Dispersion polymerization of n‐butyl acrylate

The dispersion polymerization of n‐butyl acrylate (BA) was investigated using alcohol/water mixtures as the dispersion medium, 4,4′ ‐azobis‐(4‐cyanopentanoic acid) as the initiator, and polyvinylpyrrolidone (PVP) as the stabilizer. The effects of polymerization parameters, such as the alcohol/water ratio in the medium and the type and concentration of the polymeric stabilizer, on the resulting particle size and size distribution were studied. The final particle size and the stability of the dispersion system were found to be greatly influenced by the type of alcohol used in the mixture; that is, methanol or ethanol, even though the apparent solubility parameters are almost the same for the two types of mixtures. Poly(butyl acrylate) particles with controlled size and size distribution (monodisperse), and gel content were successfully prepared in a 90/10 methanol/water medium. It was found that the particle size decreased with increasing initiator concentration. This is the opposite of what was previously reported in the dispersion polymerizations of styrene and methyl methacrylate. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2692–2709, 2002     

Uniform Polystyrene Particles by Dispersion Polymerization in Different Dispersion Medium

Using PVP K-30 as steric stabilizer and AIBN as initiator, uniform polystyrene (PS) particles were prepared by dispersion polymerization of styrene in ethanol/water and isopropanol/ water media. The effects of initiator and stabilizer concentration, alcohol/water volume ratio on the average sizes and size range of PS particles were investigated. Unifrom PS particles in the size range of 0.7-1.7 μm were obtained. The results showed that higher stabilizer concentration led to PS particles with smaller average sizes, and higher initiator concentration caused greater average particle sizes. It was also found that the average sizes reduced and size ranges became narrow as the polarity (solubility parameter) of dispersion medium employed was increased.     

分散聚合法制备亚微米级单分散聚苯乙烯微球

以醇和水的混合液为分散介质,聚乙烯基吡咯烷酮（PVP）为分散剂、偶氮二异丁腈（AIBN）为引发剂,利用分散聚合法制备亚微米级的单分散聚苯乙烯（PS）微球。分别讨论分散剂的用量以及分散介质的溶解度参数对PS微球粒径的影响。结果表明,当分散介质溶解度参数和单体苯乙烯的溶解度参数越接近时,所制得的PS微球粒径越大,反之越小;随着分散剂PVP量的增加,微球的粒径减小,粒径分布变窄;所制得的聚苯乙烯微球表面光滑,呈均匀的球形。     

Uniform star‐polystyrene nanoparticles prepared by emulsion atom transfer radical polymerization

Pentaerythritol (PT) was converted into four‐arm initiator pentaerythritol tetrakis(2‐chloropropionyl) (PT‐Cl) via reaction with 2‐chloropropionyl chloride. Uniform (monodisperse) star‐polystyrene nanoparticles were prepared by emulsion atom transfer radical polymerization of styrene, using PT‐Cl/CuCl/bpy (bpy is 2,2′‐dipyridyl) as the initiating system. The structures of PT‐Cl and polymer were characterized by Fourier transform infrared spectroscopy and nuclear magnetic resonance. The morphology, size and size distribution of the star‐polystyrene nanoparticles were characterized by transmission electron microscopy, atomic force microscopy and photon correlation spectroscopy. It was found that the average diameters of star‐polystyrene nanoparticles were smaller than 100 nm (30–90 nm) and monodisperse; moreover, the particle size could be controlled by the monomer/initiator ratio and the surfactant concentration. The average hydrodynamic diameter (D_h) of the nanoparticles increased gradually on increasing the ratio of styrene to PT‐Cl and decreased on enhancing the surfactant concentration or increasing the catalyst concentration. Copyright © 2011 Society of Chemical Industry     

Ultrasound‐assisted emulsion polymerization of poly(methyl methacrylate‐co‐butyl acrylate): Effect of initiator content and temperature

In this study, we propose an efficient method for preparation of large scale, monodisperse poly(methyl methacrylate‐co‐butyl acrylate) latexes by application of the low power ultrasound irradiation. The effect of polymerization temperature and initiator concentration on the polymerization nature, particle size, and particle size distribution were investigated. Results indicated that the ultrasound pulses in the first minutes of polymerization increase instant free radical to monomer ratio as well mixing efficiency which led to higher monomer conversion, improved polymerization rate (especially at first 15 min of the reaction), and remarkable decrease in molecular weight distribution. Transmittance electron microscopy (TEM) and dynamic light scattering (DLS) revealed that the particle size and particle size distribution were significantly affected, particle size decreased, and more uniform particles were obtained. Dynamic mechanical thermal analysis also showed that the initiator concentration affected glass transition temperature (T_g) of the final copolymers and in the case of ultrasound‐assisted emulsion polymerization T_g was in a very good agreement with theoretical predictions for copolymerization. POLYM. ENG. SCI., 56:214–221, 2016. © 2015 Society of Plastics Engineers     

微米级单分散聚苯乙烯微球的制备

以苯乙烯(St)为单体、偶氮二异丁腈(AIBN)为引发剂、聚乙烯吡咯烷酮(PVP)为分散稳定剂,在乙醇-水反应介质中,采用分散聚合法制备了微米级单分散聚苯乙烯(PS)微球。分别用电镜扫描和激光粒度仪表征了PS微球表面形貌、粒径及粒度分布,探讨了影响PS微球粒径及粒度分布的诸多因素。结果表明,AIBN用量(以单体质量计,下同)大于5.0%或PVP用量(以单体质量计,下同)小于2%时,PS粒子间有聚并现象;当St浓度为10%、AIBN用量为2.5%、PVP用量为5.5%、醇水质量比为90∶10、聚合温度为70℃时,制备的PS微球粒径为1.612μm、粒度分散系数为0.357,微球单分散性及球形度最佳。     

聚苯乙烯单分散交联纳米微球的制备和表征

以苯乙烯为单体,二乙烯基苯为交联剂、过硫酸钾为引发剂,甲基丙烯酸为稳定剂,通过无皂乳液聚合反应,合成0粒径均匀分布的聚苯乙烯高分子微球.聚苯乙烯纳米微球由于其特定的尺寸和形貌,具有其他材料所不具备的特殊功能.采用无皂乳液聚合法制备了具有单分散性的亚微米级聚苯乙烯球,考察了聚合体系单体对微球粒径的影响.通过研究聚合物微球的自组装工艺,选出最佳条件并制备具有三维有序结构的光子材料.结果表明不同半径的聚苯乙烯微球在白光照射下会显现出不同颜色.可作为填料放到涂料中.     

连续法制备单分散聚苯乙烯微球及粒径影响因素的研究

以苯乙烯为单体,偶氮二异丁腈(AIBN)为引发剂,聚乙烯吡咯烷酮(PVP)为分散剂,采用连续分段添加引发剂的方法制备微米级的聚苯乙烯微球。研究了引发剂的添加方式,各组分用量变化对聚苯乙烯微球粒径和粒径分布的影响。结果表明:在反应过程中不断地补加引发剂可以保持活性自由基的生成速率,对聚苯乙烯微球的粒径和粒径分布有着重要的影响。在此基础上,通过改变各组分的用量可以制备出表面光洁,粒径在1.3μm左右的聚苯乙烯微球,且单分散性良好,单分散系数在1.02左右。     

无皂乳液聚合法合成单分散交联PS纳米微球

介绍单分散交联PS纳米微球的合成。用电子透射显微镜研究了丙酮、引发剂和温度对交联PS纳米微球粒径和多分散性的影响 ,结果表明 ,在苯乙烯的无皂乳液聚合反应体系中加入丙酮可使交联PS纳米微球的粒径显著降低 ,并保持粒径的单分散 ,得到粒径小于 10 0nm ,分散系数 6.0 %左右的交联PS微球 ;增加引发剂KPS用量和提高反应温度可进一步使粒径变小 ,单分散性提高 ,符合Ottewill关系式     

2‐Hydroxypropylmethacrylate based mono‐ and bifunctional gel beads prepared by suspension polymerization

Spherical and swellable gel beads in the size range 35–200 µm were prepared by suspension polymerization of 2‐hydroxypropylmethacrylate (HPMA). In the proposed method, a mixture of cyclohexanol and octanol was used as a diluent phase dispersed in an aqueous medium including poly(vinyl pyrrolidone) (PVP) as the stabilizer. The polymerization was initiated within the organic phase including the monomer and the crosslinker (ethylene glycol dimethacrylate) by an oil soluble initiator benzoyl peroxide. Spherical and swellable gel beads carrying both hydroxyl and carboxyl functional groups were also prepared by suspension copolymerization of HPMA and a water soluble comonomer (methacrylic acid). For this purpose, the suspension polymerization method proposed for HPMA was modified by using poly(vinyl alcohol) as a stabilizer instead of PVP. The effect of initiator concentration, polymerization temperature, monomer/diluent ratio, crosslinker concentration, stirring rate on yield, average size, size distribution, and carboxyl content of the HPMA based gel beads, were investigated. The swelling characteristics of the gel beads were defined. © 2000 Society of Chemical Industry     

Synthesis and characterization of epoxy‐acrylate composite latex

A waterborne epoxy‐acrylate composite latex was synthesized. The effects of the concentration of the initiator, surfactant, and epoxy resin on the particle size, molecular weight, and grafting ratios of the composite latex were investigated. The increase of the concentration of the initiator and epoxy resin led to the decrease of the weight‐average molecular weight. The graft ratios increased with an increase in the initiator level and a decrease in the epoxy resin concentration whereas the variation of the concentration of the surfactant did not have much influence on the graft ratios. The increase in the initiator level caused the aggrandizement of the particle size, and the increase of the concentration of the surfactant and epoxy resin caused a decrease in the latex particle size. Fourier transform IR spectroscopy with attenuated total reflectance indicated that the epoxy resin molecules were enriched in the mold‐facing surface in the film from the composite latex. The differential scanning calorimetry analysis, dynamic mechanical analysis, and Instron test showed that the polymer films cast by the composite latex had lower tensile strength and glass transition than those by the blend latex. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1736–1743, 2002     

二氧化硅空心球的制备及研究

在乙醇/水的混合溶液中,采用聚乙烯吡咯烷酮（PVP）为分散剂,偶氮二异丁腈（AIBN）为引发剂,通过分散聚合法制备出聚苯乙烯（PS）微球。然后以微球为模板,PS粒子作为核,SiO_2作为壳,在600℃时经过热分解得到SiO_2空心球。通过热分析仪、扫描电子显微镜对制得的空心球进行了表征和分析,并讨论其影响因素。     

Synthesis and characterization of poly(N‐vinyl‐2‐pyrrolidone) grafted sodium alginate hydrogel beads for the controlled release of indomethacin

Graft copolymers of sodium alginate (NaAlg) with N‐vinyl‐2‐pyrrolidone were prepared using azobisisobutyronitrile as initiator. The graft copolymers (NaAlg‐g‐PVP) were characterized with Fourier transform infrared spectroscopy, elemental analysis, and differential scanning calorimetry. Polymeric hydrogel beads of NaAlg and NaAlg‐g‐PVP were prepared by crosslinking method using glutaraldehyde (GA) as a crosslinker in the hydrochloric acid catalyst (HCl) and these beads were used to deliver anti‐inflammatory drug, indomethacin (IM). Chemical stability of the IM after encapsulation into beads was confirmed by FTIR. Preparation conditions of the NaAlg‐g‐PVP beads were optimized by considering the percentage entrapment efficiency, particle size, swelling capacity and their release data. In vitro release studies were performed in simulated gastric fluid (pH 1.2) for the initial 2 h, followed by simulated intestinal fluid (pH 7.4) for 4 h. Effects of GA concentration, exposure time to GA, drug/polymer (d/p) ratio, and concentration of HCl on the release of IM were discussed. It was observed that IM release from the beads decreased with increasing GA concentration and exposure time. IM release also decreases with increasing d/p ratio and HCl concentration. The highest IM release was obtained to be 77% for beads crosslinked with 0.027M GA. Swelling experiments were also performed to compute molecular mass between crosslinks of the beads. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Hydrogel characteristics of a novel temperature‐sensitive polymer,poly(N‐2‐methoxyisopropylacrylamide)

In this study, a novel temperature‐sensitive polymer, poly(N‐2‐methoxyisopropylacrylamide), PNMIPA, in the crosslinked hydrogel form was obtained. The monomer, N‐2‐methoxyisopropylacrylamide (NMIPA) was synthesized by the nucleophilic substitution reactions of acryloyl chloride with 2‐methoxyisopropylamine. Hydrogel matrix of PNMIPA was obtained by the bulk polymerization method. The bulk polymerization experiments were performed at +4°C, by using N,N‐methylenebisacrylamide (MBA) as crosslinker, polyethyleneglycol (PEG) 4000 as diluent, and potassium persulfate (KPS) and tetramethylethylenediamine (TEMED) as the initiator and accelerator, respectively. The same polymerization procedures were applied by changing monomer, initiator, crosslinker and diluent concentrations in order to obtain crosslinked gel structures having different temperature–sensitivity properties. The equilibrium swelling ratio of PNIMPA gel matrices at constant temperature increased with increasing initiator concentration and decreasing monomer concentration. The use of PEG 4000 as diluent in the gel synthesis resulted in about two times increase in equilibrium swelling ratios in the low temperature region. A decrease in the equilibrium swelling ratios of gel matrices started at 30°C and the decrease became insignificant at 55°C. Temperature‐sensitivities were determined in two different media. Distilled water medium was used in order to observe the temperature‐sensitivity of the gel clearly and the phosphate buffer medium was used in order to represent the temperature‐sensitive swelling behavior of the gel when it is used in biological media. Step effect was applied on ambient temperature in two opposite directions in order to examine the dynamic swelling and shrinking behaviors of the gels. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of polystyrene/poly(methyl methacrylate) core‐shell composite particles by suspension‐emulsion combined polymerization

Suspension‐emulsion combined polymerization process, in which methyl methacrylate (MMA) emulsion polymerization constituents (EPC) were drop wise added to styrene (St) suspension polymerization system, was applied to prepare polystyrene/poly(methyl methacrylate) (PS/PMMA) composite particles. The influences of the feeding condition and the composition of EPC on the particle feature of the resulting composite polymer particles were investigated. It was found that PS/PMMA core‐shell composite particles with a narrow particle size distribution and a great size would be formed when the EPC was added at the viscous energy dominated particle formation stage of St suspension polymerization with a suitable feeding rate, whereas St‐MMA copolymer particles or PS/PMMA composite particles with imperfect core‐shell structure would be formed when the EPC was added at the earlier or later stage of St suspension polymerization, respectively. It was also showed that the EPC composition affected the composite particles formation process. The individual latex particles would exist in the final product when the concentrations of MMA monomer, sodium dodecyl sulfate emulsifier, and potassium persulfate initiator were great in the EPC. Considering the feature of St suspension polymerization and the morphology of PS/PMMA composite particles, the formation mechanism of PS/PMMA particles with core‐shell structure was proposed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of DMF on the polymerization of tert‐butyl acrylate initiated by 4‐oxo‐TEMPO‐capped polystyrene macroinitiator

BACKGROUND: In a number of studies it has been shown that 2,2,6,6‐tetramethylpiperidinooxy (TEMPO)‐mediated polymerization of acrylates is not facile. Therefore, the object of the study reported here was to prepare poly[styrene‐block‐(tert‐butyl acrylate)] (PS‐b‐PtBA) block copolymers using 4‐oxo‐TEMPO‐capped polystyrene macroinitiator as an initiator, in the presence of small amounts of N,N‐dimethylformamide (DMF). The kinetic analysis and the effect of DMF on the reaction mechanism are also discussed. RESULTS: PS‐b‐PtBA block copolymer was prepared through polymerization of tert‐butyl acrylate (tBA) initiated by 4‐oxo‐TEMPO‐capped polystyrene macroinitiator at 135 °C. The polymerization rate of tBA could be increased by adding a small amount of DMF, and the number average molecular weight of the PtBA block in PS‐b‐PtBA reached 10 000 g mol^?1 with narrow polydispersity. The activation rate constant k_act?tBA of alkoxyamine increased and the recombination rate constant k_rec?tBA decreased with increasing DMF concentration. CONCLUSION: DMF was shown to be a rate‐enhancing additive for the polymerization of tBA using a 4‐oxo‐TEMPO‐capped polystyrene macroinitiator. From the kinetic analysis, it was concluded that the improvement of polymerization with the addition of DMF was due to an increase in k_act?tBA and a decrease in k_rec?tBA. Copyright © 2008 Society of Chemical Industry     

Novel biodegradable amphiphilic poly(ε‐caprolactone)/poly(N‐vinylpyrrolidone) blends via successive in situ polymerizations

In this study, biodegradable blends of poly(ε‐caprolactone) (PCL) and poly(N‐vinylpyrrolidone) (PVP) were prepared by a new strategy in the following steps: (1) free radical polymerization of N‐vinyl‐2‐pyrrolidone (NVP) in ε‐caprolactone (CL); (2) ring‐opening polymerization of ε‐caprolactone in the presence of PVP to obtain the target blends. The structure of the blends was confirmed by FTIR and ¹H NMR, and the molecular weight of PCL and PVP were determined by GPC. SEM study revealed that this polymerization method could decrease the disperse phase size and improve the interphase when compared with solution‐blending method. The phase inversion occurred when PVP content was 15–20 wt %. Subsequently, the PCL sphere dispersed in PVP matrix and its size decreased with the increase of PVP content. The contact angle results showed that PVP has a profound effect on hydrophilic properties of PCL/PVP blends. PCL/PVP blends are believed to be promising for drug delivery, cell therapy, and other biomedical applications. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of monodisperse crosslinked poly(styrene‐co‐divinylbenzene) microspheres by precipitation polymerization in acetic acid

Poly(styrene‐co‐divinylbenzene) microspheres with size ranging from 1.6 to 1.8 μm were prepared in acetic acid by precipitation polymerization. The particle size and particle size distribution were determined by laser diffraction particle size analyzer, and the morphology of the particles was observed with scanning electron microscope. Besides, effects of various polymerization parameters such as initiator and total monomer concentration, divinylbenzene (DVB) content, polymerization time and polymerization temperature on the morphology and particle size were investigated in this article. In addition, the yield of microspheres increased with the increasing total monomer concentration, initiator loading, DVB concentration and polymerization time. In addition, the optimum polymerization conditions for synthesis of monodisperse crosslinked poly(styrene‐co‐divinylbenzene) microspheres by precipitation polymerization in acetic acid were obtained. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of aqueous comonomer solubility on the surfactant-free emulsion copolymerization of methyl methacrylate

Surfactant-free emulsion copolymerization was used to prepare methyl methacrylate-hydroxyethyl methacrylate (MMA-HEA) and methyl methacrylate-hydroxypropyl methacrylate (MMA-HPMA) latex particles. Also, glycidyl methacrylate (GMA) was grafted onto the surface of the preformed MMA-HPMA latex particles by seeded surfactant-free emulsion copolymerization. The copolymerization reactions were conducted at 75 °C using a water-soluble initiator, potassium persulfate (KPS). The morphologies of copolymer latex particles were observed using Scanning electron microscopy (SEM). The influence of different reactions parameters (the MMA saturation concentration (Sr), the KPS concentration and the aqueous solubility of the comonomers (HEA or HPMA)) on the particles average diameter and particles size dispersity was investigated. The experimental results showed that the increase of initiator concentration induces in all investigated cases the increase of particles average diameter, while the presence of HEA or HPMA as comonomers in the copolymerization reaction of MMA (1,000% Sr) lead to a decrease of particles average diameter. At small KPS concentration the latex is monodisperse, the increase of the initiator concentration leading to the formation of polydisperse latex. In the case of grafting reaction of GMA onto the monodisperse preformed MMA-HEA latex particles, although the average diameter of the final particles doubles the latex remains quasi-monodisperse.     

Monodisperse polymeric spheres in the micron size range by a single step process

A method for the formation of monodisperse polystyrene (PS) and polymethylmethacrylate (PMMA) spheres, in the micron diameter range, was developed. The polymerisation reaction was carried out in a series of alcohols, using homo- and co-polymers as steric stabilisers in combination with a quaternary ammonium salt which probably acts as an electrostatic co-stabiliser. Monodisperse PS spheres were formed in the particle size range of 1–6 μm, by a single step process. The size range could be extended by further addition of monomer to the reaction mixture during the polymerisation. The solubility parameter of the alcohol used and the nature of the surfactant determine the diameter of the resulting spheres. However, the concentration of surfactant did not seem to affect strongly the size of the spheres but only the dispersity.