Synthesis of nanosized poly(ethyl acrylate) particles via differential emulsion polymerization

Nanoparticles of poly(ethyl acrylate) were synthesized via a semibatch differential emulsion polymerization method with potassium persulfate as the initiator and sodium dodecyl sulfate as the surfactant. The effects of the reaction temperature, aging time, and surfactant/initiator/monomer ratios on the polymer particle sizes were investigated. Poly(ethyl acrylate) with particle sizes of less than 20 nm was synthesized under mild conditions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1609–1614, 2006     

聚苯乙烯和聚丙烯酸丁酯无皂核壳乳液聚合反应的研究

聚苯乙烯 (PS)和聚丙烯酸丁酯 (PBA)复合乳液是无皂乳液聚合反应生成的 ,采用丙烯酸丁酯加到聚苯乙烯种子微粒中反应得到的。PS/PBA复合微粒的结构通过红外光谱图明显的吸收峰特征而得到证实。纯PS微粒和低BA含量的PS/PBA微粒几乎是球形和规则的 ,而随着BA单体含量的增加 ,PS/PBA复合微粒的粒子尺寸变大和呈现类似高尔夫球形状。同时 ,本文进一步研究了PS/PBA复合微粒的表面形态学     

Ab initio reversible addition–fragmentation chain transfer emulsion polymerization of styrene/butyl acrylate mediated by poly(acrylic acid)‐block‐polystyrene trithiocarbonate

Ab initio reversible addition–fragmentation chain transfer (RAFT) emulsion polymerization of styrene/butyl acrylate was investigated with the trithiocarbonate macro‐RAFT agent poly(acrylic acid)‐block‐polystyrene (PAA‐b‐PS) as a stabilizer and a RAFT agent. Influences of the amount of ammonium persulfate (APS), the amount of PAA‐b‐PS and the mass ratio of monomers on emulsion polymerization and film properties are discussed. The particle morphology exhibited spherical‐like structure with particles of about 90 nm in diameter and relatively narrow particle size distribution characterized using transmission electron microscopy and dynamic laser scattering. Fourier transform infrared and ¹H NMR spectra showed that the styrene/butyl acrylate emulsion was successfully synthesized. The monomer conversion increased initially with increasing amount of APS, from 0.4 up to 0.8 wt%, and then decreased. The particle size increased and its distribution decreased gradually with increasing amount of APS. The monomer conversion increased from 76.83 to 94.21% as the amount of PAA‐b‐PS increased from 3 to 4 wt%, and then decreased with further increase of PAA‐b‐PS. The particle size decreased and its distribution increased with increasing amount of PAA‐b‐PS. The water resistance and solvent resistance of the polymer films initially increased and then decreased with decreasing mass ratio of butyl acrylate to styrene. © 2014 Society of Chemical Industry     

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     

Synthesis of poly(3,4‐ethylenedioxythiophene) nanoparticles via chemical oxidation polymerization

Poly(3,4‐ethylenedioxythiophene) (PEDOT) nanoparticles were synthesized via chemical oxidation polymerization using 3,4‐ethylenedioxythiophene as the starting monomer and ammonium peroxydisulfate (APS) as the oxidant. The effects of APS concentration, surfactant concentration and type of surfactant, namely dodecylbenzenesulfonic acid and sodium dodecylsulfate, were investigated. Distinct particle shapes were obtained: irregular, raspberry agglomerate, coralliform, orange‐peel, globular and plum shapes. The particle sizes and the electrical conductivity are in the ranges 60 to 900 nm and <1 to 153 S cm^?1, respectively, depending on the polymerization conditions. PEDOT synthesis in the absence of a surfactant yields a smaller particle size because a larger amount of initiator induces lower molecular weights and smaller PEDOT particles. The smaller PEDOT particles correspond to higher electrical conductivity because of the larger surface areas for electron transfer and a smaller amount of obstructing surfactant aliphatic segments. Moreover, particle size and shape can be varied, depending on surfactant type and concentration which dictate the micellar shapes in the polymerization reaction. This work is focused on the tailor‐made PEDOT shape and property relationship under synthesis conditions where several shapes have not been previously seen. © 2013 Society of Chemical Industry     

PMMA/BA无皂乳液聚合

以过硫酸铵为引发剂,用超声波引发PMMA/BA无皂乳液聚合;探讨了单体和引发剂的质量分数对单体转化率的影响,并对聚合物进行了FT-IR和TEM的表征。结果表明:PMMA/BA乳胶粒直径大约在100nm左右。     

Control of monodisperse particle size of styrenic–acrylate copolymers in dispersion copolymerization

Syntheses of monodisperse poly[(styrene)‐co‐(n‐butyl acrylate)] and poly[(styrene)‐co‐(2‐ethylhexyl acrylate)] were carried out by dispersion polymerization. The reactions were performed in the mixed solvent of ethanol–water in the presence of azo‐bisisobutyronitrile and poly(N‐vinylpyrrolidone) as the initiator and dispersant, respectively. The effects of reaction parameters, that is the type and concentration of dispersant, ratio of the mixed solvent, reaction temperature, agitation rate, monomer composition between styrene and n‐butyl acrylate or 2‐ethylhexyl acrylate, crosslinking agent and reaction time on the particle size, size distribution and average molecular weights of the resulting copolymer were thoroughly investigated. The resulting copolymer particles were smooth on their spherical surface and the sizes were in the range 0.6–1.8 µm with a narrow size distribution. In most cases, a correlation between small particle sizes with high average molecular weights was observed. The average particle size generally increased with increasing reaction temperature, time and acrylate monomer content. In contrast, the particle size decreased as the molecular weight, concentration of dispersant, polarity of the medium or agitation rate was increased. The glass transition temperature (T_g) of the copolymers can be controlled by the mole ratio of the comonomer. The T_g values decreased when the content of acrylate monomers in the copolymer increased, and T_g values of the synthesized copolymer were in the range 66–102 °C. Instead of using n‐butyl acrylate monomer in the copolymerization, 2‐ethylhexyl acrylate copolymerization with styrene resulted in insignificant changes in the particle sizes but there were significant decreases in T_g values. In this study, the monodisperse particles can be obtained by monitoring the appropriate conditions regarding PVP K‐30 (2–8 wt%), ethanol/water (90/10 wt%), the reaction temperature (70 °C) and the agitation rate (100 rpm). © 2000 Society of Chemical Industry     

Synthesis and properties of copolymer microemulsions of siloxane and acrylate with a high solid content

Copolymer microemulsions of methyl methacrylate, butyl acrylate, and vinyltriisopropoxysilane with high monomer/surfactant ratios were prepared through a seeded semicontinuous polymerization in the presence of a redox initiator, ammonium persulfate/sodium hydrosulfate. The mean diameter of the particles decreased with an increase in the amount of the surfactant, the monomer concentration, and the vinyltriisopropoxysilane/monomer ratio, but it increased with an increase in the concentration of the initiator. When the initiator concentration was 0.23% (ammonium persulfate/sodium hydrosulfate = 1.5 : 1), the concentration of the composite surfactant was 0.9 wt %, and the reaction temperature was 50°C; the solid content of the microemulsion could be up to 43% with a small particle size (mean diameter) of 39.8 nm. The chemical, freeze–thaw, and mechanical stability of the latexes was tested as well as the thermal stability of the films. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 851–857, 2007     

Preparation of nanometer‐sized poly(methacrylic acid) particles in water‐in‐oil microemulsions

A water‐in‐oil microemulsion, water‐in‐cyclohexane stabilized by poly(ethylene glycol) tert‐octylphenyl, was developed to prepare poly(methacrylic acid) (PMAA) particles. Up to 100% conversion of the amphiphilic monomer, methacrylic acid (MAA), which could not be converted to the polymer efficiently in a dioctylsulfosuccinate sodium salt/toluene microemulsion, was achieved. The viscosity‐average molecular weight of the PMAA prepared was 1.45 × 10⁵ g/mol. The effects of some polymerization parameters, including the reaction temperature and the concentrations of the initiator and the monomer, on the polymerization of MAA were investigated. The results showed that the polymerization rate of MAA was slower than that of acrylamide in the microemulsions reported in the literature. The degree of conversion increased with the initiator concentration, reaction temperature, and monomer concentration. However, the stable microemulsions became turbid during the polymerization when the reaction temperature was at 70°C or at a high monomer concentration (40 wt %) The synthesized PMAA particles were spherical and had diameters in the range of ～50 nm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2497–2503, 2006     

Poly(methyl methacrylate) multihollow particles by water in oil in water emulsion polymerization

Multihollow‐structured poly(methyl methacrylate) (PMMA) particles were produced employing the water in oil in water (W/O/W) emulsion polymerization technique where sorbitan monooleate was used as a primary surfactant and sodium laurylsulfate and Glucopen, a polypeptide derivative, were used as secondary surfactants. Vinyl acetate was copolymerized to improve the wettability of the particles. The agitation speed and concentration of the urethane acrylate employed as a reactive viscosity enhancer played a crucial role in determining the morphology and average size of the PMMA multihollow particles. In high agitation speed the multihollow particles displayed a small size and narrow size distribution resulting from efficient droplet breakup. Especially when the urethane acrylate was incorporated, PMMA multihollow particles with a smooth and clear surface were achieved. This was believed to be because the urethane acrylate increased the viscosity of the monomer mixture and helped to form the stable W/O/W emulsion droplets that restricted droplet coalescence during polymerization. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 38–44, 2000     

Water‐soluble copolymers. II. Inverse emulsion terpolymerization of acrylamide,sodium acrylate,and acryloyloxyethyl trimethylammonium chloride

Inverse emulsion terpolymerization of acrylamide, sodium acrylate, and acryloyloxyethyl trimethylammonium chloride was investigated. Aqueous monomer solutions were emulsified in diesel oil with a blend of two surfactants (SPAN80 and TWEEN80) using 2,2′‐azobis(2‐amidinopropen)‐dihydrochloride as the initiator. The effects of temperature, initiator concentration, monomer concentration and composition, and emulsifier content on the polymerization conversion and the polymer intrinsic viscosity were examined. Polymer intrinsic viscosity increased with a decreasing concentration of initiator and an increasing concentration of monomer. The sizes of the latex particles of the terpolymer emulsions were observed with a scanning electron microscope, and the structure of the terpolymer was identified by FTIR spectroscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1381–1385, 2006     

Phase Transfer Catalysis: Polymerization Kinetics and Mechanism of Methyl Acrylate

Kinetics and mechanism of the free-radical polymerization of methyl acrylate (MA), using potassium peroxomonosulfate (PMS) as a water-soluble initiator in the presence of benzyltributylammonium chloride (BTBAC) as a phase-transfer catalyst (PTC), were studied. The polymerization reactions were carried out under inert and unstirred conditions at a constant temperature of 60±1°C in ethyl acetate/water biphasic medium. The rate of polymerization (R_p) increased with an increase in the concentrations of MA, BTBAC and PMS. The order with respect to the monomer, initiator, and PTC was found to be 1.0, 0.5, and 0.5 respectively. R_p was independent of the ionic strength and pH of the medium. Based on the kinetic evidences a suitable mechanism is proposed.     

Formation of poly(octadecyl acrylate) brushes on a silicon wafer surface

To introduce an ultrahydrophobic polymeric phase onto a silicon wafer, an initiator‐modified silicon wafer was prepared with 2‐bromopropionyl bromide and then surface‐initiated atom transfer radical polymerization of octadecyl acrylate was carried out from the initiator‐grafted silicon wafer using CuBr and N,N,N′,N″‐pentamethyldiethylenetriamine as catalyst precursors. The resultant poly(octadecyl acrylate) [poly(ODA)] brushes were characterized by ellipsometry, X‐ray photoelectron spectroscopy, grazing angle Fourier transform infrared spectroscopy, atomic force microscopy, gel permeation chromatography and water contact angle measurements. Wettability of the poly(ODA) brushes was found to depend on the surface coverage (Γ) and the root mean square roughness. The most hydrophobic surface (Γ = 25.35 mg m^?2 and root mean square roughness 11.9 nm) exhibited a water contact angle of 171.1 ± 0.2°. Copyright © 2011 Society of Chemical Industry     

Mass transfer and radical flux effects in dispersed‐phase polymerization of isooctyl acrylate

The kinetics of dispersed phase polymerization of a highly water‐insoluble monomer (isooctyl acrylate) were explored in emulsion, miniemulsion, and microsuspension polymerization. The effects of monomer water solubility and choice of initiator (oil‐ vs. water‐soluble) strongly impact the final product (particle size and molecular weight distribution). For emulsion polymerization, as the surfactant concentration was increased, there was a transition from homogenous to micellar nucleation near the CMC, then a drop in nucleation rate at high surfactant concentration due to insufficient radical flux to support more nucleation. For miniemulsion polymerization, a slow rate of growth of (droplet) nucleation with surfactant concentration was found, followed (at the CMC) by an increase in the rate of nucleation with added surfactant as the mode of nucleation switched to micellar. The conversion‐time kinetics of microsuspensions could be modeled with a bulk polymerization model. IOA is sufficiently insoluble in the aqueous phase that emulsion polymerization may or may not be reaction limited. The presence of a stabilizer such a PAA, the use of an oil‐soluble initiator such as BPO, and the insolubility of IOA in the aqueous phase all push the polymerization locus toward droplet (microsuspension) nucleation and bulk kinetics.© 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5649–5666, 2006     

Facile preparation of cationic P (St-BA-METAC) copolymer nanoparticles and the investigation of their interaction with bovine serum albumin

Cationic copolymer nanoparticles were prepared by emulsifier-free emulsion polymerization of styrene and n-butyl acrylate, using [2-(methacryoyloxy ethyl] trimethylammonium chloride as the cationic functional comonomer and 2,2′-azobis (2-methypropionamidine) as the cationic initiator. FTIR spectroscopy, ¹H-NMR spectroscopy, and GPC were applied to characterize the chemical structure and molecular weight of the obtained copolymer. The size and size distribution of the nanoparticles were characterized through photon correlation spectroscopy. The interaction of nanoparticles with bovine serum albumin (BSA) was investigated by the means of transmission electron microscopy and fluorescence spectroscopy. It was found that the copolymer nanoparticles were monodisperse spheres with the diameter less than 90 nm and can complex well with BSA through electrostatic interaction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Ultrasonically initiated emulsion polymerization of n‐butyl acrylate

Ultrasonically initiated emulsion polymerization of n‐butyl acrylate (BA) without added initiator has been studied. The experimental results show that high conversion of BA can be reached in a short time by employing an ultrasonic irradiation technique with a high purge rate of N₂. The viscosity average molecular weight of poly(n‐butyl acrylate) (PBA) obtained reaches 5.24 × 10⁶ g mol^?1. The ultrasonically initiated emulsion polymerization is dynamic and complicated, with polymerization of monomer and degradation of polymer occurring simultaneously. An increase in ultrasound intensity leads to an increase in polymerization rate in the range of cavitation threshold and cavitation peak values. Lower monomer concentration favours enhancement of the polymerization rate. ¹H NMR, ¹³C NMR and FTIR spectroscopies reveal that there are some branches and slight crosslinking, and also carboxyl groups in PBA. Ultrasonically initiated emulsion polymerization offers a new route for the preparation of nanosized latex particles; the particle size of PBA prepared is around 50–200 nm as measured by transmission electron microscopy. © 2001 Society of Chemical Industry     

反相悬浮法合成高耐盐性的超强吸水剂

以多元醇为交联剂、烷基磷酸钠 -司盘 (NP -SP)为复合悬浮稳定剂、丙烯酸 (AA)为单体、过硫酸铵 (APS)为引发剂、环己烷为分散介质 ,采用反相悬浮法合成耐盐性聚丙烯酸钠超强吸水剂。研究了交联剂类型和用量 ,悬浮稳定剂类型、用量和质量比 ,引发剂浓度 ,单体中和度(丙烯酸钠占单体总量的摩尔分数 ) ,聚合温度等对产品物理性状、耐盐性及体系稳定性的影响。当 ρ(多元醇 ) =0 5 3g/L、ρ(NP -SP) =0 0 0 8～ 0 0 1g/mL、m(SP)∶m(NP) =(2 3～ 4 0 )∶1 0、c(APS) =40 5mmol/L、单体中和度x(丙烯酸钠 ) =79 2 %、聚合温度 70～ 76℃时 ,体系稳定 ,产品成球性好 ,吸盐水 (生理盐水 )率 199mL/ g ,吸水 (蒸馏水 )率 86 4mL/ g ,耐盐性高于其他交联剂交联型产品。     

In-situ polymerization of n-butyl acrylate in poly(vinyl chloride)

The in situ polymerization of n-butyl acrylate with poly(vinyl chloride) has been studied. Butyl acrylate was polymerized using a peroxydicarbonate initiator and a thiol chain transfer agent in the presence of poly (vinyl chloride) beads suspended in water. The products were examined, after pressing into sheets, for optical clarity and by dynamic mechanical analysis. It was found that if 10% butyl acrylate was peesent in the mixture homogeneous blends were formed but if 15% or more butyl acrylate was present two phase mixtures were formed. If homogeneous blends prepared as above were reswollen in butyl acrylate, and the latter then polymerized, homogeneous blends containing more poly(butyl acrylate) could be prepared. The interaction parameters between both poly(vinyl chloride' and poly(butyl acrylate) and butyl acrylate were estimated by inverse gas chromatography. Using these and an estimate of the polymer/polymer interaction parameter the three component phase diagram could be qualitatively explained.     

Concentrated emulsion copolymerization of butyl acrylate and vinyl acetate initiated by a redox initiator at lower temperature

The concentrated emulsion copolymerization of butyl acrylate and vinyl acetate with an ammonium persulfate/sodium hydrogen sulfate mixture as a redox initiator, with a sodium dodecyl sulfate/cetyl alcohol mixture as a compound surfactant, and with poly(vinyl alcohol) as a liquid film reinforcer was carried out at lower temperature. In less than 3 h, the polymerization conversion was greater than 95%. The effects of the surfactant, the initiator, the volume fraction of the monomer, and the temperature on the stability of the concentrated emulsion, the kinetic process, and the average size of the latices were examined. The morphology of the polymer particles was observed by transmission electron microscopy, and the average size and distribution of the particle diameter were measured by photon correlation spectroscopy. The kinetic equation was R_p = k[M]^0.38[I]^0.89[E]^?0.80 at 30°C (where R_p is the polymerization rate, [I] is the initiator concentration, [M] is the monomer concentration, and [E] is the concentration of the compound surfactant), and the apparent activation energy was 22.69 kJ/mol. The thin‐layer polymerization of the concentrated emulsions, which enabled the removal of the heat of polymerization, was performed first. In comparison with test‐tube polymerization, thin‐layer polymerization provided a more regular morphology of the polymer particles. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 570–576, 2004     

聚丙烯酸类超强吸水剂的合成与性能研究

以丙烯酸烯丙酯作为交联剂、丙烯酸(AA)为单体、过硫酸钾(KPS)为引发剂,采用溶液聚合法合成了一种聚丙烯酸类超强吸水剂。研究了合成条件对吸水性能的影响:当ρ(丙烯酸烯丙酯)=0 594g/L,ρ(KPS)=0 178g/L,单体中和度x(丙烯酸钠)=90%,c(丙烯酸钠)=4 17mol/L,聚合温度为60℃时,制得的聚合物每克吸去离子水最高达到1360mL,吸盐水(生理盐水)162mL。所得的聚合物具有良好的吸水可逆性,30min的吸水量可以达到饱和吸水量的90%。制得聚合物的热重分析表明,未吸水的该聚合物在350℃开始分解。聚合物吸水前后XRD测试结果显示:吸水前聚合物结构基本无规整性,吸水后膨胀使主链展开,结构趋于规整。