Reversible addition fragmentation transfer (RAFT) polymerization of styrene in a miniemulsion: A mechanistic investigation

The RAFT polymerization of styrene in miniemulsion using 1-phenylethyl phenyl-dithioacetate (PEPDTA) as a RAFT agent was investigated, in attempt to reveal the mechanism for the often observed inferior performance such as low polymerization rate, broad molecular weight distribution and particle size distribution in the RAFT miniemulsion polymerization with regular levels of surfactant and co-stabilizer (1 wt% sodium dodecyl sulfate and 2 wt% hexadecane). It is strongly evident that a few of large oligomer particles consisting of oligomer, RAFT agent (RAFT agent refers to the original RAFT agent), and monomer would be formed in the early stage of the polymerization due to the superswelling of the first nucleated droplets. With the regular levels of surfactant and co-stabilizer, the observed low polymerization rate, broadened molecular weight distribution, slow conversion of the RAFT agent, lower N_p, and broadened particle size distribution could be well explained by the formation of these large oligomer particles and their prolonged existence. When the formation of the oligomer particles was suppressed by increasing surfactant and co-stabilizer levels and wise selection of types of RAFT agent, the molecular weight distribution could be narrowed to around 1.3 and particle size distribution could be close to that of the conventional non-living miniemulsion polymerization.     

SiO2溶胶在微滴乳液聚合中的原位纳米复合

本文提出将正硅酸乙酯(TEOS)的非水sol-gel反应与单体的微滴乳液聚合技术相结合,制备聚丙烯酸酯/二氧化硅纳米复合乳液。首先采用凝胶时间的测定与动态光散射等手段研究TEOS在甲酸催化下的非水sol-gel反应动力学,表明当甲酸/TEOS的摩尔比大于6,有利于形成颗粒状纳米二氧化硅溶胶。以硅烷偶联剂KH-570对非水溶胶原位改性,然后引入丙烯酸酯共聚单体中,研究硅溶胶的存在对单体微滴乳液聚合的影响。结果表明,聚合动力学与单体的微滴乳液聚合基本相似,但二氧化硅的引入改变了单体微滴的均一性和剪切分散的稳定性,导致乳胶粒径逐渐增大,粒径分布变宽。复合乳胶粒是若干无机粒子以微相区被包覆于有机聚合物中的纳米复合结构形态。     

Synthesis of polystyrene encapsulated nanosaponite composite latex via miniemulsion polymerization

The synthesis and characterization of polystyrene encapsulated nanosaponite composite suspension via miniemulsion polymerization are reported in this study. The particle size of nanoclay and its pre-modification are critical to successfully producing a stable complex suspension. The final products were characterized by X-ray diffraction spectra, transmission electron microscopy (TEM), scanning electron microscopy (SEM), thin window energy dispersive spectroscopy (EDS), and light scattering. The results show that ar-vinylbenzyltrimethylammonium chloride (VBTAC) modified nanosaponite could be fully exfoliated and encapsulated inside the polystyrene latex via in situ miniemulsion polymerization. When the concentration of hexadecane (a co-stabilizer used in the miniemulsion polymerization) was high, the final composite particles are composed mainly of spherical particles with size less than 100 nm, and a small number of hemispherical or bowl-structured particles of size ∼100 nm to 1000 nm. The phase separation due to the existence of large amounts of hexadecane accounted for the formation of a variety of morphologies.     

Encapsulation of titanium dioxide in styrene/n‐butyl acrylate copolymer by miniemulsion polymerization

Miniemulsion copolymerization of styrene/n‐butyl acrylate was investigated as a means of encapsulating hydrophilic titanium dioxide (TiO₂) in a film‐forming polymer. Dispersion studies of the TiO₂ were first carried out to determine the choice of stabilizer, its concentration, and the dispersion process conditions for obtaining stable TiO₂ particles with minimum particle size. Through screening studies of various functional stabilizers and shelf‐life stability studies at both room and polymerization temperatures, Solsperse 32,000 was selected to give relatively small and stable TiO₂ particles at 1 wt % stabilizer and with 20–25 min sonification. The subsequent encapsulation of the dispersed TiO₂ particles in styrene/n‐butyl acrylate copolymer (St/BA) via miniemulsion polymerization was carried out and compared with a control study using styrene monomer alone. The lattices resulting from the miniemulsion encapsulation polymerizations were characterized in terms of the encapsulation efficiencies (via density gradient column separations; DGC) and particle size (via dynamic light scattering). Encapsulation efficiencies revealed that complete encapsulation of all of the TiO₂ by all of the polymer was not achieved. The maximum encapsulation efficiencies were 79.1% TiO₂ inside 61.7% polystyrene and 63.6% TiO₂ inside 38.5% St/BA copolymer. As the density of the particles collected from the DGC increased from one layer to another, both the average particle size and the number of the TiO₂ particles contained in each latex particle increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3479–3486, 2006     

Polymeric particles prepared with fluorinated surfmer

Fluoro-containing particles have been obtained by miniemulsion polymerization of styrene and n-butyl methacrylate in presence of fluorinated monomer mono-fluoroalkyl maleate (MFM) which acts as a surfmer providing efficient stability to obtained dispersion and functionalization of particle surface with fluoro-groups. Increase of the MFM concentration in reaction mixture reduces the particle size and dispersions with narrower particle size distribution can be obtained. Blends of fluorinated latexes with styrene-butadiene copolymer latex were examined with regard to formation of low free energy surfaces. It has been shown that blends containing MFM-functionalized polymeric particles possess more hydrophobic surfaces then similar latex films, where particles prepared by polymerization of expensive fluorinated monomer have been applied.     

Miniemulsion copolymerization of styrene and butyl acrylate initiated by redox system at lower temperature: Reaction kinetics and evolution of particle‐size distribution

The kinetics of the miniemulsion copolymerization of styrene (St) and butyl acrylate (BA) initiated by redox initiators, (NH₄)₂S₂O₈/NaHSO₃, at lower temperature (45°C) was studied. The polymerization rate in miniemulsion copolymerization is lower than that of the corresponding conventional emulsion copolymerization. In regard to the rate of polymerization, the initiator concentration plays a more important role in miniemulsion copolymerization than in conventional emulsion polymerization, while the surfactant concentration has a more important role in conventional emulsion polymerization than in miniemulsion polymerization. These are attributed to their different nucleation mechanisms, which are the same as those found in the miniemulsion polymerization carried out at higher temperatures. While by eliminating nucleation via micelle and ensuring against homogeneous nucleation, miniemulsion polymerization can be carried out by the sole nucleation mechanism—monomer droplet nucleation—at lower temperature. Because of this, the particles become narrower during the polymerization and, finally, monodisperse polymer particles are obtained. The result of the particle numbers indicated that a continuous nucleation will cease at about 60% conversion. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 315–322, 1999     

Photo-initiated miniemulsion polymerization as a route to the synthesis of gold nanoparticle encapsulated latexes

We report the first use of photo-initiated miniemulsion polymerization for the synthesis of well defined poly(methyl methacrylate) (PMMA) latexes. Furthermore, the application of photo-initiation is employed to the incorporation of decanethiol-capped gold nanoparticles (AuNPs). The procedure provides a low temperature polymerization for an oil-in-water miniemulsion with temperatures not exceeding 40 °C and polymerization times of only one hour. Using these mild reaction conditions allows the use of miniemulsion polymerization for the encapsulation of temperature sensitive species within the latex. Furthermore, we demonstrate the applicability of this method for the incorporation of decanethiol-capped AuNPs. Particle size distribution and morphology was studied using dynamic light scattering (DLS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). PMMA latexes ranged between 100 and 200 nm in diameter showing good particle size distribution and tendencies to form semi-ordered domains. We show that variations in surfactant, hydrophobe and initiator concentrations behave in the same manner as miniemulsions initiated through conventional thermal methods. TEM observations revealed that the latexes with encapsulated AuNPs displayed even distributions of AuNPs throughout the PMMA latex with no aggregation witnessed.     

Convenient method for removing and concentrating hydrophobic organic compounds from water with amphiphilic polymers

A stable fluoroacrylate copolymer emulsion was successfully prepared by miniemulsion polymerization with fluoroacrylate, lauryl methylacrylate, and methyl methacrylate as monomers. Extremely hydrophobic fluoroacrylate, instead of conventional cosurfactants, was used as a reactive cosurfactant to stabilize the miniemulsions. The results indicated that fluoroacrylate retarded Ostwald ripening and allowed the production of stable miniemulsions. The chemical compositions of the copolymer were studied with Fourier transform infrared and ¹H‐NMR. The average composition of the copolymers prepared with miniemulsions was in good agreement with the feed ratio according to ¹H‐NMR from the integration ratios corresponding to typical protons of the individual monomers. The particle size distribution and morphology of the latex particles were determined with laser particle analysis and transmission electron microscopy. The particle size of the latex underwent no change in the process of miniemulsion polymerization, but the particle size distributions were broader than those of conventional emulsion polymerization. The effects of various reaction parameters, including the temperature and concentrations of the emulsifier and initiator, on the miniemulsion polymerization were also investigated, and the polymerization rate and conversion increased with increasing concentrations of nonylphenol polyethoxylate (with an average of 40 ethylene oxide units per molecule), cetyltrimethylammonium, and 2,2′‐azobisisobutyronitrile. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 641–647, 2007     

Nanocomposite particles with core‐shell morphology. I. Preparation and characterization of Fe3O4–poly(butyl acrylate‐styrene) particles via miniemulsion polymerization

Colloidal particles with magnetic properties have become increasingly important both technologically and for fundamental studies. Here, chemical initiator‐free miniemulsion polymerization of styrene and butyl acrylate has been performed for preparation of magnetic nanocomposite particles with the diameter of 81–150 nm in the presence of sodium dodecyl sulfate as surfactant, span 80 as stabilizer, and hexadecane as hydrophobe. The polymerization reaction was initiated and progressed under ultrasonic irradiation, generated by immersed probe into the latex. The key point in achievement of encapsulation of modified Fe₃O₄ nanoparticles was preparation of a stable colloidal dispersion at the end of the reaction. The obtained products in each step were characterized by FTIR spectroscopy. Dynamic light scattering analysis was used to follow particle size diameter of the samples. Morphology of the particles and formation of core‐shell structure were analyzed by SEM and TEM micrographs, respectively. TGA and magnetometry of the polymeric films confirmed the extent of insertion of used magnetite and their corresponding behavior. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

微滴乳液聚合制备PDMS/SiO2纳米复合材料

采用超声分散的方法,以少量八甲基环四硅氧烷(D₄)对硅溶胶粒子进行表面接枝改性。然后在改性硅溶胶存在下,以十二烷基苯磺酸(DBSA)为乳化剂兼催化剂进行D₄的微滴乳液聚合,得到聚硅氧烷(PDMS)/二氧化硅(SiO₂)纳米复合乳液。采用FTIR、TGA、纳米粒度仪、TEM和拉力机分别对样品进行了表征。结果表明:采用超声分散的方法,能够有效地实现硅溶胶粒子的表面改性。通过微滴乳液聚合得到的复合乳胶粒是聚合物包覆二氧化硅粒子的核壳结构形态。SiO₂的引入提高了有机硅复合膜力学性能,增强了热稳定性。     

Seeded emulsion polymerization of n-butyl acrylate utilizing miniemulsions

Nucleation of polymer particles in the seeded emulsion polymerization of n-butyl acrylate (BuA) was studied through experiments designed to control the amount of new particles formed. The results show that for the batch and semicontinuous seeded polymerization of BuA, a small amount of new particles was formed in the system in which the monomer was added neat, whereas a singificant amount of new particles was formed when the monomer was added as a miniemulsion. This suggests that new particles formed in the miniemulsion process were from nucleation of the monomer droplets. These experiments also showed that monomer-droplet nucleation decreased with increasing seed concentration in the reactor. For the seeded semicontinuous polymerizations, monomer-droplet nucleation decreases with decreasing BuA miniemulsion feed rate. The results also show that monomerdroplet nucleation takes place whenever miniemulsion droplets exist in the reactor. This study suggests that miniemulsions can be used to control the particle size distribution of a polymer latex system.     

Homogeneously distributed magnetite in the polystyrene spherical particles using the miniemulsion polymerization

The polystyrene spherical particles with homogeneously distributed magnetites were prepared using the conventional miniemulsion polymerization. In the first, the magnetite nanoparticles were coated with oleic acid in aqueous Fe³⁺/Fe²⁺ solution using excess ammonium hydroxide via co-precipitation method. In the second, the miniemulsion polymerization of styrene was carried out using various concentrations of potassium persulfate (KPS) as an initiator, H-08E as an emulsifier, hexadecane as a co-emulsifier and acrylic acid as a dispersing agent in the presence of oleic acid coated magnetite at 70 °C for 24 h. The particle size and its distribution of the homogeneously embedded magnetites were influenced by the concentration of the initiator (KPS) and acrylic acid (AAc). In addition, the emulsifier, H-08E, affects the size and the shape of the PS particles. The optimum conditions for the homogeneously distributed magnetite in the spherical PS particles with the narrow distribution were 5 wt.% styrene, 0.2 g KPS, 0.2 g AAc, and 0.12 g H-08E by inducing 364 nm in diameter, 12.04% in the coefficient of variation (C_v) and 22.1% of the maximum magnetite content.     

High pressure semibatch emulsion and miniemulsion copolymerization of vinyl acetate and ethylene

This study presents the experimental study of semibatch emulsion and miniemulsion copolymerization of vinyl acetate (VAc) and ethylene to vinyl acetate-ethylene (VAE) copolymer at 60°C and 80–300 psig. In the miniemulsion copolymerization, a water-soluble initiator (K₂S₂O₈) is used and VAc miniemulsion is prepared in presence of surfactant and cosurfactant using a sonicator or a high-shear homogenizer. Then, ethylene gas is supplied to the reactor at constant partial pressure. In a miniemulsion process, the mass transfer limitations of VAc from monomer droplets to the aqueous phase, and to micelles or polymer latex particles that are present in conventional macro-emulsion polymerization can be eliminated and the transfer of ethylene dissolved in the aqueous phase to the miniemulsion droplets is the major ethylene transport process for the polymerization. The experimental data show that the amount of ethylene incorporation into the copolymer is higher in miniemulsion polymerization than in emulsion polymerization. The ethylene pressure has been found to have a strong impact on the ethylene incorporation into the copolymer phase in both emulsion and miniemulsion copolymerizations but the increase is more pronounced in miniemulsion case. The VAE copolymer latex particles prepared by miniemulsion polymerization exhibited higher storage stability than those prepared by macro-emulsion polymerization.     

Particle nucleation and growth in seeded semibatch miniemulsion polymerization of hybrid CeO2/acrylic latexes

CeO₂/acrylic hybrid coatings with high solids content and with nanoparticle percentages up to 5 wt% have been successfully synthesized by seeded semibatch miniemulsion polymerization process. The droplet nucleation efficiency has been assessed by Capillary Hydrodynamic Chromatography and TEM analysis. The effect of the stability of the miniemulsion, the type of initiator and the number of particles of the seed on the efficiency of the nucleation of the nanodroplets fed has been investigated. It was found that the less stable the hybrid miniemulsion, the higher the diffusion of the monomer out of the droplets and hence, the seed latex particles grew in size. However, the CeO₂ nanoparticles did not diffuse out with the monomer and remained in very small droplets that eventually nucleate leading to a bimodal population. When stable miniemulsions were produced by using a polymer as hydrophobe, droplet size increased reducing the number of particles in the seed and monomer diffusion was minimized enhancing nucleation of droplets with larger sizes that produced broad PSDs. Coalescence of droplets was negligible because the size distribution of the nanoceria particles did not change from the seed particles to the final latex. The UV–Vis absorption capacity of the films prepared with increasing the amount of CeO₂ increased, but scattering effects were observed at high loading of CeO₂ due to the large size of the CeO₂ aggregates.     

In-situ polyurethane/polyacrylate microemulsion formation: the effects of acrylic content in wood coating application

In-situ surfactant-free emulsion polymerization was utilized to prepare polyacrylate/polyurethane (PUA) microemulsions in the absence of surfactant and organic solvent. For this purpose, PUA with higher acrylate content was successfully prepared, with the aim to reduce the coating cost. The dynamic light scattering results showed that the particle size of PUA microemulsion displayed a unimodal distribution and the particle size was ranged from 33 to 61 nm. In comparison with PUA prepared with conventional miniemulsion polymerization, the particle size distribution coefficient dropped by one order. Atomic force microscopy, together with thermogravimetric analyzer, demonstrated good compatibility and interaction between PU and acrylic components, and no phase separation was detected even at 58 wt% acrylic content. With the incorporation of acrylic component, the thermal stability and maximum stress were improved. The maximum stress greatly increased from 4.6 to 30.9 MPa, and the maximum stress of in-situ PUA was nearly three times larger than that of PUA prepared by miniemulsion polymerization. The effects of acrylic content on water resistance, pencil hardness, adhesion, and impact strength of wood coating were evaluated. With increasing the acrylic content, the water resistance and pencil hardness increased, though the impact strength of in-situ PUA films was slightly reduced.     

Comparison of styrene reversible addition–fragmentation chain‐transfer polymerization in a miniemulsion system stabilized by ammonlysis poly(styrene‐alt‐maleic anhydride) and sodium dodecyl sulfate

In this study, we conducted the reversible addition–fragmentation chain‐transfer (RAFT) polymerization of styrene (St) in a miniemulsion system stabilized by two different stabilizers, ammonlysis poly(styrene‐alt‐maleic anhydride) (SMA) and sodium dodecyl sulfate (SDS), with identical reaction conditions. The main objective was to compare the polymerization kinetics, living character, latex stability, and particle morphology. The macro‐RAFT agent used in both systems was SMA, which was obtained by RAFT solution polymerization mediated by 1‐phenylethyl phenyldithioacetate. The experimental results show that the St RAFT miniemulsion polymerization stabilized by SDS exhibited a better living character than that stabilized by ammonlysis SMA. The final latices were very stable in two systems, but different stabilizers had an obvious effect on the polymerization kinetics, living character, and particle morphology. All of the particles obtained by RAFT miniemulsion polymerization stabilized by SDS were solid, but an obvious core–shell structure was observed in the miniemulsion system stabilized by ammonlysis SMA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of poly(styrene‐co‐butyl acrylate)/clay nanocomposite latexes in miniemulsion by AGET ATRP

Polymer/clay nanocomposite latexes in the form of positively charged nanoparticles were synthesized by a newly developed initiating system, activators generated by electron transfer (AGET), which has been employed in atom transfer radical polymerization (ATRP). These clay‐dispersed latexes were synthesized using AGET ATRP of styrene and butyl acrylate in a miniemulsion system in which, ascorbic acid as a reducing agent was added drop wise to reduce termination reactions. Particle size and particle size distribution of resulted nanocomposite latexes were characterized by dynamic light scattering (DLS). These latexes were in the range of 138 to 171 nm in size. Gel permeation chromatography (GPC) was used to characterize the molecular weight and molecular weight distribution of the resultant copolymer nanocomposites. GPC traces showed that polymers of narrow molecular weight distribution and low Polydispersity Index (PDI) have been synthesized; this clearly shows ATRP reaction is conducted successfully. By increasing nanoclay content, molecular weight of the nanocomposites decreases. The presence of the nanofiller increases the thermal stability of the nanocomposites as investigated by thermogravimetric Analysis (TGA). Glass transition temperature of nanocomposites increases compared with the neat copolymer which was studied by differential scanning calorimetry (DSC). scanning electron microscope (SEM) showed sphere morphology of polymer particles synthesized by miniemulsion polymerization. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) results showed that mixed intercalated and exfoliated morphology is obtained. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

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     

细乳液聚合制备二氧化钛/聚苯乙烯复合微球及其形貌分析

采用细乳液聚合法,以γ-甲基丙烯酰氧基丙基三甲基硅烷改性的TiO2粒子为核,制备了核壳结构的TiO2/聚苯乙烯(PS)复合微球。研究了超声细乳化时间、乳化剂十二烷基硫酸钠(SDS)的浓度、TiO2用量对细乳液粒径及其分布的影响。通过纳米粒度与Zeta电位分析仪、红外光谱、透射电镜等分析手段对产物进行了表征。结果表明,随着超声细乳化时间的增加,初始液滴的粒径变小。聚合后的乳胶粒粒径随着SDS浓度的增大而减小;TiO2用量不足导致乳胶粒粒径分布变宽,且出现双峰;制备所得的TiO2/PS复合微球粒度分布较为均匀,平均直径为176.5 nm,球形规整度较好。     

Kinetics of miniemulsion polymerizations of ethylene glycol dimethacrylate and/or methyl methacrylate

Two types of reactive acrylic microgel particles of methyl methacrylate (MMA)/ethylene glycol dimethacrylate (EGDMA) (66.4/33.6 and 0/100 (mol/mol)) were prepared by miniemulsion polymerization with 2,2′‐azobisisobutyronitrile as the initiator in the temperature range 60–80 °C. Ostwald ripening occurred during the very early stage of polymerization. In addition to the predominant droplet nucleation, homogeneous nucleation was also observed. The polymerization rate for MMA/EGDMA miniemulsion was higher than that for EGDMA miniemulsion. By contrast, comparable apparent limiting conversions were observed for the polymerizations of MMA/EGDMA and EGDMA. The mole fractions of MMA and EGDMA units incorporated into the copolymer product were estimated to be 0.62 and 0.38, respectively, for the polymerization of MMA/EGDMA at 70 °C. The mole fraction of the EGDMA unit containing one ? C?C? within the MMA/EGDMA microgel particle product was estimated to be 0.23, which was comparable to that (0.22) of the EGDMA unit containing one ? C?C? within the EGDMA microgel particle product. © 2015 Society of Chemical Industry