Radiation polymerization of acrolein at low temperatures

Radiation polymerization of acrolein in the presence of the additives such as 2-hydroxyethyl methacrylate, acrylic acid, and water at low temperatures (0–78°C) was studied. The polyacrolein resulting from the polymerization gave a small particlelike microsphere (0.5–5 μm in diameter). The rate of the polymerization reaction of acrolein appeared to be accelerated by the addition of a small amount of 2-hydroxyethyl methacrylate or acrylic acid. The particle size of the polyacrolein particle varied with the condition of the polymerization and increased or decreased with an increase in the addition concentration of 2-hydroxyethyl methacrylate or acrylic acid.     

Preparation of copolymer microspheres of diethylene glycol dimethacrylate

Preparation of copolymer microspheres of diethylene glycol dimethacrylate (2G) with several comonomers by radiation-induced radical polymerization is described. Ethyl methacrylate (EMA), acrylamide, maleic anhydride, and styrene gave microspheres successively. The copolymerization resulted in gelation more easily than the 2G homopolymerization. The allowed ratio of copolymerization is up to about 0.4 as the mole fraction of comonomer for the solution containing 10 vol % 2G monomer. Copolymerization affected the size of microspheres by keeping its narrow distribution. The size of microspheres was increased by the copolymerization with EMA and styrene and, was decreased with acrylamide. The formation of microsphere strongly depends on the crosslinking ability of monomers. The crosslinking ability and reactivity in the copolymerization cause the change of the size of the microspheres. © 1992 John Wiley & Sons, Inc.     

聚二乙烯基苯微球的合成及其表征研究

采用分散聚合方法制备了聚二乙烯基苯微球 ,研究了引发剂、稳定剂、单体 溶剂比例和溶剂种类对微球粒径及其分布的影响 ,在适当的条件下可以得到平均粒径较大、粒径分布较窄的微球 .用红外光谱法研究了聚合物微球内稳定剂、悬挂双键以及对位和间位二乙烯基苯含量随聚合过程的进行发生的变化 .测得的微球TG曲线表明 ,聚合物微球具有良好的热稳定性 .     

聚甲基丙烯酸甲酯/聚甲基丙烯酸-2-羟乙酯复合微球的合成及药物吸放性能

采用在甲基丙烯酸甲酯（MMA）悬浮聚合过程中滴加甲基丙烯酸-2-羟乙酯（HEMA）乳液聚合组分的悬浮-乳液耦合聚合方法,制备了大粒径聚甲基丙烯酸甲酯／聚甲基丙烯酸-2-羟乙酯（PMMA／PHEMA）复合微球。PMMA／PHEMA复合微球表面以HEMA乳液聚合物为主,且具有微孔结构。PMMA／PHEMA复合微球在水和苄醇中的平衡溶胀率大于PMMA微球。PMMA／PHEMA复合微球48h异丁苯丙酸负载百分比为35．6％,PMMA为27．6％。在磷酸盐缓冲液中释放时间达到360h,释放量占负载总量的82％;而PMMA微球的释放时间为216h,释放量仅占负载总量的60％。     

Immunoactivity of polymer microspheres with their hydrophilic/hydrophobic heterogeneous surface sensitized with an antibody

Styrene/2-hydroxyethyl methacrylate polymer microspheres consisting of various polymer compositions were produced by emulsifier-free seeded emulsion polymerization technique. Using these microspheres, which should have hydrophilic/hydrophobic heterogeneous surface, the effects of surface hydrophilicity on the main, fundamental requirements for an immunomicrosphere — high colloidal stability, sensitive immunologic agglutinability and insensitive non-specific agglutinability — were studied in detail. There was a region of the surface hydrophilicity that satisfied the three requirements simultaneously.Part CII of the series Studies on Suspension and Emulsion.     

Covalent immobilization of albumin on micron‐sized magnetic poly(methyl methacrylate‐divinylbenzene‐glycidyl methacrylate) microspheres prepared by modified suspension polymerization

Micron‐sized magnetic poly(methyl methacrylate‐divinylbenzene‐glycidyl methacrylate) microspheres were prepared by a modified suspension polymerization in the presence of oleic acid‐coated magnetite nanoparticles. The magnetic microspheres were functionalized by reacting the epoxy groups with ammonia solution to provide amino groups. After activated with glutaraldehyde (GA), bovine serum albumin was covalently immobilized on these magnetic microspheres. The influence of initial protein concentration, pH and ionic strength of the protein solution on covalent immobilization was studied. Scanning electron micrographs showed that the magnetic microspheres had an average size of 6.4 µm and relative narrow size distribution. Magnetic measurement revealed the magnetic microspheres were superparamagetic with saturation magnetization of 7.32 emu/g. The successful amination of the magnetic microspheres was confirmed by Fourier transform infrared spectroscopy (FT‐IR). Copyright © 2005 John Wiley & Sons, Ltd.     

Role of dispersion stabilizer with hydroxy groups in preparation of monodisperse polylactide microspheres

Monodisperse poly(D ,L ‐lactide) (PDLLA) microspheres were prepared by dispersion polymerization of D ,L ‐lactide in xylene/heptane (1/2, v/v) with poly[(dodecyl methacrylate)‐co‐(2‐hydroxyethyl methacrylate)] (P(DMA‐co‐HEMA)) as a dispersion stabilizer. P(DMA‐co‐HEMA) contains hydroxy groups, which act as an initiation group for pseudoanionic dispersion polymerization. The best coefficient of variation (CV) values concerning particle diameter distribution and the particle diameter of obtained PDLLA microspheres were 3.7% and 5.3 μm, respectively. The particle diameter decreased with increasing concentration of P(DMA‐co‐HEMA) and HEMA maintained low CV (<10%) values. As a result, monodisperse PDLLA microspheres ranging from 1.3 to 5.3 μm were obtained. In addition, it was found that monodisperse PDLLA microspheres were obtained by sufficient capture of growing polymers and monomers in the particle growth stage. Therefore, the HEMA concentration in P(DMA‐co‐HEMA) strongly affecting the capturing capability is the most important factor. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5230–5240, 2009     

Magnetic poly(2‐hydroxyethyl methacrylate‐co‐ethylene dimethacrylate) microspheres by dispersion polymerization

Crosslinked poly(2‐hydroxyethyl methacrylate)‐based magnetic microspheres were prepared in a simple one‐step procedure by dispersion polymerization in the presence of several kinds of iron oxides. Cellulose acetate butyrate and dibenzoyl peroxide were used as steric stabilizer and polymerization initiator, respectively, and ethylene dimethacrylate was a crosslinking agent. The resulting product was characterized in terms of particle size, particle size distribution, iron(III) content, and magnetic properties. In the presence of needle‐like maghemite in the polymerization mixture and under suitable conditions, magnetic microspheres with relatively narrow size distribution were formed. An increase in the particle size and, at the same time, a decrease in molecular weight of uncrosslinked polymers resulted, as the continuous phase became richer in 2‐methylpropan‐1‐ol. Coercive force of needle‐like maghemite‐containing particles was higher than that of cubic magnetite‐loaded microspheres. Coercive force increased with the decreasing iron content in the particles. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1161–1171, 2000     

HAP/P(MMA-St)复合微球的制备及其吸附性能

以微孔纳米羟基磷灰石（HAP）为无机载体,甲基丙烯酸甲酯（MMA）和苯乙烯（St）为聚合单体,采用悬浮聚合法制备了HAP/P(MMA-St)复合微球。研究了影响球体粒度及其分布的主要因素和微球的吸附性能。结果表明,表面活性剂用量（质量分数,下同）为1‰、MMA用量为2%,HAP用量为30%,转速为300r/min时复合微球的合格球收率最高为86.4%。当微球中HAP的含量为36.07%时,HAP/P(MMA-St)微球对牛血清蛋白的最大吸附量Qe=18.70 mg/g,比未加HAP时,增加了4.65 mg/g。     

Polymer particle formation in soapless emulsion polymerization

Polymer particle formation in soapless emulsion polymerization for monomers that are soluble in diluent is studied theoretically and experimentally. A kinetic model is proposed assuming that polymer particles are formed by homogeneous nucleation of both growing radicals and dead polymer molecules above the critical size in solution. Based on this model, the dependence of the number of polymer particles on the concentration of initiator and monomer in solution is discussed for the polymerization system of methyl methacrylate–potassium persulfate–water. Experimental results of the number of polymer particles in this system can reasonably be interpreted by this model.     

Further insight into the mechanism of poly(styrene‐co‐methyl methacrylate) microsphere formation

Polymeric microspheres have been used in a broad range of applications from chromatographic separation techniques to analysis of air flow over aerodynamic surfaces. The preparation of microspheres from many polymer families has consequently been extensively studied using a variety of synthetic approaches. Although there are a myriad of polymeric microsphere synthesis methods, free‐radical initiated emulsion polymerization is one of the most common techniques. In this work, poly(styrene‐co‐methyl methacrylate) microspheres were synthesized via surfactant‐free emulsion polymerization. The effects of co‐monomer composition and addition time on particle size distribution, particle formation, and particle morphology were investigated. Particles were characterized using dynamic light scattering and scanning electron microscopy to gain further insight into particle size and size distributions. Reaction kinetics were analyzed through consideration of characterization results. A particle formation mechanism for poly(styrene‐co‐methyl methacrylate) microspheres was proposed based on characterization results and known reaction kinetics. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2249–2259     

Synthesis of bio-based poly(methacrylates) using SG1-containing amphiphilic macroinitiators by nitroxide mediated miniemulsion polymerization

SG1-based amphiphilic macroinitiators were synthesized from oligoethylene glycol methyl ether methacrylate and 10 mol% acrylonitrile or styrene (as the controlling comonomer) to conduct the nitroxide mediated polymerization of bio-based methacrylic monomers (isobornyl methacrylate (IBOMA) and C13 alkyl methacrylate (C13MA)) in miniemulsion. The effect of the addition of surfactant (DOWFAX 8390), co-stabilizer (n-hexadecane) and different reaction temperatures (80, 90 and 100°C) on polymerization kinetics was studied. We found that the NMP of IBOMA/C13MA using amphiphilic macroalkoxyamines were most effective during miniemulsion polymerization (linear trend of M_n versus conversion and high latex stability) in presence of 2 wt% surfactant and 0.8 wt% co-stabilizer (relative to monomer) at 90°C. The effect of surfactant, co-stabilizer and temperature on particle size during the polymerization was studied and suggested a decrease in initial particle size with the addition of surfactant and co-stabilizer. Finally, the thermal properties of IBOMA/C13MA polymers, prepared by amphiphilic macroinitiators, were examined thoroughly, indicating a T_g in the range of −44°C < T_g < 109°C.     

Preparation of monodisperse PMMA microspheres using 2-vinyl-4,4′-dimethylazlactone as a particle Stabilizer

Polymeric microspheres of methyl methacrylate (PMMA) have been prepared via emulsion polymerization using potassium persulfate as initiator. The polymeric spheres were also prepared with varied concentration of an additional component, 2-vinyl-4,4′-dimethylazlactone (VDMA), which greatly affected the properties of the spheres. NMR analysis indicates the presence of VDMA in the polymer particles, and FT-IR analysis shows hydrolysis of VDMA in the polymer which produced N-acryloylmethylalanine, (NAMA). The VDMA hydrolysis thus led to carboxyl functionality which served to stabilize the microspheres during the emulsion polymerization showing a significant effect on particle size, distribution, and morphology, but little effect on molecular weight or thermal properties of the polymer. Also the effect of varying the concentration of initiator (potassium persulfate, KPS) was investigated, and had little effect on particle size or distribution or molecular weight of the polymer particles.     

控制自由基聚合制备Fe_3O_4/SiO_2/P(AA-MMA-St)磁性复合微球

用原硅酸乙酯对Fe3O4纳米粒子进行表面改性得到Fe3O4/SiO2磁流体.在Fe3O4/SiO2磁流体存在下,以1,1-二苯基乙烯(DPE)为自由基聚合控制剂,利用乳液聚合法制备了Fe3O4/SiO2/P(AA-MMA-St)核-壳磁性复合微球.用红外光谱(FTIR)、振动样品磁强计(VSM)、透射电镜(TEM)、X光电子能谱(XPS)、热重分析(TGA)、示差扫描量热仪(DSC)对所制备的磁流体、磁性高分子复合微球的结构、形态、性能进行了表征.研究发现,原硅酸乙酯水解后能在Fe3O4表面形成硅膜保护层从而避免Fe3O4的酸蚀,使Fe3O4/SiO2/P(AA-MMA-St)复合微球的比饱和磁化强度比同样条件下制备的Fe3O4/P(AA-MMA-St)微球提高了28%;DPE能有效控制自由基在Fe3O4/SiO2磁流体表面均匀地引发单体聚合,得到平均粒径为422 nm,无机粒子含量为40%,比饱和磁化强度为34.850 emu/g,表面羧基含量为0.176 mmol/g的磁性复合微球.     

Reactive poly(glycidyl methacrylate) microspheres prepared by dispersion polymerization

Poly(glycidyl methacrylate) [poly(GMA)] microspheres of narrow size distribution were prepared in a simple one‐step procedure by dispersion radical polymerization. Depending on the solvent used, poly(GMA) particle size could be controlled in the range of 0.5–4 μm by changing the solubility parameter of the reaction mixture. In N,N′‐dimethylformamide (DMF)/methanol mixture, the particle size increased and the size distribution broadened with decreasing initial solubility parameter. While in the DMF/methanol solvent system, hydroxypropyl cellulose (HPC) or cellulose acetate butyrate (CAB) were taken as steric stabilizers of the dispersion polymerization, poly(vinylpyrrolidone) (PVP) was used in alcoholic media. Contrary to the DMF/methanol system, narrow particle size distributions were obtained with PVP‐stabilized polymerizations in ethanolic, methanolic, propan‐1‐olic or butan‐1‐olic medium. Both the particle size and polydispersity were reduced with increasing stabilizer concentration. If lower molecular‐weight PVP was used, larger microspheres were obtained. Poly(GMA) samples prepared in a neat alcoholic medium virtually quantitatively retained oxirane group content after the polymerization. Reactivity of the poly(GMA) microspheres was confirmed by their hydrolysis and aminolysis. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3855–3863, 2000     

Synthesis and release profile analysis of thermo-sensitive albumin hydrogels

Novel thermo-responsive hydrophilic microspheres were prepared by free radical polymerization of methacrylate bovine serum albumin and N-isopropylacrylamide, as cross-linker and functional monomer, respectively. The incorporation of monomers in the network was confirmed by infrared spectroscopy, while the network density and shape of hydrogels strictly depend on concentration of monomers in the polymerization feed. The thermal analyses showed negative thermo-responsive behavior with pronounced water affinity of microspheres at temperature lower than lower critical solution temperature (LCST). The in vitro release studies of drug-loaded thermo-sensitive hydrogels were performed. Experimental data showed, for the copolymers with functional monomer/cross-linker ratio ≤ 1, a predominant drug release in the collapsed state, while the copolymers with functional monomer/cross-linker ratio > 1 showed prominent drug release in the swollen state. Below the hydrogel LCST, drug release through the swollen polymeric networks was observed, while a squeezing-out effect at temperature above the LCST was predominant.     

In situ synthesis of polystyrene/nano-CdSe core/shell microspheres in aqueous solution at room temperature

Polystyrene/nano-CdSe (PS/CdSe) core/shell microspheres were synthesized via in situ soap-free emulsion polymerization using various functional monomers such as 2-(dimethylamino)ethyl methacrylate, 1-vinylimidazole, 2-vinylpridine, and 4-vinylpridine. They were co-polymerized with styrene monomer and provided the location for coordinating with Cd²⁺ ions on the PS particle surfaces. Then, we used an alkaline selenium solution as a selenium source. Reaction of the alkaline selenium solution with the previous emulsion produced nanocrystalline CdSe onto the surface of PS particles at room temperature under atmospheric pressure. The different kinds of functional monomers and the amount of both Cd²⁺ ion and functional monomer were playing important roles to obtain stable and uniform morphologies of CdSe particles. Morphological observations were carried out by both scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Through the SEM and TEM microphotographs, we could confirm the formation of PS/nano-CdSe composite particles. Ultraviolet–visible absorption measurement indicated the quantum dot effect in the resulted PS/nano-CdSe core/shell microspheres.     

PREPARATION AND CHARACTERIZATION OF AFFINITY POLYMER BASIC MICROSPHERES BY SOAP-FREE EMULSION POLYMERIZATION

 Poly(styrene-co-glycidyl methacrylate) latex microspheres with uniform size and high-density epoxy groups on the surface were prepared by soap-free emulsion polymerization with batch wise operation mode in the presence of 2,2&#61602;-azobis(2-methylpropionamidine) dihydrochloride as an initiator. The kinetics of soap-free emulsion polymerization and the effects of polymerization factors were examined. In addition, the optimum polymerization conditions of poly(styrene-co-glycidyl methacrylate) latex microspheres for immobilization of biomolecules were obtained.     

Dispersion copolymerization of styrene and glycidyl methacrylate in polar solvents

Monodispersed copolymer microspheres consisting of styrene and glycidyl methacrylate have been prepared by dispersion polymerization. The effects of various polymerization parameters on the particle size and size distribution were systematically investigated. The initial solubility parameter of the system had a significant effect on the final particle size and size distribution. With decreasing initial solubility parameter, the particle size increased and the size distribution broadened. The particle size decreased with increasing stabilizer concentration, the amount of styrene in the monomer mixture, and decreasing initiator concentration. Received: 30 September 1998 Accepted in revised form: 10 December 1998     

Precipitation polymerization in acetonitrile and 1‐propanol mixture: synthesis of monodisperse poly(styrene‐co‐divinylbenzene) microspheres with clean and smooth surface

Precipitation polymerization of styrene (St)–divinylbenzene (DVB) has been carried out using acetonitrile/1‐propanol mixture as the reaction media and 2,2′‐azobisisobutyronitrile (AIBN) as initiator. Monodisperse micron‐sized poly(St‐co‐DVB) microspheres with clean and smooth surface were synthesized in the absence of any stabilizing agent such as surfactants or steric stabilizers. The effects of various polymerization parameters such as 1‐propanol fraction in the reaction media, initiator and total monomer concentration, DVB content, polymerization time and polymerization temperature on the morphology, particle size and size distribution were investigated. It was found that smoothly shaped stable particles were obtained when less than 70 vol% of 1‐propanol was used in the media. The particle size increased with the AIBN concentration, whereas the change of uniformity was less obvious. Monodisperse microspheres were obtained when the total monomers loading ranged from 0.5 to 3 vol%. The particle diameter ranged from 2.73 to 1.87 µm with an increasing DVB content and the uniformity was enhanced. In addition, the yield of microspheres increased with the increasing total monomer, initiator, and DVB concentration and polymerization time. Copyright © 2010 John Wiley & Sons, Ltd.