribution of latex particles indicated that the composite emulsifier of sodium dodecyl sulfonate/polyoxyethylene nonyl phenyl ether (SDS/OP-10) had the best emulsified effect. The optimal ratio of SDS/OP-10 was 1:1 and its optimum dosage was 1.0% of monomer amount. FTIR analysis results confirmed that ITA participated in the copolymerization reaction and the chemical bond between P(MMA-ITA) copolymer and PBA core existed in the interfacial of core and shell. DSC analysis results showed that the glass transition temperature (T _g) of P(MMA-ITA) copolymer increased with the increase of the ITA dosage and decreased with the increase of the core shell mass ratio. TEM images revealed that CSR particles had core-shell morphology indeed, but the particles’ core-shell morphology would be changed at higher ITA dosage and core shell mass ratio. The size of CSR particles was 330 nm, and the diameter of PBA core was 290 nm. ITA content in the shell of CSR particles was analyzed by non-aqueous acid-base titration. ITA content was the highest at 6% of ITA dosage, ITA amount which chemically bonded with PBA core was the highest at 8% of ITA dosage. When the core shell mass ratio was 60/40, ITA content and ITA amount which grafted onto PBA core were both the highest. ITA content of CSR particles achieved above 1.11% in this work, and it is completely possible for using CSR particles toughening and compatibilizing polyamide 6 (PA 6).     

Simultaneous ROMP and ATRP in Aqueous Dispersed Media: A Straightforward Strategy to Prepare Polymer Composite Particles with Original Morphologies

Summary: The simultaneous ring-opening metathesis polymerization of norbornene and atom-transfer radical polymerization of methyl methacrylate is used as a convenient tool to prepare polymer composite particles in a single step and using a single catalyst. The current article reviews the use of miniemulsion and microemulsion conditions to reach this goal. The two developed approaches are assessed on chemical and colloidal levels and the prepared composite particles are scrutinized from a morphological point of view.     

PMMA-PAN核壳结构复合乳胶的制备与表征

采用疏水引发剂引发的半连续无皂乳液聚合法,合成了Z均流体力学直径约70nm的聚甲基丙烯酸甲酯(PMMA)纳米乳胶。以PMMA纳米乳胶为种子,采用疏水引发剂引发的种子乳液聚合法,制备了PMMA-聚丙烯腈(PAN)核壳结构复合乳胶。采用动态光散射、傅里叶红外光谱、扫描电镜和透射电镜表征了各种乳胶粒的组成、尺寸、结构和微观形态。研究了反应温度、单体用量和表面活性剂用量对PMMA-PAN复合乳胶粒的结构和形态的影响。结果表明:PMMAPAN复合乳胶粒为核壳结构,其壳层厚度可通过改变单体用量进行调整。     

Liquid-Crystalline Polymer Particles Prepared by Classical Polymerization Techniques

Liquid-crystalline polymer particles prepared by classical polymerization techniques are receiving increased attention as promising candidates for use in a variety of applications including micro-actuators, structurally colored objects, and absorbents. These particles have anisotropic molecular order and liquid-crystalline phases that distinguish them from conventional polymer particles. In this minireview, the preparation of liquid-crystalline polymer particles from classical suspension, (mini-)emulsion, dispersion, and precipitation polymerization reactions are discussed. The particle sizes, molecular orientations, and liquid-crystalline phases produced by each technique are summarized and compared. We conclude with a discussion of the challenges and prospects of the preparation of liquid-crystalline polymer particles by classical polymerization techniques.     

以胶体粒子为模板制备核壳纳米复合粒子

核壳纳米复合粒子具有许多不同于单组分胶体粒子的独特的光、电、磁、催化等物理与化学性质,是构筑新型功能复合材料的重要组元,在光子带隙材料、微波吸收材料、电磁流变液、催化剂和生物等领域有重要应用.本文从控制核壳复合粒子的微观结构及壳层均匀性与厚度的角度,详细评述了目前以胶体粒子为模板制备粒径从纳米到微米尺度的核壳复合粒子的方法.指出利用胶体粒子模板表面与壳层物质或其前驱物间的特殊相互作用(包括静电和化学相互作用),是完善现有制备方法和发展新方法来制备具有设定组成、结构和性能的核壳复合粒子的关键,同时也是将来的粒子表面纳米工程和获取有序的、先进纳米复合材料的主要方向。     

In Situ Incorporation of Doxorubicin in Copolymer Particles During Suspension Polymerization

Summary: This work reports the kinetic behavior and the molecular properties of obtained copolymers during vinyl acetate and methyl methacrylate suspension copolymerizations in presence of doxorubicin. The obtained spherical particles are intended for use as chemoembolization agents. It is shown that the presence of doxorubicin in the reaction medium promotes significant changes in the copolymerization kinetics and final molecular weight averages of the polymer product.     

超声法制备硫化铅/二氧化硅核壳结构亚微米粒子

0 引言 纳米微粒具有的小尺寸效应,表面效应、量子尺寸效应及宏观量子隧道效应等导致纳米粒子的热、磁、光、敏感特性和表面稳定性等不同于常规粒子,这就使得它具有广阔的应用前景.     

The Effect of Cyclodextrins in Polymer Particles Synthesis

The free radical polymerization of styrene in water in the presence of β-cyclodextrin (β-CD) is described.It is found that β-CD could greatly accelerate the polymerization,enhance the final conversion of monomer.The particle-size distribution of the final polymer is also improved than that without β-CD in the system.     

Template Polymerization-solvent Extraction：A New Method for Fabrication of Hollow Polysiloxane Particles

Hollow polysiloxane particles with diameters between 1.40 and 1.60 micrometres were fabricated by consecutive cocondensation of methyltrimethoxysilane and diphenyldimethoxysilane monomers onto polydiphenylsiloxane,subsequently removing the templated polydiphenylsiloxane by exposure to solvents.TEM and AFM measurement reveal that there are obvious hollow sphere structures for the polysiloxane microsphere particles.The hollow spheres are envisioned to have applications in areas ranging from dye-industry,catalysis,pharmaceutics to materials science.     

种子聚合法制备非球形聚合物颗粒的研究进展

十年前,光子晶体的需求促进了非球形颗粒的研究热潮。非球形颗粒由于其对称性下降,带来了新的性能和应用前景,成为当前材料领域研究的热点,得到了较广泛研究,目前其制备方法包括种子聚合法、自组装法、粒子聚集法、微流体法和机械拉伸法等。本文简述了种子聚合法的发展历程,介绍了种子聚合法制备非球形聚合物颗粒的相关机理,以种子微球材质分类综述了种子聚合法制备非球形聚合物颗粒的形貌和结构控制技术进展,概述了其潜在的应用领域,展望了可能的发展趋势。     

亚微米级聚苯乙烯/聚硅氧烷核壳粒子的制备及其应用

以乳液聚合制备的聚苯乙烯乳液为种子,加入甲基三甲氧基硅烷(MTMS)水解溶液进行缩聚反应,合成亚微米级聚苯乙烯/聚硅氧烷核壳粒子,并以此作为光散射剂添加至聚甲基丙烯酸甲酯(PMMA)树脂中,制备了光散射材料;考察了亚微米级核壳粒子添加在PMMA树脂中的分散性。结果表明:经过双螺杆剪切作用的挤出加工后,可以实现核壳粒子在PMMA树脂中的良好分散。核壳粒子可以大幅度提高PMMA的雾度,当聚苯乙烯/聚硅氧烷核壳粒子(NS82)的含量为1%时,制得的PMMA样片(厚度为2 mm)的雾度为89%,透光率为69%,有效光散射系数为61%。     

聚合物/水两相界面自由基引发聚合制备不对称粒子

报导了一种新的制备不对称粒子的简单方法. 首先, 利用旋转涂膜法在云母片表面涂上一层聚4-乙烯基吡啶(P4VP)薄膜, 并且P4VP薄膜中分散有自由基引发剂偶氮二异丁腈(AIBN)和二乙烯基苯(DVB); 然后将云母片插入溶解有N-异丙基丙烯酰胺(NIPAM)的水溶液, 在氮气保护下升高温度, 实施自由基聚合. 聚合起始阶段, AIBN分解的自由基主要是在P4VP薄膜中引发DVB聚合. 由于相分离, DVB聚合后形成的PDVB在P4VP中形成粒子. 随着聚合的进行, 由于PDVB粒子的不断长大或向水/P4VP界面迁移, 使得粒子的一侧暴露在水相中. 在界面上, PDVB粒子上的大分子自由基或AIBN新分解产生的自由基与PDVB中剩余双键继续反应形成的大分子自由基引发水相中的NIPAM反应, 从而在粒子的一侧形成PNIPAM接枝; 而PDVB粒子的另一侧则嵌在P4VP膜中, 不会参加接枝反应. 最后, 实施与P4VP层分离后即可得到两亲性的PDVB-PNIPAM不对称粒子.     

Preparation of Micron‐Sized Monodisperse Poly(ionic liquid) Particles

Micron‐sized monodisperse poly(ionic liquid) (PIL) particles, poly([2‐(methacryloyloxy)ethyl]trimethylammonium bis(trifluoromethanesulfonyl)amide), were prepared by dispersion polymerization at 70 °C in methanol with poly(vinylpyrrolidone) as a stabilizer. The obtained particle size could be controlled by addition of ethanol to the methanol medium while maintaining narrow monodispersity. The PIL particles exhibit unique properties; they can be observed by scanning electron microscopy without platinum coating, which is generally used to avoid an electron charge. Moreover, the solubility of the PIL particles can be easily changed by changing the counter anion, similar to the process for ionic liquids.     

Evaluation of Thermal Properties of Composites Prepared from Pistachio Shell Particles Treated Chemically and Polypropylene

The purpose of the present work was to prepare polypropylene (PP) matrix composited filled with chemically treated pistachio shell particles (PTx), and evaluate their effect on the composites’ thermal properties. PP-PTx composites were formulated in different PTx content (from 2 to 10 phr) in a mixing chamber, using the melt-mixing process. The PTx were chemically treated using a NaOH solution and infrared spectroscopy (FTIR). According to thermogravimetric analysis (TGA), the treatment of pistachio shell particles resulted in the remotion of lignin and hemicellulose. The thermal stability was evaluated by means of TGA, where the presence of PTx in composites showed a positive effect compared with PP pristine. Thermal properties such as crystallization temperature (Tc), crystallization enthalpy (∆Hc), melting temperature (Tm) and crystallinity were determinate by means differential scanning calorimetry (DSC); these results suggest that the PTx had a nucleation effect on the PP matrix, increasing their crystallinity. Dynamic mechanical analysis (DMA) showed that stiffness of the composites increase compared with that PP pristine, as well as the storage modulus, and the best results were found at a PTx concentration of 4 phr. At higher concentrations, the positive effect decreased; however, they were better than the reference PP.