Emulsifier‐free miniemulsion polymerization of styrene and the investigation of encapsulation of nanoparticles with polystyrene via this procedure using an anionic initiator

Emulsifier‐free miniemulsion polymerization of styrene was investigated in the presence of potassium persulfate (KPS) as an anionic initiator and cetyl alcohol as a costabilizer using ultrasonic irradiation and comparison of this procedure with conventional emulsifier‐free emulsion polymerization showed that this method has a remarkably higher polymerization rate (R_p), smaller size of particles, and narrower molecular weight distribution via gravimetric measurement, transmission electron microscopy (TEM), and gel permeation chromatography techniques, respectively. Then, the encapsulation of magnetite (Fe₃O₄) and titanium dioxide (TiO₂) nanoparticles with polystyrene was investigated using this procedure. Attempt to encapsulate magnetite nanoparticles failed; however, the encapsulation of titanium dioxide nanoparticles was successfully carried out via this procedure using KPS in both cases. TEM proved the presence of TiO₂ nanoparticles in polymer particles, and thermogravimetric analysis was used to determine the percentage of TiO₂ in the products. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Emulsifier‐free emulsion polymerization of styrene

Polystyrene latex particles in an emulsifier‐free emulsion were prepared by purified styrene (St) as monomer and 2,2′‐azobis (2‐amidino propane) dihydrochloride (ABA, 2HCl) as initiator. The optimized condition of polymerization of styrene was obtained by using the various parameters such as different amounts of monomer (0.009, 0.051, and 0.071 mol styrene/mol Water), different amounts of initiator (6.02, 4.62, 2.41, and 1.00 weight percent of initiator relative to styrene), and pH (range 1–7). Quantitative and qualitative analyses of prepared polymer were performed by Scanning Electron Microscopy (SEM), Differential Scanning Calorimetry (DSC), Gel Permeation Chromatography (GPC), and ¹H‐NMR and FT‐IR spectroscopy, that were used, respectively, to show the morphology of particles, the glass transition temperature (T_g), the average molecular weight, and the structure of the prepared polymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1898–1904, 2004     

IBN partition between st monomer/polymer and water and its application in miniemulsion polymerization initiated by AIBN

Isobutyronitrile has been selected as a stable substitute for the 2‐cyano‐2‐propyl radical originating from 2,2′‐azobis(isobutyronitrile) to study the behavior of this radical in miniemulsion polymerization. The partition of isobutyronitrile between styrene monomers/polymers and water has been investigated by carrying out equilibrium experiments under different conditions. Prediction based on a published kinetic model using the newly measured partition coefficient has also been compared with published experimental data and prediction based on the partition coefficient of 2,2′‐azobis(isobutyronitrile). The partition coefficients for isobutyronitrile were found to be 10.98 for the styrene/water system and 4.34 for the polystyrene/water system, respectively. The partition coefficient was found to be unaffected by selected conditions. The model prediction based on the partition coefficient of isobutyronitrile agreed well with the published experimental data, thus, indicating that the partition coefficient of the primary radical should be used in theoretical calculations rather than that of the initiator. © 2011 American Institute of Chemical Engineers AIChE J, 58: 3135–3143, 2012     

Emulsifier‐free emulsion copolymerization of styrene with quaternary ammonium cationic monomers

Emulsifier‐free emulsion binary copolymerizations of styrene with four types of quaternary ammonium cationic monomers, diallyldimethylammonium chloride (DADMAC), (3‐(methacryloylamino) propyl) trimethyl ammonium chloride (MAPTAC), (2‐methacryloyloxy) ethyl) trimethyl ammonium chloride (MATMAC), and vinylbenzyl trimethyl ammonium chloride (VBTMAC), were conducted at 70°C. 2, 2'‐azobis (2‐methylpropionamidine) dihydrochloride (V50) and potassium persulphate (KPS) were used as cationic and anionic initiator, respectively. Ternary copolymerizations were also carried out in the presence of acrylamide as a second comonomer. Monomer conversions were followed by ultraviolet spectroscopy and the polymer microparticles were characterized using photon correlation spectroscopy, electrophoresis, colloid titration, and scanning electron microscopy. The results indicated that VBTMAC and MATMAC were highly reactive in the copolymerization with styrene whereas the incorporation of DADMAC was slow. MAPTAC had an intermediate reactivity. Binary copolymerization with VBTMAC, MATMAC, and MAPTAC produced particles smaller in size, but higher in surface‐charge density, than styrene homopolymer particles. However, significant agglomerates were detected in the VBTMAC and MATMAC‐containing latexes. In contrast, DADMAC‐containing polymer particles were almost identical to styrene particles. Continuous nucleation took place in the binary copolymerizations with VBTMAC and with MATMAC when using V50 initiator. In the case of using KPS, VBTMAC‐containing particles grew continuously to a mean size much larger than the corresponding particles initiated by V50. The presence of acrylamide reduced DADMAC‐containing particle size and diminished the agglomeration in the VBTMAC‐ and MATMAC‐containing latexes. The results were interpreted via particle formation mechanism. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1129–1140, 2000     

Polymer microgels prepared by emulsifier‐free emulsion polymerization of unsaturated polyesters and styrene

In the present work polymer microgels were prepared by emulsifier‐free emulsion copolymerization of unsaturated polyesters (UPs) with end carboxyl groups and styrene (St). The nucleation mechanism of UP‐St emulsifier‐free emulsion polymerization was proposed. The effects of the ratio of the monomers to water, pH, and the ratio of UP to St on the stability of polymerization and the yield of microgels were studied. It was found that the polymer microgels can be used to markedly improve the impact strength of UP. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3049–3053, 2000     

Synthesis of clay‐dispersed poly(styrene‐co‐methyl methacrylate) nanocomposite via miniemulsion atom transfer radical polymerization: A reverse approach

Poly(styrene‐co‐methyl methacrylate) nanocomposites were synthesized using reverse atom transfer radical polymerization (RATRP) in miniemulsion. Cetyltrimethylammonium bromide (CTAB) as a cationic surfactant applicable at higher temperatures was used for miniemulsion stabilization. Successful RATRP was carried out by using 4,4′‐dinonyl‐2,2′‐bipyridine (dNbPy) as ligand. Monodispersed droplets and particles with sizes in the range of 200 nm were revealed by dynamic light scattering (DLS). Conversion and molecular weight study was carried out using gravimetry and size exclusion chromatography (SEC) respectively. By adding clay content, a decrease in the conversion and molecular weight and an increase in the PDI value of the nanocomposites are observed. Thermal stability of the nanocomposites in comparison with the neat copolymer is revealed by thermogravimetric analysis (TGA). Increased T_g values by adding clay content was also obtained using differential scanning calorimetry (DSC). Scanning electron microscopy (SEM) images of the nanoconposite with 1 wt % of nanoclay loading, display monodispersed spherical particles with sizes in the range of ～ 200 nm. SEM findings are more compiled with dynamic light scattering (DLS) results. Well‐dispersed exfoliated clay layers in the polymer matrix of the nanocomposite with 1 wt % nanoclay loading is confirmed by transmission electron microscopy (TEM) images and X‐ray diffraction (XRD) data. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Kinetics of reversible addition–fragmentation transfer (RAFT) miniemulsion polymerization of styrene using dibenzyl trithiocarbonate as RAFT reagent and costabilizer

The roles of dibenzyl trithiocarbonate (DBTTC) as both costabilizer and reversible addition–fragmentation transfer (RAFT) reagent in RAFT miniemulsion polymerizations of styrene were investigated. The effectiveness of DBTTC costabilizer in retarding Ostwald ripening involved in the storage stability of miniemulsion is comparable to that of conventional low‐molecular‐weight costabilizers such as cetyl alcohol, but inferior to that of hexadecane. The major variables chosen for studying kinetics of RAFT miniemulsion polymerizations include the type of initiators and levels of DBTTC and surfactant. At a constant level of DBTTC, the rate of polymerization for benzoyl peroxide (BPO)‐initiated polymerization is slower than that for sodium persulfate (SPS)‐initiated polymerization. Furthermore, the polymerization rate decreases with increasing level of DBTTC for polymerizations initiated by BPO (or SPS). It is the monomer droplet nucleation that governs BPO‐initiated polymerizations. In contrast, for SPS‐initiated polymerizations, the probability for homogeneous nucleation to take place is greatly increased, especially for polymerizations with lower levels of DBTTC and higher levels of surfactant. © 2015 Society of Chemical Industry     

Radical polymerization of styrene by a hexa‐substituted‐ethane type thermal iniferter

The bulk polymerization of styrene (St) initiated with a hexa‐substituted‐ethane type initiator, diethyl 2,3‐dicyano‐2,3‐diphenylsuccinate (DCDPS), was investigated. It was found that DCDPS served as a thermal iniferter for polymerization of St and the polymerization had some characteristics in common with living radical polymerization, ie, both the yield and the molecular weight of the resulting polymers increased with increasing reaction time. The resultant polystyrene can act as a macroinitiator for chain‐extension polymerization of St or for radical polymerization of methyl methacrylate to give a block copolymer. © 2001 Society of Chemical Industry     

Preparation and characterization of P(St‐co‐4VP) particles produced by using emulsifier‐free emulsion polymerization

Emulsifier‐free emulsion polymerization of styrene (St) and copolymerization of St and 4‐vinyl pyridine (4VP) in the presence of ammonium persulfate were studied. A comparison between the two polymerization systems was made. It was found that there were big differences comparing polymerization rate, the number and size of the particles and distribution, and molecular weight. For the St–4VP system, it was found that the additional amount of 4VP influenced the copolymerization of St and 4VP, molecular weight, and particle size. The formation mechanism of the particles was discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1502–1507, 1999     

Effects of ethyl acetate on the soap‐free emulsion polymerization of 4‐vinylpyridine and styrene

The properties and morphologies of poly(4‐vinylpyridine‐co‐styrene) [P(4VP/St)] lattices, prepared by soap‐free emulsion polymerization using the water‐soluble initiator 2,2′‐azobis(2‐amidinopropane) · 2HCl (V50), were greatly affected by the addition of ethyl acetate (EA). The properties and morphologies of the resultant lattices were characterized by measuring the zeta potential, viscosity average molecular weight, particle size and distribution, glass‐transition temperature (T_g), and photographs taken by SEM and TEM. The effects of two kinds of monomer feeding modes, that is, the batch and semicontinuous emulsion copolymerization, were also investigated. For batch emulsion copolymerization, by charging EA, the core–shell morphology resulting from the disparate reactivity ratios of the 4VP(1)/St(2) copolymerization system (r₁ = 1.04, r₂ = ?0.73) disappeared. Instead, first a bimodal particle size distribution, with an apparently asymmetric composition structure, and then spherical microspheres were obtained as the amount of EA charged increased from 2 to 10 wt %. The particle size increased twofold by the addition of EA. The zeta potential of particles increased from +64.4 to more than +100 mV, and viscosity average molecular weight decreased from 9.70 to 0.97 × 10⁵ g/mol, as EA increased from 0 to 8 wt %. With the semicontinuous copolymerization, raspberry‐like particles were obtained by charging 10 wt % EA, whereas a sandwich‐like morphology was obtained without EA. The DSC curves showed one T_g for all the lattices prepared with charging EA, but two T_g's for the latex prepared without using EA, regardless of the monomer feeding modes. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1988–2001, 2001     

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     

Mathematical modeling of molecular weight distribution in miniemulsion polymerization with oil‐soluble initiator

A mathematical model for the study of reaction kinetics and molecular weight distributions in miniemulsion polymerization systems with oil‐soluble initiators is presented. The mathematical model allows the computation of the evolution of the complete molecular weight distribution with chain lengths of up to 10⁵ mers in miniemulsion polymerization by direct integration in reasonable computational time. Also, no restriction in the kinetic regime is needed, as the model is able to represent both compartmentalized and pseud‐bulk systems. The model was validated with experimental results for methyl methacrylate and styrene homopolymerizations, with two different oil‐soluble initiators, and adequately represented both the kinetics and molecular weight distributions of these systems. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2128–2140, 2017     

Emulsifier‐free emulsion polymerization of acrylonitrile: Effect of in situ developed Cu(II)/glycine chelate complex initiated by monopersulfate

The catalytic effect of various Cu(II) salts and Cu(II) chelate complexes of certain amino acids on the emulsion polymerization of acrylonitrile in the absence of added emulsifier was investigated in experiments. The CuSO₄/glycine chelate complex was chosen for a detailed kinetic study of acrylonitrile polymerization. The polymerization was studied at varying concentrations of initiator, monomer, Cu(II), glycine, solvents, and TiO₂ over a temperature range of 30–60°C. The overall activation energy and the viscosity average molecular weight of the polymer were computed. From the kinetic and spectrophotometric studies, the mechanism of KHSO₅ decomposition by the Cu(II)/glycine complex and initiation of polymerization was suggested. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2785–2790, 1999     

Grafting vinyl monomers onto silk (Bombyx mori) using different initiators: Properties of grafted silk

The graft–copolymerization of silk with methacrylamide (MAA), 2‐hydroxyethyl methacrylate (HEMA), and methyl methacrylate (MMA) was studied using three different free‐radical initiators: an inorganic peroxide [ammonium persulfate (APS)] and two azo compounds [2,2′‐azobisisobutyronitrile (AIBN) and 2,2′‐azobis(2‐methylpropionamidine) dihydrochloride (ADC)]. The rate and yield of grafting followed the order: APS > AIBN > ADC. The performance of AIBN was close to that of APS in terms of weight gain attained. The degree of yellowing of grafted silk varied as a function of the initiator–monomer system used. APS induced the highest degree of yellowing, regardless of which monomer was used, whereas silk grafted with the MAA/AIBN system displayed the lowest level of yellowing. Moisture regain of grafted silk changed as a function of the hydrophilic/hydrophobic character of the grafted polymer, regardless of the kind of initiator used. Accordingly, tensile properties showed a tendency to decrease with increasing weight gain of grafted silk, the extent of which was independent of the kind of monomer and initiator used. The different initiators did not induce any appreciable change in the fine structure of silk, as demonstrated by optical measurements. Uneven surface deposition of homopolymer was detected to variable extent with MMA and HEMA grafting, whereas the surface of MAA‐grafted silk was completely free of any foreign deposit, independently of the initiator used. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1401–1409, 2001     

Toughening modification of PS with n‐BA/MMA/styrene core–shell structured copolymer from emulsifier‐free emulsion polymerization

Core–shell structured particles, which comprise the rubbery core and glassy layers, were prepared by emulsifier‐free emulsion polymerization of poly(n‐butyl acrylate/methyl methacrylate)/polystyrene [P(n‐BA/MMA)/PS]. The particle diameter was about 0.22 μm, and the rubbery core was uncrosslinked and lightly crosslinked, respectively. The smaller core–shell structured particle–toughened PS blends were investigated in detail. The dynamic mechanical behavior and observation by scanning electron microscopy of the modified blend system with core–shell structured particles indicated good compatibility between PS and the particles, which is the necessary qualification for an effective toughening modifier. Notched‐impact strength and related mechanical properties were measured for further evaluation of the toughening efficiency. The notched‐impact strength of the toughened PS blends with uncrosslinked particles reached almost sixfold higher than that of the untoughened PS when 15 phr of the core–shell structured particles was added. For the crosslinked particles the toughening effect for PS was not obvious. The toughening mechanism for these smaller particles also is discussed in this article. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1290–1297, 2003     

One‐step synthesis of star‐block copolymers via simultaneous free radical polymerization of styrene and ring opening polymerization of ε‐caprolacton using tetrafunctional iniferter

Star‐block copolymers comprised of poly(styrene) (S) core and four poly(ε‐caprolacton) (ε‐CL) arms were synthesized by the combination of free radical polymerization (FRP) of S and ring opening polymerization (ROP) of ε‐CL in one‐step in the presence of tetrafunctional ineferter. The block copolymers were characterized by ¹H‐NMR and FTIR spectroscopy, gel permeation chromatography (GPC), and fractional precipitation method. ¹H ‐NMR and FTIR spectroscopy and GPC studies of the obtained polymers indicate that star‐block copolymers easily formed as result of combination FRP and ROP in one‐step. The γ values (solvent/precipitant volume ratio) were observed between 1.04–2.72 (mL/mL) from fractional measurements. The results show that when the initial S feed increased, the molecular weights of the star‐block copolymers also increased and the polydispersities of the polymers decreased. M_w/M_n values of the products were measured between 1.4 and 2.86 from GPC. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polyisoprene,poly(styrene‐cobutadiene) and their blends. III. Tensile properties of tetramethylthiuram disulfide/sulfur and 2‐bisbenzothiazole‐2,2'‐ disulfide/sulfur compounds

Polyisoprene (IR), poly(styrene‐cobutadiene) (SBR) and IR/SBR blends were vulcanized with tetramethylthiuram disulfide (TMTD)/sulfur and 2‐bisbenzothiazole‐2,2′‐disulfide (MBTS)/sulfur formulations and their tensile properties were determined. MBTS vulcanized IR has inferior tensile properties to TMTD vulcanizates. This is attributed in part to main chain modification in MBTS vulcanizates decreasing the ability of chains to crystallize or to align as effective load‐bearing chains under stress. A similar discrepancy is not found in SBR compounds that cannot stress‐crystallize. Polybutadiene, which readily crystallizes on cooling, is used to demonstrate differences in the effect of MBTS and TMTD on the ability of chains in the vulcanizates to align. These differences are confirmed by X‐ray diffraction studies of stressed IR vulcanizates. The addition of zinc stearate reduces main chain modification, promotes crystallization, and improves tensile properties. Blends have inferior properties to IR, and tests involving the pulling apart of laminates and analysis of the tear surfaces are used to illustrate that failure does not occur in adhesion, but within the IR phase close to the interface. It is argued that diffusion of curatives from SBR to the faster curing IR phase, leads to the development of a layer of highly crosslinked material in IR close to the phase boundary. Failure occurs in this layer and may be attributed to a decrease in the number of effective load‐bearing chains in this region or to the shorter chains in this layer becoming taut. Less diffusion of the accelerator occurs with MBTS than with TMTD, leading to a less highly crosslinked IR zone close to the interface. Consequently, higher loads are required to initiate failure. Failure in blends is likewise considered to initiate in the highly crosslinked region in the IR phase close to the phase boundary with SBR. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2143–2149, 1999     

Synthesis and characterization of novel polyaspartimides derived from 2,2′‐dimethyl‐4,4′‐bis(4‐maleimidophenoxy)biphenyl and various diamines

A novel bismaleimide, 2,2′‐dimethyl‐4,4′‐bis(4‐maleimidophenoxy)biphenyl, containing noncoplanar 2,2′‐dimethylbiphenylene and flexible ether units in the polymer backbone was synthesized from 2,2′‐dimethyl‐4,4′‐bis(4‐aminophenoxy)biphenyl with maleic anhydride. The bismaleimide was reacted with 11 diamines using m‐cresol as a solvent and glacial acetic acid as a catalyst to produce novel polyaspartimides. Polymers were identified by elemental analysis and infrared spectroscopy, and characterized by solubility test, X‐ray diffraction, and thermal analysis (differential scanning calorimetry and thermogravimetric analysis). The inherent viscosities of the polymers varied from 0.22 to 0.48 dL g⁻¹ in concentration of 1.0 g dL⁻¹ of N,N‐dimethylformamide. All polymers are soluble in N‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide, dimethylsulfoxide, pyridine, m‐cresol, and tetrahydrofuran. The polymers, except PASI‐4, had moderate glass transition temperature in the range of 188°–226°C and good thermo‐oxidative stability, losing 10% mass in the range of 375°–426°C in air and 357°–415°C in nitrogen. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 279–286, 1999     

Delocalized π‐electrons in 2‐oxazoline rings resulting in negatively charged nitrogen atoms: revealing the selectivity during the initiation of cationic ring‐opening polymerizations

The inventory of the single‐crystal X‐ray structures of aliphatic and aromatic 2‐oxazolines, namely 2‐nonyl‐2‐oxazoline, 2,2′‐tetramethylenebis(2‐oxazoline) and 2‐phenyl‐2‐oxazoline, reveals significant delocalization of π‐electrons along the N? C? O segment. The delocalization of π‐electrons is stabilized by inductive and resonance contributions of the side‐chains; in 2‐phenyl‐2‐oxazoline, also π‐arene interactions between the benzene ring and the C? N and the C? O bond stabilize the crystalline phase. This delocalization gives a partial negative charge to the nitrogen atom and a partial positive charge to the oxygen atom. The partial negative charge of the nitrogen atom makes this atom the exclusive reaction partner also for highly reactive non‐selective cations, which explains the regioselectivity of electrophilic attacks in cationic ring‐opening polymerizations. Copyright © 2011 Society of Chemical Industry     

Kinetics and particle nucleation mechanism of St/BA/qBVPBr emulsifier‐free cationic emulsion polymerization

Stable functional cationic latices were prepared by emulsifier‐free emulsion copolymerization of styrene (St) and butyl‐acrylate (BA) with 1‐butyl‐4‐vinylpyridinium bromide (qBVPBr) as functional comonomer and azobis(isobutyramidine hydrochloride) (AIBA) as initiator at (70 ± 1)°C. The influences of the reaction temperature, the initiator concentration, and comonomer concentration on the polymerization conversion (x %), polymerization rate (R_p) of poly(St/BA/qBVPBr) emulsions were investigated. The results indicated that x % and R_p increase with increasing qBVPBr or AIBA concentration and temperature, and R_p can be expressed as R_p = K_p[AIBA]^0.73[qBVPBr]^0.08 (r_AIBA = 0.9968; r_qBVPBr = 0.9946, both r_AIBA and r_qBVPBr are linear correlation coefficient) and the apparent activation energy (E_a) is 47.89 kJ mol^?1. In the absence of emulsifier condition, curves of R_p versus reaction time obeyed the typical behavior characterized by Intervals I, II, and III as similar conventional emulsion polymerization. The formation and growth of poly(St/BA/qBVPBr) latex particles has been studied at different reaction times. The results indicate that N_p decrease gradually with time at the early polymerization stages and then reach a constant value after about 20% conversion, but D_p by photon correlation spectroscopy grow continuously as all polymerization proceed. Both the particle size distribution and molecular weight distribution curves are of bimodal size distribution and indicate the participation of at least two mechanisms of particle formation, namely, homogeneous nucleation in the aqueous phase and micellar nucleation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009