Seeded dispersion polymerization

Micron‐size poly(n‐butyl acrylate) (PBA) and polystyrene (PSt) particles were used as seed in second‐stage seeded dispersion polymerizations. The effects of various polymerization parameters on the morphology of the structured particles resulting from the second‐stage seeded dispersion polymerizations were studied, and a series of uniform micron‐size structured particles was successfully prepared. In addition to the polymerization medium, the type of stabilizer (i.e., the molecular weight of the polyvinylpyrrolidone [PVP] stabilizer) that was used in the seed preparation and the subsequent seeded dispersion polymerization was found to be important. The final outcome of a seeded dispersion polymerization, that is, the morphology of the structured particles and the formation of secondary particles, was found to be primarily governed by thermodynamic factors. It was also found that the latex particles in these dispersion systems are virtually stabilized by the small amount of grafted PVP molecules. The dispersions maintain colloidal stability after repeated washing of the particles, which removes all of the soluble PVP. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2710–2720, 2002     

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     

Study on synthesis and morphology control of poly(4‐vinylpyridine‐co‐butyl acrylate)/poly(styrene‐co‐butyl acrylate) composite microspheres

Monodispersed crosslinked cationic poly(4‐vinylpyridine‐co‐butyl acrylate) [P(4VP‐BA)] seed latexes were prepared by soapless emulsion polymerization, using 2,2′‐azobismethyl(propionamidine)dihydrochloride (V₅₀) as an initiator and divinylbenzene (DVB) or ethylene glycol dimethacrylate (EGDMA) as a crosslinker. The optimum condition to obtain monodispersed stable latex was investigated. It was found that the colloidal stability of the P4VP latex can be improved by adding an adequate amount of BA (BA/4VP = 1/4, w/w), and adopting a semicontinuous monomer feed mode. Subsequently, poly(4‐vinylpyridine‐co‐butyl acrylate)/Poly(styrene‐co‐butyl acrylate) [P(4VP‐BA)/P(ST‐BA)] composite microspheres were synthesized by seeded polymerization, using the above latex as a seed and a mixture of ST and BA as the second‐stage monomers. The effects of the type of crosslinker, the degree of crosslinking, and the initiators (AIBN and V₅₀) on the morphology of final composite particles are discussed in detail. It was found that P(4VP‐BA)/P(ST‐BA) composite microspheres were always surrounded by a PST‐rich shell when V₅₀ was used as initiator, while sandwich‐like or popcorn‐like composite particles were produced when AIBN was employed. This is because the polarity of the polymer chains with AIBN fragments is lower than for the polymer with V₅₀ fragments, hence leading to higher interfacial tension between the second‐stage PST‐rich polymer and the aqueous phase, and between PST‐rich polymer and P4VP‐rich seed polymer. As a result, the seed cannot be engulfed by the PST‐rich polymer. Furthermore, the decrease of T_g of the second‐stage polymer promoted phase separation between the seeds and the PST‐rich polymer: sandwich‐like particles formed more preferably than popcorn‐like particles. It is important knowledge that various morphologies different from PST‐rich core/P4VP‐rich shell morphology, can be obtained only by changing the initiator, considering P4VP is much more hydrophilic than PST. The zeta potential of composite particles initiated by AIBN in seeded polymerization shifted from a positive to a negative charge. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1190–1203, 2002     

Seeding as a means of controlling particle size in dispersion polymerization

Two distinctively different seeded dispersion polymerization processes employing micron and submicron size seed particles, respectively, have been used to gain a better mechanistic understanding of the dispersion polymerization process. Using monodisperse micron-size PMMA particles as seed, it was found that when low monomer/polymer ratios (M/P < 2.50) were used in methyl methacrylate (MMA) seeded dispersion polymerizations, particle growth dominates and the number of particles remains unchanged (i.e., narrow distributions are preserved). However, when higher M/P ratios (>2.50) were applied, bimodal or trimodal particle size distributions were produced, which is considered to result from the competition between particle growth and secondary nucleation. When small amounts of submicron seeds were used with the initial intention of gaining a better understanding of the nucleation process, it was surprisingly found that the final number of micron size particles was nearly the same as the initial number of submicron seed particles over a relatively wide range of reaction conditions, including seed, initiator, stabilizer, and monomer concentrations, and the medium composition. These results indicate that within certain limits seeded dispersion polymerization can be a more robust means of controlling particle size than ab initio dispersion polymerization in terms of reproducibly producing a target particle size. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Morphologies of polybutylacrylate/poly(styrene‐co‐methyl methacrylate) latex prepared by starved emulsion polymerization Part I. Thermodynamics equilibrium morphology

Heterogeneous latexes were prepared by a semicontinuous seeded emulsion polymerization process under monomer starved conditions at 80 °C using potassium persulfate as the initiator and sodium dodecyl sulfate as the emulsifier. Poly(butyl acrylate) latexes were used as seeds. The second‐stage polymer was poly(styrene‐co‐methyl methacrylate). By varying the amounts of methyl methacrylate (MMA) in the second‐stage copolymer, the polarity of the copolymer phase could be controlled. Phase separation towards the thermodynamic equilibrium morphology was accelerated either by ageing the composite latex at 80 °C or by adding a chain‐transfer agent during polymerization. The morphologies of the latex particles were examined by transmission electron microscopy (TEM). The morphology distributions of latex particles were described by a statistical method. It was found that the latex particles displayed different equilibrium morphologies depending on the composition of the second‐stage copolymers. This series of equilibrium morphologies of [poly(butyl acrylate)/poly(styrene‐co‐methyl methacrylate)] (PBA/P(St‐co‐MMA)) system provides experimental verification for quantitative simulation. Under limiting conditions, the equilibrium morphologies of PBA/P(St‐co‐MMA) were predicted according to the minimum surface free energy change principle. The particle morphology observed by TEM was in good agreement with the predictions of the thermodynamic model. Therefore, the morphology theory for homopolymer/homopolymer composite systems was extended to homopolymer/copolymer systems. © 2002 Society of Chemical Industry     

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     

Kinetics of polymerization and particle stabilization mechanism on dispersion copolymerization of styrene and divinylbenzene

Monodisperse highly crosslinked microspheres were prepared by dispersion copolymerization of styrene and divinylbenzene in an ethanol/water medium using poly(N‐vinylpyrrolidone) (PVP) as the stabilizer. The locus of polymerization and growth of particles were investigated. The polymerization kinetics, average particle diameter (D_n), polydispersity index (PDI), and numbers of particles (N_p) were presented. When the initial styrene concentration is below 20%, the results indicate that the polymerization occurs in the particles, and the particles grow to their final size by the diffusion of monomer and oligomer into the existing particles. The polymerization rate can be described by the equation R_p = k[l]^0.87 ([St]^1.91 + [DVB]^0.09) (1 + [PVP]^0.01) exp(? 45.35/RT). The data from infrared spectroscopy demonstrated that the graft stabilizer was present. The dissolution experiments show that the crosslinking reaction occurred irregularly in batch dispersion polymerization. Using the postaddition approach, up to 3% divenylbenzene (DVB) was successfully incorporated in the synthesis of coagulum‐free substance, and monodisperse crosslinked 5 μ m microspheres with a superior resistance to solvents have been prepared. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2230–2238, 2002     

Morphology of poly(butyl acrylate)/poly(styrene‐co‐methyl methacrylate) latex prepared by starved emulsion polymerization: II. Development of particle morphology

Heterogeneous latexes were prepared by a two‐stage seeded emulsion polymerization process under monomer starved conditions at 80 °C using potassium persulfate as the initiator and sodium dodecyl sulfate as the emulsifier. Poly(butyl acrylate) latexes were used as seeds. The second‐stage polymer was poly(styrene‐co‐methyl methacrylate). By varying the amount of methyl methacrylate (MMA) in the second‐stage copolymer, the polarity of the copolymer phase could be controlled. It was found that the latex particles displayed different morphologies depending on the monomer ratio. The amount of MMA had a significant effect on the evolution of morphology. The morphologies were observed by transmission electron microscopy. In addition, the evolution of the particle morphology was predicted by the mathmatical model for cluster migration. The model gave the same trends as the experimental results. © 2002 Society of Chemical Industry     

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     

Preparation of hemispherical poly(4‐vinylpyridine‐co‐butyl acrylate)/poly(styrene‐co‐butyl acrylate) composite microspheres by seeded preswelling emulsion polymerization

Seeded preswelling emulsion polymerization was carried out by using monodispersed poly(4‐vinylpyridine‐co‐butyl acrylate) [P(4VP‐BA)] particles as the seed, and styrene and butyl acrylate as the second‐stage monomers under different polymerization conditions, to obtain hemispherical polystyrene (PST)‐rich–P4VP‐rich microspheres. Prior to polymerization, toluene was added into the preswelling system together with the second‐stage monomers. It was found that, with the increase of the amount of toluene, the particle morphology showed a tendency toward desirable hemispherical structure, and the colloidal stability of composite latex was improved. When the weight ratio of toluene/seed latex was increased up to 7.5/40 (g/g), the stable hemispherical latex could be obtained. However, when toluene was not added, the coagulum formed on the wall of the reactor during polymerization, and the composite particles with multiple surface domains (such as sandwich‐like, popcorn‐like) were formed. In addition, the final morphology of composite particles was influenced by the polarity of the seed crosslinker and the hydrophilicity of the second‐stage initiator, which could affect the mobility of poly(styrene‐co‐butyl acrylate) [P(ST‐BA)] chains. The morphology development during the polymerization was investigated in detail, and a schematic model was derived to depict the formation mechanism of hemispherical P(4VP‐BA)/P(ST‐BA) composite microspheres. The results revealed that the mobility of the P(ST‐BA) chains influenced the diffusion of the P(ST‐BA) domains on the surface of the P(4VP‐BA) matrix. When the mobility of the P(ST‐BA) chains allowed small‐size P(ST‐BA) domains to coalesce into one larger domain, complete phase‐separated morphology (hemisphere) could be achieved. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3811–3821, 2003     

Morphology of micron‐sized,monodisperse, nonspherical polystyrene/poly(n‐butyl methacrylate) composite particles produced by seeded dispersion polymerization

Nonspherical polystyrene (PS)/poly(n‐butyl methacrylate) (PBMA) composite particles with uneven surfaces were produced by seeded dispersion polymerization of BMA with 1.65‐μm, monodisperse, spherical PS seed particles. The composite particles consisted of a PS core and an incomplete PBMA shell. The formation mechanism of such nonspherical particles was discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2013–2021, 2002     

Dispersion polymerization of methyl methacrylate: Effect of stabilizer concentration

In dispersion polymerizations of methyl methacrylate (MMA), little difference was found in the polymerization kinetics with varying stabilizer (PVP K‐30) concentration, indicating that in contrast to emulsion polymerization, the kinetics of these dispersion polymerizations are independent of the number of particles. Comparing MMA precipitation and dispersion polymerizations revealed that nuclei formation in the latter results from precipitation polymerization occurring in the continuous phase, which can contribute significantly to the kinetics, and especially to the molecular weight distributions. No change was found in the molecular weight distribution of the PVP during a dispersion polymerization, nor was there any measurable difference between using fresh and recycled stabilizer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Kinetics and mechanism of seeded dispersion polymerization

The kinetics and mechanism of seeded dispersion polymerization of methyl methacrylate (MMA) was studied by applying both micron and submicron PMMA seeds. Using a 1.7 μm PMMA seed (N_p = 1 × 10¹²/L) and a monomer polymer ratio (M/P) of 28/1, secondary nucleation was found to occur and the number of new particles exceeded that produced in a parallel ab initio dispersion polymerization. This was explained by the paradoxical initiator concentration effect seen in dispersion polymerizations where the number of particles decreases with increasing initiator concentration. In contrast, using 194 nm (N_p = 26 × 10¹²/L; M/P = 833/1) and 317 nm (N_p = 5.6 × 10¹²/L; M/P = 714/1) submicron seeds, it was found that the final particle number was similar to (or less in a few cases) the initial seed number over a relatively wide range of initiator concentrations. With increasing initiator concentration, the initial reaction rate increased but the maximum reaction rate decreased slightly. This was explained by increased radical termination particularly in unstable nuclei, leading to a reduced radical entry rate. The reaction rate was found to be moderately dependent on the number of seed particles, but was independent of the seed surface area. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Kinetic investigations of acrylic–polyurethane composite latex

The effect of various reaction parameters on the rate of polymerization, R_p, and on the particle size and morphology of aqueous acrylic–polyurethane hybrid dispersions, prepared by semibatch emulsion polymerization, was investigated. The particles of polyurethane dispersion were used as seeds during the polymerization of acrylic component: methyl methacrylate (MMA), butyl acrylate (BA), and a mixture of MMA and BA with the ratio of 1:1. These emulsions were found to form structured polymer particles in aqueous media using scanning electron microscopy. The kinetics of the emulsion polymerization was studied on the basis of Wessling's model. The influence of emulsifier and initiator concentrations, including the monomer feed rates, R_m, on the rates of polymerization and on the properties of the resulting dispersions were studied. The number of particles and the particle size were also measured during the polymerization process. The final values were found to be independent of the concentration of the emulsifier, initiator and the monomer feed rate in monomer starved conditions. In the steady‐state conditions, during the seeded semibatch hybrid emulsion polymerization, the rate of polymerization and the monomer feed rate followed the Wessling relationship 1/R_p = 1/K + 1/R_m. The dispersions MMA/PU, BA/PU, and MMA/BA/PU have K values of 0.0441, 0.0419 and 0.0436 mol/min, respectively. The seeded BA/PU hybrid polymerization proceeded according to Smith‐Ewart Case I kinetics, while the MMA/PU hybrid emulsions demonstrate Case II of the Smith‐Ewart kinetic model. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2639–2649, 2002     

中空聚合物微球的制备——种子及核乳胶粒的制备

为了制得具有中空结构的聚合物微球,首先以十二烷基苯磺酸钠(SDBS)为乳化剂,在其用量低于CMC的条件下,进行甲基丙烯酸甲酯(MMA)、甲基丙烯酸(MAA)和丙烯酸丁酯(BA)的乳液聚合,制备了带羧基的种子乳胶粒.然后采用MMA、MAA和二乙烯基苯为单体进行种子乳液聚合,制备了轻度交联的带羧基的核乳胶粒.该核乳胶粒经过核-壳乳液聚合和适当的碱处理工艺就可成为具有中空结构的聚合物微球.采用粒度仪测定了乳胶粒的直径及其分布,采用TEM对乳胶粒结构形态进行了表征.研究了种子及核乳胶粒制备过程中单体加料方式、乳化剂用量及羧基单体种类等因素对聚合稳定性、乳胶粒直径及其分布以及最终的中空聚合物微球结构形态的影响,确定了制备种子及核乳胶粒的最佳工艺条件.在制备种子阶段,SDBS用量为单体总量的0.5%,采用一次性加入单体的进料工艺;在核乳胶粒制备阶段,以MAA为羧基单体,所有单体采用"饥饿式"加料,半连续补加乳化剂并使乳化剂用量为核单体总量的0.15%时可保持聚合稳定性并保证无新乳胶粒生成.     

Synthesis of polystyrene/poly(butyl acrylate) core–shell latex and its surface morphology

A polystyrene (PS)/poly(butyl acrylate) (PBA) composite emulsion was produced by seeded emulsion polymerization of butyl acrylate (BA) with PS seed particles which were prepared by emulsifier‐free polymerization of styrene with potassium persulfate (KPS) under a nitrogen atmosphere at 70°C for 24 h with stirring at 60 rpm and swelled with the BA monomer in an ethanol/water medium. The structure of the PS/PBA composite particles was confirmed by the presence of the characteristic absorption band attributed to PS and PBA from FTIR spectra. The particles for pure PS and PS/PBA with a low content of the BA monomer were almost spherical and regular. As the BA monomer content was increased, the particle size of the PS/PBA composite particles became larger, and more golf ball‐like particles were produced. The surface morphology of the PS/PBA composite particles was investigated by AFM and SEM. The T_g's attributed to PS and PBA in the PS/PBA composite particles were found at 110 and ?49°C, respectively. The thermal degradation of the pure PS and PS/PBA composite particles occurred in one and two steps, respectively. With an increasing amount of PBA, the initial thermal decomposition temperature increased. On the contrary the residual weight at 450°C decreased with an increasing amount of PBA. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 595–601, 2003     

Highly crosslinked micron‐sized,monodispersed polystyrene particles by batch dispersion polymerization,Part 1: Batch,delayed addition,and seeded batch processes

The seeded batch dispersion polymerization with or without monomer absorption was compared with the batch polymerization and delayed addition by batch polymerization, to prepare the highly crosslinked, monodispersed polystyrene (PS) particles. The seeded batch polymerization was carried out under the variation of styrene (in second stage)/styrene (in PS seed) (St/St) ratio, divinylbenzene (DVB) concentration, and polymerization temperature using 1.9‐μm monodispersed PS seed particles. The experimental results imply that the seeded batch process is more efficient method that could avoid the sensitive particle nucleation step in the presence of the crosslinker than the batch and delayed addition processes. Without monomer absorption, 2.3‐μm uniform crosslinked PS particles with 7 wt % of the DVB were prepared in 1/1 (St/St) ratio. In comparison, with the monomer absorption, monodispersed and smooth‐surfaced PS particles containing 20 wt % of the DVB were formed. A total of 5% weight loss of the crosslinked PS particles determined by TGA occurred from 353.8 to 374.8°C, and the degree of swellability in toluene decreased from 150 to 104.5% with increasing the DVB concentration from 5 to 20 wt % because of the increase of the crosslink density of the particles. The seeded polymerization, especially through monomer absorption procedure, is a novel way to obtain highly crosslinked, monodispersed PS particles. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Syntheses of acrylate core/shell imbiber beads by seeded suspension copolymerization and one‐stage copolymerization for solvent absorption–desorption

Seeded suspension copolymerization or a one‐stage copolymerization was used to synthesize acrylate core/shell imbiber beads. A two‐stage polymerization technique was used for seeded suspension polymerization. The seed particles for poly(methyl acrylate) or poly(2‐ethylhexyl acrylate) were synthesized first in a mixed solvent of toluene/isooctane containing the ethylene glycol dimethacrylate (EGDMA) crosslinking agent. These beads were swollen in styrene‐EGDMA‐BPO (benzoyl peroxide) and then polymerized in the aqueous phase to produce the polystyrene (PS) shell. The one‐stage copolymerization was carried out in toluene/isooctane containing methyl methacrylate (MMA), styrene (St), EGDMA, and BPO at 75°C for 10 h to give a core/shell copolymer of St‐MMA morphology. The appearance of core/shell imbiber beads prepared from these two techniques varied from monomer to monomer. This article describes the preparation, characterization, and application of the core/shell beads for organic solvent absorption/desorption. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 670–682, 2002     

The effects of acrylate monomers and polystyrene addition on the morphology of DOP‐plasticized styrene–acrylate polymer particles prepared by SPG emulsification and suspension polymerization

Fairly uniform copolymer particles of methyl acrylate (MA), butyl acrylate (BA), or butyl methacrylate (BMA) were synthesized via Shirasu porous glass (SPG) membrane and followed by suspension polymerization. After a single‐step SPG emulsification, the emulsion composed mainly of the monomers. Hydrophobic additives of dioctyl phthalate (DOP), polystyrene molecules, and an oil‐soluble initiator, suspended in an aqueous phase containing poly(vinyl alcohol) (PVA) stabilizer and sodium nitrite inhibitor (NaNO₂), were subsequently subjected to suspension polymerization. Two‐phase copolymers with a soft phase and a hard phase were obtained. The composite particles of poly(St‐co‐MA)/PSt were prepared by varying the St/PSt ratios or the DOP amount. The addition of PSt induced a high viscosity at the dispersion phase. The molecular weight slightly increased with increasing St/PSt concentration. The multiple‐phase separation of the St‐rich phase and PMA domains, observed by transmission electron microscopy, was caused by composition drift because the MA reactivity ratio is greater than that of St. The addition of DOP revealed the greater compatibility between the hard‐St and soft‐MA moieties than that without DOP. The phase morphologies of poly(St‐co‐MA), poly(St‐co‐BMA), and their composites with PSt were revealed under the influence of DOP. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1195–1206, 2006     

Vibration damping and electrical conductivity of styrene–butyl acrylate random copolymers filled with carbon black

Emulsion‐polymerized poly(styrene‐rand‐butyl acrylate) (St–BA) copolymers exhibit damping capabilities over a wide temperature range with changes in the monomer ratio. Blending copolymers of different compositions results in a multidamping peak, further widening the effective damping temperature range. Adding carbon black (CB) reduces the peak damping intensity but enhances damping at higher temperatures. The addition of dodecyl benzene sulfonic acid to an St–BA/CB aqueous dispersion improves the dispersion of CB in the polymer, reducing the percolation threshold and improving the conductivity while slightly affecting the mechanical behavior. The electrical properties of the St–BA/CB system are affected by the copolymer composition, influencing the polymer surface tension. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010