Effect of 1-pentanol on the styrene emulsion polymerization

The influence of 1-pentanol (C₅OH) on the ST emulsion polymerization mechanisms and kinetics is investigated. The CMC of the ST emulsions first decreases rapidly and then levels off when the C₅OH concentration ([C₅OH]) increases from 0 to 72 mM. The effect of C₅OH increases to a maximum and then decreases when the SDS concentration ([SDS]) increases from 2 to 18 mM. At [SDS]=2 mM, homogeneous nucleation controls the polymerization kinetics regardless of [C₅OH]. At [SDS]=4 mM, the effect of [C₅OH] appears due to the transition from homogeneous nucleation to a mixed mode of particle nucleation (homogeneous nucleation and micellar nucleation) occurs when [C₅OH] increases from 0 to 72 mM. The effect of [C₅OH] is the strongest at [SDS]=6 mM since the particle nucleation mechanisms span homogeneous nucleation (low [C₅OH]), a mixed mode of particle nucleation (homogeneous nucleation and micellar nucleation) (medium [C₅OH]) and micellar nucleation (high [C₅OH]). At [SDS] >6 mM, in which micellar nucleation controls the polymerization kinetics, the effect of [C₅OH] decreases rapidly with increasing [SDS].     

Dispersion polymerization of styrene in CO2-expanded ethanol

Dispersion polymerization of styrene has been performed in CO₂-expanded ethanol at ≤9 MPa and 70 °C using PVP as stabilizer. The polymerizations proceeded with good colloidal stability, resulting in spherical particles of diameters of ∼2 μm. Pressurization with CO₂ leads to an increase in particle size (∼1 μm in the corresponding CO₂-free system), and a decrease in both polymerization rate and molecular weight. The main effect of CO₂ is proposed to be its influence on the partitioning of monomer between the continuous and the particle phase–the results indicate that CO₂-pressurization causes a reduction in monomer concentration in the particles. Overall, the results are consistent with literature data on the effects of the polarity of the continuous phase in dispersion polymerization of styrene in alcohols and alcohol/water mixtures.     

Winsor I-like (micro)emulsion polymerization of styrene initiated by oil-soluble initiator

Batch emulsion polymerization of styrene initiated by an oil-soluble initiator and stabilized by non-ionic emulsifier (Tween 20) has been investigated. The rate of polymerization vs. conversion curve shows the two non-stationary rate intervals typical for the non-stationary-state polymerization. This behavior is a result of the continuous particle nucleation and the decrease of monomer concentration at the reaction loci with increasing conversion. The initial increase of the polymerization rate is attributed to the increase of particle number and the polymerization proceeding under the monomer-saturated condition—the Winsor I-like (micro)emulsion polymerization. The decrease of the polymerization rate is the result of the depressed transfer of monomer from the monomer reservoir to the reaction loci. Above 50 °C the monomer emulsion separates into two phases: the upper transparent monomer phase and the lower blue colored (microemulsion) phase. The polymerization mixture consists of the microdroplets (act as the reaction loci) and large degradable monomer droplets (act as the reservoir monomer and emulsifier). The continuous release of emulsifier from the monomer phase and the microdroplets induce the continuous particle nucleation up to high conversion. The initial formation of large particles results from the agglomeration of unstable growing particles and monomer droplets. The size of large (highly monomer-swollen) particles decreases with conversion and they merge with the growing particles at ca. 40-50% conversion. The coarse initial emulsion transformed during polymerization to the fine (semitransparent) polymer emulsion as a result of the continuous particle nucleation, the shrinking of highly monomer-swollen polymer particles and the depletion of monomer droplets. The low overall activation energy of polymerization is mainly ascribed to the decreased barrier for entering radicals into the latex particles with increasing temperature.     

Entry in emulsion polymerization using a mixture of sodium polystyrene sulfonate and sodium dodecyl sulfate as the surfactant

A mixture of sodium polystyrene sulfonate (NaPSS) and anionic surfactant, sodium dodecyl sulfate (SDS), was used as the emulsifier in the emulsion polymerization of styrene at 60 °C. The latexes prepared were stable, bearing the better resistance to the addition of electrolyte, and have the larger values in particle size and the higher polymerization rates than those counterparts prepared using SDS only. The NaPSS was prepared by a series of process: a concentrated cyclohexane solution of an anionically polymerized polystyrene (PS) was sulfonated with sulfuric acid at 80 °C, and then neutralized and purified through dialysis. The data of average polymer number per particle (n_p) were found useful in investigating the surfactant content effect on the entry of radicals into particles, where the latex particle size plays an important role.     

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     

Particle formation mechanism in radical polymerization in miniemulsion based on in situ surfactant formation without high energy homogenization

Conventional radical polymerization of styrene at 70 °C in aqueous miniemulsion generated using the in situ surfactant technique, without use of high energy mixing, has been investigated in detail. The surfactant potassium oleate was formed in situ by reaction between oleic acid and potassium hydroxide at the styrene/water interface. The particle formation mechanism was investigated by use of pyrene as a probe, revealing that under suitable conditions with an oil-phase initiator, particle formation occurs primarily via monomer droplet nucleation. The droplet/particle stability is however inferior to that in a typical miniemulsion generated employing ultrasonication, as manifested by a marked increase in droplet/particle size with conversion and a bimodal droplet/particle size distribution by weight. The droplet/particle stability increases with increasing amount of oleic acid, hexadecane, water, and the ratio potassium hydroxide:oleic acid, respectively.     

Secondary particle formation in suspension polymerization using a particulate surfactant

ABSTRACT

Suspension polymerization is widely used for the preparation of microsphere and microcapsules for many applications. However, the formation of secondary particle byproducts decreases drastically the obtained microsphere yield and microcapsule shell strength. It is surprisingly finding that the secondary particles were not observed in the preparation of polymethyl methacrylate particles by suspension polymerization using particulate surfactant called Pickering emulsion. Therefore, in this work, the mechanism of secondary particle formation during suspension polymerization was investigated using various surfactants (zinc oxide, titanium dioxide, and silica nanoparticles compared to polyvinyl alcohol) and monomers (styrene, methyl methacrylate, and methyl acrylate) with different water solubilities. Results showed that submicrometer-sized secondary particles were still formed by homogeneous nucleation mainly due to radical exit from the monomer droplets. However, the formed secondary particles were unstable and then adsorbed on the main microsphere surface. The number of secondary particles increased when monomers with higher water solubility were used.     

Methacrylic acid-based amphiphilic block-random copolymer stabilizers for emulsion polymerization

The emulsion polymerization of styrene was investigated using polystyrene-b-[polystyrene-r-poly(methacrylic acid)] amphiphilic block-random copolymers (BRCs) of different compositions as stabilizers. These stabilizers with molar masses <20,000 g/mol, which possess unique dispersion behaviour (i.e., self-assembly with low aggregation numbers) when dissolved in aqueous medium at alkaline pH, were prepared by the nitroxide-mediated bulk polymerization of styrene to achieve a desired molar mass followed by chain extension by batchwise addition of styrene and methacrylic acid monomers to obtain the stabilizing group. Emulsion polymerizations of styrene stabilized by these BRCs yielded stable latexes with particle diameters that range between 30 and 150 nm. When different concentrations of the stabilizer (2–3.5 mM) were utilized for emulsion polymerization of styrene, a similar novel emulsion polymerization mechanism observed previously by our group for the acrylic-acid based amphiphilic BRCs was also seen, further validating the difference between this class of polymeric surfactants and conventional small molecule surfactants, block copolymers, or alkali soluble resins. The performance of methacrylic-acid based BRCs was more efficient and yielded higher surface coverage of the polystyrene latexes when compared to the acrylic-acid based BRCs as a result of the more hydrophobic nature of the former.     

On the role of an unconventional rigid rodlike cationic surfactant on the styrene emulsion polymerization. Kinetics, particle size and particle size distribution

An unconventional amphiphile (1-[ω-(4′-methoxy-4-biphenylyloxy)octyl]pyridinium bromide, PC8) was used as surfactant in the emulsion polymerization of styrene. At low surfactant concentration (6, 12 or 36 mmol l⁻¹), curves of polymerization rate versus conversion obeyed the typical behavior characterized by intervals I, II and III. However, at high concentration (48 or 72 mmol l⁻¹) the interval II was not observed. The particle size distribution curves showed two families of polymer particles, indicating the participation of at least two mechanisms of particle formation, one being the simple micellar nucleation and the other probably the coagulative nucleation of precursor particles. The latter was considered to occur during the nucleation interval.     

Monodisperse, micrometer-sized low molar mass polystyrene particles by two-stage dispersion polymerization

Free-radical dispersion polymerization of styrene was carried out in ethanol and in ethanol-water mixtures in the absence and presence of carbon tetrabromide (CBr₄) as a chain transfer agent. When CBr₄ was present at the onset of the reaction, particles with a broad size distribution were obtained. If, however, the addition of CBr₄ was delayed ca 1 h, so that the particle nucleation step was complete, then 1-2 wt% chain transfer agent, dissolved in monomer plus solvent, could be added to the reaction without a deleterious affect on particle formation. The particle size and size distribution was essentially identical to that obtained in the absence of CBr₄. When more CBr₄ was added, other problems arose. These problems appeared to be due to solubility of low molar mass polymer in the reaction medium. They could be overcome by running the reaction in ethanol-water mixtures (e.g. 5 wt% water) to decrease the solubility of oligo-styrene at 70 °C, the reaction temperature. In this way, monodisperse particles could be prepared in the presence of 3 wt% CBr₄ based upon total styrene, consisting of polymers with M_n=7060, M_w/M_n=2.4.     

Population balance modeling of particle size distribution in monomer‐starved semibatch emulsion polymerization

The evolution of particle size distribution (PSD) in the monomer‐starved semibatch emulsion polymerization of styrene with a neat monomer feed is investigated using a population balance model. The system under study ranges from conventional batch emulsion to semicontinuous (micro)emulsion polymerization depending on the rate of monomer addition. It is shown that, contrary to what is often believed, the broadness of PSD is not necessarily associated with the length of nucleation period. The PSDs at the end of nucleation are found to be independent of surfactant concentration. Simulation results indicate that at the completion of nucleation the particle size is reduced and the PSD narrows with decreasing rate of monomer addition despite nucleation time increasing. The broad distribution of particles frequently encountered in semibatch emulsion polymerizations is therefore attributed to stochastic broadening during the growth stage. The zero‐one‐two‐three model developed in this article allows perceiving that the dominant kinetic mechanism may be different for particles with different sizes. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

The dissociation rate coefficient of persulfate in emulsion polymerization systems

The effects of various components in an emulsion polymerization system on the dissociation rate coefficient of persulfate at 50 °C are examined using iodometry. Styrene monomer is found to enhance greatly the dissociation, while there is either no effect or possibly a slightly reduced rate of dissociation with methyl methacrylate monomer. The saturated analogues of these monomers (ethylbenzene and methyl isobutyrate) also enhance the dissociation, although not as much as styrene. Thus, such analogues should not be used as model compounds for determining the effect of a monomer on decomposition rate. The presence of metal parts in the reactor (e.g. as part of the agitation system) also could enhance the dissociation. The accelerations are consistent with literature mechanisms involving transfer reactions of aqueous-phase species. These results have significant implication for the interpretation and prediction of entry efficiencies and particle formation rates in emulsion polymerization systems.     

Microemulsion polymerization kinetics and mechanisms

The mechanisms of microemulsion polymerizations stabilized by sodium dodecyl sulfate in combination with pentanol were investigated with a water‐insoluble dye as the probe. The major parameters chosen for study were the types of initiators [water‐soluble sodium persulfate (SPS) vs oil‐soluble 2,2′‐azobisisobutyronitrile (AIBN)] and the polarity of the monomers [relatively hydrophobic styrene (ST) vs relatively hydrophilic methyl methacrylate (MMA)]. Both continuous particle nucleation and limited particle flocculation had a significant influence on the polymerization kinetics. For the polymerizations investigated in this work, the relatively low initiation efficiency of AIBN resulted in a reaction system showing a quite different particle nucleation mechanism than that of the ST polymerization with SPS. The formation of particle nuclei in water was suppressed to some extent, and microemulsion droplet nucleation predominated in the ST polymerization initiated by AIBN. Homogeneous nucleation played an important role, and a mixed mode of particle nucleation (microemulsion droplet nucleation and homogeneous nucleation) was operative in the MMA polymerization. The MMA polymerization experienced stronger particle flocculation than its ST counterpart. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2005–2013, 2005     

Direct synthetic route for water-dispersible polythiophene nanoparticles via surfactant-free oxidative polymerization

Water-dispersible poly(thiophene-co-3-thiopheneacetic acid) (PThTA) nanoparticles were successfully prepared by Fe³⁺-catalyzed oxidative polymerization in the absence of a surfactant. This facile method adopted the recyclable FeCl₃/H₂O₂ initiator couple to yield a high conversion of approximately 97%, and the sodium salt of 3-thiopheneacetic acid (TA) was used for the colloidal stability of the PThTA nanoparticles. The particle formation and growth of PThTA were examined with photoluminescence (PL) spectroscopy and time-evolution variation of the particle number in the early period of polymerization. The final average particle size of PThTA was 320 nm, measured by dynamic light scattering (DLS). The number-average molecular weight of PThTA was about 2 × 10⁴ g/mol. The light-emitting properties of the PThTA nanoparticles in an emulsion state were studied with UV–vis absorption and PL spectroscopy, and it was found that the quantum efficiency increased from 1.43 to 3.22 with the polymerization time at an excitation wavelength of 405 nm. Our results provide new insights on surfactant-free oxidative polymerization and may serve as guidelines for the preparation of new conjugated polymer emulsion systems for potential optoelectronic devices.     

Semibatch styrene suspension polymerization processes

Emulsion and suspension polymerization processes have widely been studied for more than 40 years. Although both polymerization processes are performed in heterogeneous media, each one presents its own typical characteristics, such as the particle size distribution, molecular weight distribution, polymer particle nucleation rate, and polymerization rate. In this study, semibatch styrene suspension polymerizations were carried out with feed compositions typical of emulsion processes. The initial reactor charge resembled the recipe of standard styrene suspension polymerizations, and the emulsion polymerization constituents were added during the batch. The influence of the moment at which the emulsion feed was started on the course of the polymerization and the effects of the feed on the polymer properties were analyzed. The polymer particle morphology and the average molecular weights changed very significantly with the emulsion feed time, and the changes could lead to the production of broad molecular weight distributions. Core–shell polymer particles could also be obtained, with the core being formed of polymer particles originating from the suspension polymerization process and the shell being formed of polymer particles originating from the emulsion polymerization. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3021–3038, 2003     

乳液聚合成核阶段的模拟与分析

建立了乳液聚合成核阶段的Monte Carlo模型，并用计算机对一个体积为10^-17m^3的微型反应器中苯乙烯的乳液聚合进行了模拟。以计算机生成随机数作为自由基被胶束和乳胶粒捕获的几率，模拟了在微型反应器中每一个自由基的生成、被胶束或乳胶粒捕获的过程以及每一个乳胶粒的生成及增长过程。通过对每一个乳胶粒在增长过程中各参数的统计计算，研究了乳液聚合成核阶段诸参数(乳胶粒数目、乳胶粒直径与粒径分布、单体转化率、聚合反应速率等)与乳化剂浓度[S]及引发剂浓度[I]的关系。结果表明，苯乙烯的乳液聚合体系中乳胶粒数目与[S]^0.5996[I]^0.4016成正比：在成核阶段乳胶粒直径分布先变宽后变窄，乳液聚合过程中乳胶粒直径分布有自动变窄的趋势；成核阶段持续时间t12与[S]^0.60[I]^0.60成正比，成核阶段结束时的单体转化率X12与[S]^1.20[I]^0.20成正比。     

Particle nucleation mechanism for the emulsion polymerization of styrene with a novel polyester emulsifier

The particle nucleation mechanism in emulsion polymerization of styrene with a novel polyester emulsifier, 5‐sulfoisophthalic acid dimethyl ester sodium salt‐modified tetracarboxylic acid‐terminated polyester (SMTAPE), was investigated. The consumption of SMTAPE micelles was monitored by the measurement of surface tension during the emulsion polymerization. Kinetic studies and emulsifier consumption clearly showed that a continuous nucleation mechanism without Smith–Ewart interval II was characteristic of this system. It was attributed to the high concentration of SMTAPE emulsifier in the polymerization, which led to a large surface area and a vast number of micelles around 10 nm in size that served as the major locus of particle nucleation. A broad particle size distribution was observed throughout the reaction, and the nucleation period lasted well into the reaction until the disappearance of the micelles or the disappearance of monomer droplets. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1061–1070, 2001     

Hyperbranched polymers from divinylbenzene and 1,3-diisopropenylbenzene through anionic self-condensing vinyl polymerization

Hyperbranched polymers were synthesized using anionic self-condensing vinyl polymerization (ASCVP) by forming ‘inimer’ (initiator within a monomer) in situ from divinylbenzene (DVB) and 1,3-diisopropenylbenzene (DIPB) using anionic initiators in THF at −40 °C. The reaction of equimolar amounts of DVB and nBuLi results in the formation of hyperbranched poly(divinylbenzene) through self-condensing vinyl polymerization (SCVP). The hyperbranched polymers were invariably contaminated with small amount of gel (<15%). No gelation was observed when using DIBP with anionic initiators. The presence of monomer-polymer equilibrium in the SCVP of DIPB restricts the growth of hyperbranched poly(DIPB). The inimer synthesized from DIPB at 35 °C undergoes intermolecular self-condensation to different extent depending on the nature of anionic initiator at −40 °C. The molecular weight of the hyperbranched polymers was higher when DPHLi was used as initiator. A small amount of styrene ([styrene]/[Li⁺]=1) was used to promote the chain growth by inducing cross-over reaction with styrene, and subsequent reaction of styryl anion with isopropenyl groups of inimer/hyperbranched oligomer. The hyperbranched polymers were soluble in organic solvents and exhibited broad molecular weight distribution (2<M_w/M_n<17).     

Particle nucleation and growth mechanisms in miniemulsion polymerization of styrene

Styrene miniemulsion polymerizations stabilized by sodium lauryl sulfate in combination with a reactive costabilizer, lauryl methacrylate (LMA) or stearyl methacrylate (SMA), were studied. A small amount of extremely hydrophobic dye was incorporated into monomer droplets (10² nm in diameter) to investigate particle nucleation and growth mechanisms. In addition to monomer droplet nucleation, particle nuclei generated in the aqueous phase (homogeneous nucleation) also play an important role in both LMA‐ and SMA‐containing polymerization systems. The way that these two nucleation mechanisms compete with each other is closely related to the water solubility of the costabilizer (LMA > SMA). The fraction of latex particles originating from homogeneous nucleation increases with decreasing hydrophobicity of the costabilizer. Zeta potential data of latex particles and the molecular weight and molecular weight distribution of emulsion polymers provide supporting evidence for the proposed competitive particle nucleation and growth mechanisms. © 2002 Society of Chemical Industry     

Miniemulsion polymerization of styrene with polymeric costabilizers

The polymeric costabilizers poly(stearyl methacrylate‐co‐2‐hydroxyethylmethacrylate) (PSH) and poly(lauryl methacrylate‐co‐2‐hydroxyethylmethacrylate) (PLH), composed of a hydrophilic backbone and several hydrophobic alkyl (stearyl or lauryl) side chains, were prepared by the free‐radical copolymerization of stearyl methacrylate (SMA) or lauryl methacrylate (LMA) with 2‐hydroxyethylmethacrylate and evaluated in the miniemulsion polymerization of styrene (ST). For comparison, the reactive costabilizers SMA and LMA were also included in this work. The hydrophobicity of costabilizers in increasing order was PLH < PSH < LMA < SMA. Only a small amount of these comb‐like copolymers was capable of producing kinetically stable ST emulsion droplets. The more hydrophobic the costabilizer was, the more effective was the costabilizer in the retardation of Ostwald ripening. About 30–40% of the monomer droplets were successfully converted into latex particles during the polymerization. The degree of monomer droplet nucleation increased with increasing hydrophobicity of the costabilizer. The formation of particle nuclei in the continuous aqueous phase played a crucial role in the polymerization kinetics. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1961–1969, 2004