分散共聚合制备PSt-AA-EGDMA功能性单分散微米级交联微球的研究

以苯乙烯(St)为主单体,丙烯酸(AA)为功能单体,乙二醇二甲基双丙烯酸酯(EGDMA)为交联单体,聚乙烯吡咯烷酮(PVP)为稳定剂,偶氮二异丁腈(AIBN)为引发剂,乙醇/水混合溶剂为分散介质,用分散聚合法一步合成了功能性单分散大粒径(10～20μm)交联聚苯乙烯微球.研究了PSt-AA-EGDMA三元分散共聚合体系的动力学,由转化率-时间关联得到动力学方程;R_p=k[I]^0.13([St]^1.87+[AA]^0.13+[EGDMA]^0.2)·(1+[PVP]^0.2)exp(-E/RT).详细讨论了AA,EGDMA,PVP的浓度和溶剂极性对羧基分布的影响,阐述了AA和EGDMA对粒子形态、粒径及粒径分布的影响.     

Polysaccharides as a source of advanced materials: Cellulose hollow microspheres for drug delivery in cancer therapy

Biocompatible hollow poly(methyl acrylic acid-co-N-isopropylacrylamide-co-ethyleneglycol dimethacrylate)@cellulose succinate (P(MAA-co-NIPAAM-co-EGDMA)@CS) microspheres have been synthesized by employing uniform silica-MPS microspheres as template. Silica spheres were synthesized via Stöber method involving tetraethyl orthosilicate. The surface of resulting silica Stöber microspheres was modified using 3-methacryloxypropyltrimethoxysilane (MPS), a polymerizable silane coupling agent. The above reagent introduces carbon–carbon double bonds on microspheres’ surface. This strategy uses the copolymerization of the following monomers, methacrylic acid (MAA), N-isopropyl acrylamide (NIPAAM) and the ethyleneglycol dimethacrylate (EGDMA), which was used as cross-linker, aiming at fabricating the first shell. Distillation precipitation polymerization method was carried out with 2,2-azobis(2-methylpropionitrile) as initiator in acetonitrile aiming at coating the inorganic microspheres with organic shell of the above-mentioned copolymer. In continuation, cellulose succinate and cellulose powder was absorbed through electrostatic interactions onto microspheres’ surface and the isolated product was cross-linked through esteric bonds formation. The cellulose succinate hollow microspheres were obtained after the silica core removal. The resulting spheres were characterized by Fourier transform infrared spectroscopy and observed by scanning and transmission electron microscopy. Dynamic light scattering was used to study the hydrodynamic diameter of the synthesized microspheres. The anticancer drug daunorubicin was loaded in the spheres, and its release behavior was evaluated at acidic and slightly basic pH conditions, aiming at evaluating its behavior at the healthy and pathogenic tissues.     

Core‐shell microspheres with surface grafted poly(vinyl alcohol) as drug carriers for the treatment of hepatocellular carcinoma

Core(polyvinyl neodecanoate‐ethylene glycol dimethacrylate)‐shell(polyvinyl alcohol) (core (P(VND‐EGDMA))‐shell(PVA)) microspheres were developed by seeded polymerization with the use of conventional free radical and RAFT/MADIX mediated polymerization. Poly(vinyl pivalate) PVPi was grafted onto microspheres prepared via suspension polymerization of vinylneodecanoate and ethylene glycol dimethacrylate. The amount of grafted polymer was found to be independent from the technique used with conventional free radical polymerization and MADIX polymerization resulting into similar shell thicknesses. Both systems—grafting via free radical polymerization or the MADIX process—were found to follow slightly different kinetics. While the free radical polymerization resulted in a weight gain linear with the monomer consumption in solution the growth in the MADIX controlled system experienced a delay. The core‐shell microspheres were obtained by hydrolysis of the poly(vinyl pivalate) surface grafted brushes to form poly(vinyl alcohol). During hydrolysis the microspheres lost a significant amount of weight, consistent with the hydrolysis of 40–70% of all VPi units. Drug loading was found to be independent of the shell layer thickness, suggesting that the drug loading is governed by the amount of bulk material. The shell layer does not appear to represent an obstacle to the drug ingress. Cell testing using colorectal cancer cell lines HT 29 confirm the biocompatibility of the empty microspheres whereas the clofazimine loaded particles lead to 50% cell death, confirming the release of the drug. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3256–3272, 2007     

Different synthetic routes to obtain hydrophilic matrices

The aim of this study was to examine two different synthetic routes for obtaining new hydrophilic matrices either by the modification of a synthetic matrix or by the copolymerization of hydrophilic monomers. First, the acrylic acid‐ethylene glycol dimethacrylate (AAc‐EGDMA) matrix, obtained from suspension with cyclohexane as the diluent at 70 °C after 2 h of reaction, was used as a base to be modified with TRIS(hydroxymethyl)aminomethane (TRIS). Experimental variables affecting the carbodiimide‐mediated amide‐bond development (i.e., the type of carbodiimide, reaction time, pH, and concentration of the matrix in the reaction medium) on the synthetic AAc‐EGDMA matrix with TRIS were studied. Second, the N‐acryloyl‐TRIS(hydroxymethyl)aminomethane‐ethylene glycol dimethacrylate (NAT‐EGDMA) matrix was obtained under the same experimental conditions as reported for AAc‐EGDMA. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 489–497, 2000     

Synthesis of titania/polymer core-shell hybrid microspheres

Monodisperse titania/polymer core-shell microspheres were prepared by a two-stage reaction with titania as core and poly(ethyleneglycol dimethacrylate) (PEGDMA) as shell, in which the titania cores were synthesized by a sol-gel method and subsequently grafted with 3-trimethoxysilyl methacrylate as the first-stage reaction to incorporate the vinyl groups on the surface of inorganic core. The PEGDMA shell was then encapsulated over the MPS-modified titania core by distillation precipitation polymerization of ethyleneglycol dimethacrylate in neat acetonitrile during the second-stage polymerization via capture of the radicals of EGDMA with the aid of the reactive vinyl groups on the surface of inorganic core without any stabilizer or surfactant. The shell thickness of the core-shell hybrid microspheres was controlled by the feed of EGDMA monomer during the polymerization. The resultant titania particles and core-shell microspheres were studied by transmission electron microscopy, Fourier-transform infrared spectra, X-ray photoelectron spectroscopy, and thermogravimetric analysis.     

Synthesis of pH‐responsive magnetic yolk–shell nanoparticles: A comparison between conventional etching and new deswelling approaches

Iron oxide (Fe₃O₄) magnetic nanoparticles as movable cores were used to synthesize yolk–shell nanoparticles with pH‐responsive shell composed of ethylene glycol dimethacrylate (EGDMA)‐crosslinked poly(acrylic acid) (PAA) via two different routes. In the first more common route, Fe₃O₄ nanoparticles were coated with silica layer via the Stöber process to yield Fe₃O₄@SiO₂ core–shell nanoparticles, subsequently used as seeds in the distillation precipitation copolymerization of AA and EGDMA to yield Fe₃O₄@SiO₂@P(AA‐EGDMA). The silica layer was selectively removed through alkali etching to yield Fe₃O₄@air@P(AA‐EGDMA). In the second route, Fe₃O₄ nanoparticles without any stabilization were used as seeds in the distillation precipitation copolymerization of AA and EGDMA to yield Fe₃O₄@P(AA‐EGDMA) core–shell nanoparticles. The nanoparticles were subsequently dispersed in acidic medium of pH = 2. Yolk–shell Fe₃O₄@air@P(AA‐EGDMA) nanoparticles were formed through deswelling of crosslinked PAA because of protonation of carboxyl groups at low pH values. Various techniques were utilized to investigate the characteristics of the synthesized core–shell nanoparticles. Formation of yolk–shell nanostructure was observed for both synthesis routes, namely etching of silica layer and deswelling approaches, from vibrating sample magnetometry and transmission electron microscopy results. Both types of nanoparticles showed pH‐responsive behaviour, i.e. decrease in absorption with increase in pH, as examined using UV–visible spectroscopy.     

Suspension polymerization of poly(ethylene glycol) methacrylate: a route for swellable spherical gel beads with controlled hydrophilicity and functionality

 Spherical and swellable gel beads were obtained by the suspension polymerization of poly(ethylene glycol) methacrylate macromonomer (PEG-MA). The average size and size distribution properties, the equilibrium swelling behaviour and the protein adsorption characteristics of PEG-MA-based gel beads were determined. In the suspension polymerization system, the organic phase including monomer, cross-linker and diluent solution was dispersed in an aqueous medium by using poly(vinylpyrrolidone) as the stabilizer. The diluent solution was prepared by mixing cyclohexanol and octanol at different volume ratios. The suspension polymerization experiments were designed in two separate parts. In the first part, ethylene glycol dimethacrylate was selected as the cross-linker and swellable PEG-MA-based gel beads were obtained by changing the cross-linker concentration, the monomer/diluent ratio and the stirring rate. In the second part, a more hydrophobic structure, divinylbenzene (DVB) was tried as a cross-linker. In this part, PEG-MA-DVB copolymer beads were obtained by changing the DVB/PEG-MA feed ratio. Then, the hydrophicility of the resulting gel beads could be controlled by changing the feed ratio of hydrophilic macromonomer to hydrophobic cross-linker. This property was also used to control the extent of nonspecific protein adsorption onto the surface of the gel beads. The non specific albumin adsorption onto the gel beads decreased with increasing PEG-MA content. No significant nonspecific adsorption at the isoelectric point of albumin was detected onto the gel beads produced with the higher PEG-MA/DVB feed ratios. For specific albumin adsorption, a triazinyl dye (i.e., cibacron blue, CB F3G-A) was covalently attached onto the surface of the copolymer beads via terminal hydroxyl groups of PEG-MA. The results of albumin adsorption experiments with the CB F3G-A carrying beads indicated that an appreciable specific albumin adsorption capacity could be obtained with the gel beads produced with a PEG-MA/DVB feed ratio of 1.5/4.0. Received: 16 August 1999/Revised: 27 December 1999     

表面图案化磁性复合微球的原位制备与表征

采用反相悬浮聚合法合成了丙烯酸(AA)含量不同的N-异丙基丙烯酰胺-丙烯酸共聚物P(NIPAM-co-AA)微凝胶, 并以其作为微反应器, 通过原位外源沉积法制备了一系列微米级、表面具有图案化结构的SiO₂-Fe₃O₄-P(NIPAM-co-AA)磁性复合微球. 实验结果表明, 复合微球的表面结构与微凝胶的组成、Fe₃O₄和SiO₂的沉积量有关. 在微球表面进行修饰, 可得到表面带有氨基等官能基团的磁性复合材料. 将这种功能化磁性微球用于识别生物大分子并进一步用于生物医学领域具有重要的意义.     

Poly(vinylphosphonate)s functionalized polymer microspheres via rare earth metal‐mediated group transfer polymerization

We demonstrate a facile, yet efficient method for the functionalization of crosslinked polystyrene (PS) microspheres with biocompatible poly(vinylphosphonate)s via the combination of a UV grafting polymerization and a surface‐initiated group transfer polymerization. Self‐initiated photografting and photopolymerization of ethylene glycol dimethacrylate results in direct photografting of poly(ethylene glycol dimethacrylate) on the PS microspheres with dangling methacrylate functionalities, which are used to immobilize ytterbocene complexes to form the surface‐bound rare‐earth metal catalyst system. The surface‐initiated GTP of dialkyl vinylphosphonates from the initiator system leads to the functionalization of PS microspheres with poly(vinylphosphonate) brushes. Polymerization kinetic investigation indicates that surface‐initiated GTP leads to a constant and remarkably rapid weight gain of the microsphere (a microsphere weight increase of 600% within 3 min), owing to the highly living and efficient character of GTP. The surface‐initiated GTP occurring inside the microsphere causes an accumulation of the tension between the polymer chains in the microsphere, which eventually induces fracture of the microsphere for longer polymerization time. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2919–2925     

Daidzein-imprinted membranes using co-functional monomers

Daidzein-imprinted poly(methacrylamide-co-acrylic acid) composite membranes with different ratios of methacrylamide (MAM) versus acrylic acid (AA) were prepared via UV initiated photo-copolymerization on the commercial filter paper with ethylene glycol dimethacrylate (EGDMA) as cross-linker and mixed cellulose ester as agglutinant. Infra-red (IR) spectroscopy and scanning electron microscope (SEM) were used to visualize the surface of the membranes. Binding and recognising properties of the imprinted composite membranes to daidzein and its analogues genistein were evaluated by static adsorption experiment. It was found that the daidzein-imprinted membranes showed high selectivity to daidzein, with the highest selectivity when the composite membrane with the ratio of MAM vs AA as 4:1. The results suggested that the molecularly imprinted composite membranes were potentially useful for daidzein enrichment.     

Synthesis and characterization of spherical and hemispherical polyepoxide micrometer‐sized particles of narrow size distribution by a single‐step swelling of uniform polystyrene template microspheres with glycidyl methacrylate

Polystyrene template microspheres of narrow size distribution were prepared by dispersion polymerization of styrene in a mixture of ethanol and 2‐methoxy ethanol. Spherical and hemispherical polystyrene/poly(glycidyl methacrylate) microspheres of narrow size distribution were prepared by a single‐step swelling of the polystyrene template microspheres with the swelling solvent monomer glycidyl methacylate, followed by polymerization of the monomer within the swollen template microspheres at 73 °C. Uniform polystyrene/poly(glycidyl methacylate‐ethylene glycol dimethacrylate) polyepoxide composite microspheres were synthesized similarly, substituting glycidyl methacylate for glycidyl methacylate and ethylene glycol dimethacrylate. Uniform crosslinked poly(glycidyl methacylate‐ethylene glycol dimethacrylate) polyepoxide microspheres have been prepared by dissolution of the PS template polymer of the former composite microspheres. Particles with different properties, for example size, size distribution, shape, surface morphology, surface area, and so forth, were prepared by changing various parameters belonging to the swelling and/or polymerization steps, for example, volume of the swelling monomer/s and/or the swelling solvent dibutyl phthalate. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4612–4622, 2007     

Synthesis and modification of supports with an alkylamine and their use in albumin adsorption

The morphological effect of polymeric networks (R) modified with terminal amino groups was studied on the adsorption of bovine serum albumin (BSA). Networks of ethylene glycol dimethacrylate and 2‐hydroxyethyl methacrylate [poly (EGDMA‐co‐HEMA)] were synthesized by suspension polymerization, using different EGDMA contents and agitation speeds. These matrices were characterized by FTIR, mercury intrusion porosimetry, SEM, and swelling degree. The increase of the EGDMA concentration led to the formation of networks with the highest crosslinking degree and porosity. An earlier phase separation yielded a higher aggregation of rigid microspheres, also forming stable pore systems. The increase in coalescence frequency, together with the impeller speed, and the decrease of the stabilizer molecules led to an increment in drop size. Large fused aggregates of microspheres were formed with additional loss of small pores as the stirring was increased, attaining also a higher pore volume (V_p) and a slight decrease of the surface area. Once characterized, networks were activated with butanediolglycidyl ether (BDGE), and then reacted with hexamethylenediamine (HMDA) through coupling reaction. Only the R‐BDGE‐HMDA networks synthesized with the highest EGDMA content and agitation speed showed BSA adsorption. Their base matrices exhibited a V_p higher than 1.4 mL/g, which allows easier protein diffusion into the support. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2557–2566, 2008     

One Pot Synthesis of Surface PEGylated Core–Shell Microparticles by Suspension Polymerization with Surface Enrichment of Biotin/Avidin Conjugation

Core–shell microparticles that consist of poly(vinyl neodecanoate) (VND) crosslinked with poly(ethylene glycol dimethacrylate) (EGDMA) as the core and poly(ethylene glycol methacrylate) (PEGMA) ( = 360 or = 526 g · mol^?1) as the shell have been synthesized using suspension polymerization by a conventional free radical polymerization process. Interfacial tension and stability tests show that PEGMA acts as an amphiphilic macromonomer and is located on the oil/water interface of the suspension system, thus forming an outer layer during the polymerization. Kinetic studies of the monomers' conversion of VND, EGDMA, and PEGMA have been carried out using ¹H NMR spectroscopy. EGDMA and PEGMA were found to have faster reaction rates compared to VND. Moreover, scanning electron microscopy showed that the polymerization of these particles starts from the shell and finishes towards the core. Consequently, the resulting microsphere is found to have a multi‐layer structure. Biotin was covalently bound to the surface by the PEGMA hydroxy groups. Conjugation of biotin with streptavidin PE (phycoerythrin) was subsequently carried out. Confocal microscopy was used to confirm the presence of fluorescing streptavidin. The amount of avidin conjugated to the microspheres was calculated by the release of a 2‐(4‐hydroxyphenylazo)benzoic acid/avidin complex using UV/vis spectroscopy. One avidin molecule was found to occupy 7 nm² on the surface of the microspheres.

     

Influence of the Nature of Crosslinking Agent on the Oxidation Behavior of Crosslinked Polystyrene‐Supported Polyoxyethylene Bound Permanganate

Abstract

Polystyrene‐supported polyoxyethylene (PSPOE) bound permanganate with varying crosslinking agents have been prepared and used as a new class of recyclable oxidizing agents for low molecular weight alcohols and aldehydes. The effect of the nature of crosslinking agents on the oxidation reactions was studied in detail. The crosslinking agents used were ethyleneglycol dimethacrylate (EGDMA), 1,4‐butanediol dimethacrylate (BDDMA), and 1,6‐hexanediol diacrylate (HDODA). Polymer supports were synthesized by free radical suspension polymerization. Chloromethylation was done using the Friedel‐Crafts reaction. A cyclic polyether type compound was developed by the reaction of functionlized resin with polyethylene glycol (PEG₆₀₀) and sodium. Polystyrene‐supported polyoxyethylene was equilibrated with potassium permanganate in benzene to give the oxidizing agent. The results reveal that the reactivity of HDODA‐crosslinked system shows higher reactivity than the BDDMA, and EGDMA‐crosslinked systems. This is due to higher flexibility of the HDODA‐crosslinked system compared to the BDDMA, and EGDMA‐crosslinked systems. The effect of solvent, temperature, and molar concentration of the reagent on oxidation were carried out using benzoin to benzil as the model reaction. For a less flexibile EGDMA‐crosslinked resin, tetrahydrofuran (THF) is the best solvent, for BDDMA‐crosslinked system dioxane and for the highly flexible HDODA‐crosslinked system CHCl₃ is found to be best. In all cases, the reactivity of the reagent increased with an increase in temperature and molar excess of the reagent.     

Efficient synthesis of monodisperse,highly crosslinked,and “living” functional polymer microspheres by the ambient temperature iniferter‐induced “living” radical precipitation polymerization

The facile and efficient one‐pot synthesis of monodisperse, highly crosslinked, and “living” functional copolymer microspheres by the ambient temperature iniferter‐induced “living” radical precipitation polymerization (ILRPP) is described for the first time. The simple introduction of iniferter‐induced “living” radical polymerization (ILRP) mechanism into precipitation polymerization system, together with the use of ethanol solvent, allows the direct generation of such uniform functional copolymer microspheres. The polymerization parameters (including monomer loading, iniferter concentration, molar ratio of crosslinker to monovinyl comonomer, and polymerization time and scale) showed much influence on the morphologies of the resulting copolymer microspheres, thus permitting the convenient tailoring of the particle sizes by easily tuning the reaction conditions. In particular, monodisperse poly(4‐vinylpyridine‐co‐ethylene glycol dimethacrylate) microspheres were prepared by the ambient temperature ILRPP even at a high monomer loading of 18 vol %. The general applicability of the ambient temperature ILRPP was confirmed by the preparation of uniform copolymer microspheres with incorporated glycidyl methacrylate. Moreover, the “livingness” of the resulting polymer microspheres was verified by their direct grafting of hydrophilic polymer brushes via surface‐initiated ILRP. Furthermore, a “grafting from” particle growth mechanism was proposed for ILRPP, which is considerably different from the “grafting to” particle growth mechanism in the traditional precipitation polymerization. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

多层核-壳结构P(AM-co-MAA)/W/UF复合微球制备研究

以反相悬浮聚合技术合成的丙烯酰胺(acrylamide,AM)和甲基丙烯酸(methacrylic acid,MAA)共聚高分子微凝胶P(AM-co-MAA)为模板,通过离心沉积法将微米级钨粉沉积于高分子微凝胶表面,得到具有核-壳结构的P(AM-co-MAA)/W复合微球材料;再以P(AM-co-MAA)/W复合微球为模板,通过控制甲醛和尿素的缩聚反应在模板与油/水相界面进行,制备得到了具有多层核-壳结构的高分子/钨/脲醛树脂[P(AM-co-MAA)/W/Urea-formaldehyde resin]复合微球材料.利用扫描电子显微镜(SEM)、红外(FT-IR)、X射线衍射(XRD)和热分析(TGA)等手段对复合微球进行了表征.实验结果表明,外壳层脲醛树脂的包覆量、复合微球的表面形貌可通过改变甲醛和尿素溶液的浓度、甲醛和尿素的物质的量之比等因素进行控制.复合微球的导电性测试结果表明,P(AM-co-MAA)/W复合微球表面壳层脲醛树脂包覆前后,其电导率由1.9×10-3降低为0.9×10-8S·m-1.该研究获得的三层核-壳复合微球材料其外层脲醛树脂的包覆较为完整、致密,其导电性接近于绝缘材料,为含钨复合微球作为电子元件的抗辐射涂层材料打下了基础.     

Thermosensitive and control release behavior of poly (N‐isopropylacrylamide‐co‐acrylic acid) latex particles

In this work, poly(N‐isopropylacrylamide‐co‐acrylic acid) (poly(NIPAAm‐AA)) copolymer latex particles (microgels) were synthesized by the method of soapless emulsion polymerization. Poly(NIPAAm‐AA) copolymer microgels have the property of being thermosensitive. The concentration of acrylic acid (AA) and crosslinking agent N,N′‐methylenebisacrylamide were important factors to influence the lower critical solution temperature (LCST) of poly(NIPAAm‐AA) microgels. The effects of AA and crosslinking agent on the swelling behavior of poly(NIPAAm‐AA) microgels were also studied. The poly(NIPAAm‐AA) copolymer microgels were then used as a thermosensitive drug carrier to load caffeine. The effects of concentration of AA and crosslinking agent on the control release of caffeine were investigated. How the AA content and crosslinking agent influenced the morphology and LCST of the microgels was discussed in detail. The relationship of morphology, swelling, and control release behavior of these thermosensitive microgels was established. A new scheme was proposed to interpret the control release of the microgels with different morphological structures. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5734–5741, 2008     

沉淀聚合法制备右旋邻氯扁桃酸分子印迹聚合物微球

以右旋邻氯扁桃酸为模板,丙烯酰胺、乙二醇二甲基丙烯酸酯分别为功能单体和交联剂,采用沉淀聚合法制备了分子印迹聚合物微球,讨论了反应介质用量、聚合温度、引发剂的种类和用量对印迹微球的影响。实验表明：分子印迹微球与传统本体聚合法制备的聚合物相比具有更高的特异识别能力,通过Scatchard分析研究了聚合物的选择结合性能,结果表明分子印迹聚合物微球在识别右旋邻氯扁桃酸分子的过程中存枉两类结合位点,而空白聚合物微球只存在一类结合位点。     

1,1-二苯基乙烯存在下无皂乳液聚合制备磁性复合微球

报道了一种制备磁性复合微球的方法——DPE法.在自由基控制剂1,1-二苯基乙烯(DPE)存在条件下,甲基丙烯酸甲酯(MMA)与丙烯酸(AA)发生无皂乳液聚合,制备能与Fe3O4粒子相螯合的活性短链共聚物,加入Fe3O4粒子把短链共聚物引到其表面,引发其它单体继续在Fe3O4粒子表面聚合,制备磁性复合微球.研究了AA、DPE、引发剂及Fe3O4粒子加入量等对制备磁性复合微球的影响.并在此基础上,对优化后工艺制备的磁性复合微球进行了TEM、TGA及磁响应性表征.结果表明,利用该新的方法制备出了磁含量为20%、比饱和磁化强度为32.2emu/g、平均粒径为265nm且表面不含任何杂质的磁性复合微球.     

Photoinitiated precipitation polymerization in liquid CO2: Fast formation of crosslinked poly(acrylic acid‐co‐methoxy polyethylene glycol acrylate) microspheres

Photoinitiated precipitation polymerization of acrylic acid (AA) and methoxy polyethylene glycol acrylate (MPEGA) was carried out in liquid carbon dioxide using ethanol as cosolvent and trimethylol propane triacrylate (TMPTA) as crosslinker. Monodisperse crosslinked microspheres were obtained with size polydispersity index as low as 1.027. The particle yield rose sharply after irradiation and reached to 52% at 5 min, then gently increased to 65% at 60 min, suggesting that most of microspheres were produced in the first 5 min of irradiation. The particle number increased incessantly till very late stage of reaction, which could be attributed to the direct generation of stable nuclei from the fast crosslinking polymerization instead of oligomer aggregation. The effect of ethanol content, feeding ratio of monomers and crosslinker concentration on the morphologies, size, and dispersity of microspheres has been investigated. X‐ray photoelectron spectroscopy showed that the microspheres obtained by this procedure were covered with abundant carbon double bonds. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011