Semibatch emulsion polymerization of butyl acrylate. I. Effect of monomer distribution

The effects of initial monomer charge on the particle formation and on the rate of polymerization were investigated for semibatch emulsion polymerization of butyl acrylate using sodium lauryl sulfate (SLS) as a surfactant and potassium persulfate (KPS) as an initiator. For the semibatch process with monomer (M) feed, it was found that by varying the monomer distribution ratio between the initial reactor charge and the feed it is possible to alter the contribution of monomer‐flooded and monomer‐starved nucleation mechanisms to the whole nucleation process. The number of particles increases as the initial monomer charge decreases, if the monomer concentration is below a critical value for any fixed system. The increase in number of particles is associated with a broad particle‐size distribution which might depict an emerging second peak on the particle‐size distribution curve. For low emulsifier concentration systems, a larger number of particles was obtained for a lower amount of monomer charge. Particle coagulation and emulsifier adsorption on the monomer droplets were counted as the main reasons for such behavior. For a semibatch process with monomer emulsion (ME) feed, the larger number of particles was formed at a lower initial monomer charge, similar to an M‐add semibatch process. However, the application of monomer charge to an ME‐add process was found to increase the possibility of secondary nucleation and led to the occurrence of a bimodal particle‐size distribution. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3094–3110, 1999     

Semibatch anionic ring-opening polymerization of octamethylcyclotetrasiloxane in emulsion

The semibatch anionic ring-opening polymerization of octamethylcyclotetrasiloxane in emulsion was studied under the condition of no seed particles used in polymerization system. Concentration of emulsifier was set above critical micelle concentration. Effect of monomer feed rate on the chemical kinetics, average particle size and distribution and on the polymer molar mass and distribution was investigated. During monomer addition, polymerization rate was constant and controlled by the monomer feed rate. According to the proposed mechanism for anionic polymerization in emulsion, it was assumed that also the number of active polymerization sites and monomer concentration at the particle surface, where propagation occurs, remain constant. A continuous increase of average particle size and absence of extensive condensation reactions at high conversion suggested that the freshly added monomer diffuses toward hydrophobic polymer particles, where it is consumed in propagation reaction and/or accumulated in the particle core.     

Study of different types of monomer emulsion feedings to semibatch emulsion polymerization reactors

Semibatch emulsion polymerization processes with a monomer emulsion feed are of great importance in both academia and industry. Monomer emulsion feeds can be applied to semibatch reactors using either a stream of an emulsified monomer or two streams of a neat monomer feed and an aqueous solution of an emulsifier. The effect of the feeding policy on the rate of polymerization and on the secondary particle formation was studied for a seeded semibatch emulsion polymerization of styrene. When a single-stream monomer emulsion feed is applied to a semibatch process, the monomer-swollen micelles formed in the feed might become the locus of initiation upon entering the reaction vessel. Under the conditions of this study, the application of monomer emulsion feed in either one stream or two streams did not result in secondary particle formation. The incoming monomer-swollen micelles were disintegrated to supply emulsifier molecules for the stability of growing particles, before they can capture radicals and become polymer particles. The rate of polymerization was found to be independent of the way that the monomer emulsion feed is added. In the absence of nitrogen, the rate of polymerization decreased more appreciably for the monomer emulsion feed, due to the oxygen dissolved in the emulsified monomer. The number of particles, however, was not affected by the purging policy. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2472–2477, 2001     

Semibatch anionic ring‐opening polymerization of octamethylcyclotetrasiloxane in emulsions: effect of the amount of seed polymer particles

Semibatch anionic ring‐opening polymerization of octamethylcyclotetrasiloxane with the use of seed polymer particles in emulsions was studied. The concentration of the emulsifier was set above the critical micelle concentration. We investigated the effect of the amount of seed polymer particles on the chemical kinetics and the average particle size and distribution. During monomer starving conditions the polymerization rate strongly depended on the monomer feed rate and not on the amount of seed particles. Throughout the entire monomer feed period the average particle size increased. This increase depended on the number and the size of seed particles. In emulsions with higher particle sizes higher equilibrium conversions were obtained. In our opinion, a greater extent of backbiting reactions is responsible for lower equilibrium conversions during and at the end of the process. The seeded semibatch process seems a reasonable choice for designing emulsion products with high monomer conversion and desired particle size. © 2012 Society of Chemical Industry     

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     

Particle size distribution control in emulsion polymerization

Effects of the operating policies—the initial initiator amount; the initial emulsifier amount; the monomer addition mode: batch or semibatch; and the monomer addition rate under “monomer‐starved conditions” for the control of particle size distribution (PSD)—were studied through a model that simulates batch and semibatch reactor operations in conventional emulsion polymerization. The population balance model incorporates both the nucleation stage and the growth stage. The full PSDs were reported, which have normally been omitted in earlier studies. It was shown through simulations that the broadness of the distributions, both initial (obtained after the end of nucleation) and final (after complete conversion of monomer), can be controlled by the initial initiator amount and the emulsifier amount. The higher initiator amounts and the lower emulsifier amounts favor narrower initial and final distributions. The shape of the initial PSDs and the trends in the average size and range were preserved with subsequent addition of monomer in the batch or in the semibatch mode, although the final PSD was always considerably narrower than that of the initial PSD. The addition of monomer in the semibatch mode gave narrower distribution compared to that of the batch mode, and also, lower monomer addition rates gave narrower distributions (larger average sizes), which was a new result. It was further shown through simulations that, under monomer‐starved conditions, the reaction rate closely matched the monomer feed rate. These conclusions are explained (1) qualitatively—the shorter the length of the nucleation stage and the larger the length of the growth stage (provided the number of particles remains the same), the narrower is the distribution; and (2) mathematically—in terms of the “self‐sharpening” effect. Experimental evidence in favor of the self‐sharpening effect was given by analyzing the experimental particle size distributions in detail. The practical significance of this work was proposed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2884–2902, 2004     

Thiol-ene emulsion polymerization using a semi-continuous approach

The thermally initiated thiol-ene emulsion polymerization of diallyl phthalate (DAP) diene and ethylenedioxy diethanthiol (EDDT) dithiol monomers in batch and semibatch emulsion polymerization is investigated. The batch process leads to larger and broader particle sizes than when the polymerization is carried out in semibatch. The evolution of the particle size and the final particle size distribution indicate that the stability of the latexes is limited and, hence, aggregation phenomena occurred in both processes. In particular, the evolution of the particle size distribution (PSD) in the semibatch process indicates nucleation, growth, and aggregation occurring simultaneously that produced a bimodal particle size. When the diene monomer was changed to diallyl terephthalate (DATP), the semibatch polymerization yielded smaller particles and narrow distribution without any indication of aggregation. The partial substitution of the dithiol by a trithiol monomer that is substantially more water insoluble affected nucleation of the particles, yielding for both systems smaller particles. The polythioether polymers synthesized present low glass transition temperatures (~ −30/−40°C) and those containing the therephthalate yield crystalline films. The potential application of the polymers as pressure sensitive adhesives (PSAs) was preliminarily assessed.     

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。     

Preparation and characterization of cationic copolymer latex. 1. Emulsion copolymerization of styrene with 4-vinylpyridine in the presence of non-ionic emulsifier

A study was made of the effect of 4-vinylpyridine (VP) on the kinetics of the emulsion polymerization of styrene (St) and on the distribution of polymeric VP in the cationic latex. Bimodal distribution of particle diameter was obtained in the polymerization under the conditions of low emulsifier concentration and high VP fraction in monomer feed. This would be caused by insufficient stabilization of resulting particles and by some changes in the character of growing radicals in aqueous phase with conversion. Polymerization under acidic conditions was affected by the amphiphilicity of VP-rich radicals which depended on VP fraction in monomer feed. On the surface of the latex particles prepared at pH 2 polymeric VP located preferentially whereas the latex particles prepared at pH 11 had a nearly statistical distribution of VP on their surface.     

Some factors affecting the particle growth in semicontinuous emulsion polymerization of acrylic monomers

Semicontinous emulsion polymerization of ethyl acrylate/ethyleneglycol dimethacrylate (90/10) and butyl acrylate/ethyleneglycol dimethacrylate (90/10) was studied. In the process a monomer emulsion feed was used, and the particle growth and the particle flocculation were found to be a competitive process. This was affected by distribution of water phase as well as by the distribution of emulsifier between the initial reactor charge and the emulsion of monomers. Several periods of particle generation were found during the process. The extent of particle flocculation was strongly affected by electrolyte concentration in the system and by copolymerization of acid groups containing comonomers.     

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     

Stability of nanoparticles during semibatch emulsion polymerization of butyl methacrylate,in the presence of methacrylic acid via RSM

The size and stability of latex particles in the semibatch emulsion polymerization of butyl methacrylate (BMA), in the presence of 0–10% methacrylic acid (MAA), were investigated. Response surface methodology (RSM), as a design of experiment, was used to obtain a more systematic understanding of the role of emulsifier and MAA in the stability of the particles. The amount of coagulum can be greatly reduced by increasing the concentration of sodium lauryl sulfate (SLS) in the monomer emulsion feed (MEF) and initial reactor charge (IRC). On the other hand, increasing the concentration of SLS in the IRC can result in a decrease of the particles size. According to the experimental data, the yield of reaction can be improved with incorporation of MAA into the emulsion polymers. The size and morphology of particles were obtained by scanning electron microscopy (SEM). FTIR and titration were used to determine the percentage of MAA in the copolymer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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.     

A combinatorial approach to evaluation of monomer conversion and particle size distribution in vinyl chloride emulsion polymerization

This work is targeted to study emulsion polymerization of vinyl chloride monomer (VCM) using experimental and mathematical methods. To fulfill this goal, a computer code was developed on the basis of zero–one population balance by which the effects of initiator and emulsifier concentration on the evolution of VCM conversion were investigated in the course of polymerization. The model was also trained to capture the coagulation of the particles. This enabled to adopt a reliable way of evaluating the particle size distribution (PSD). In particular, the rates of homogeneous and micellar nucleation mechanisms were simulated and reasonably predicted alterations in the PSD and the number of polymer particles under the influence of aforementioned parameters. The results from modeling were satisfactorily consistent with the experimental outputs and obviously visualized the impact of initiator and surfactant concentration on the PSD of the prepared PVC latexes.     

Particle coagulation at semicontinuous emulsion polymerization. II. Characterization of surface groups

Semicontinuous emulsion polymerization of acrylic monomers with a monomer emulsion feed has been investigated. The amount of coagulum appearing during the polymerization under conditions of insufficient covering of particle surface by emulsifier was studied from the point of view of particle surface charge. Increasing the surface group concentration via copolymerization of butyl acrylate with acrylic acid or sulfoethyl methacrylate caused increased colloid stability of the system and a rapid decrease in coagulum formation. It was established that during the polymerization acid hydrolysis of ester groups took place, which caused an increase in the carboxyl groups concentration at the particle surface. These carboxyl groups contribute to the colloid stability of the polymerizing system.     

Anionic ring-opening polymerization of octamethylcyclotetrasiloxane in emulsion above critical micelle concentration

Batch anionic ring-opening polymerization of octamethylcyclotetrasiloxane in emulsion using nonionic and cationic emulsifiers was studied. The concentration of emulsifiers was set above their critical micelle concentration. Effects of emulsifier concentration, nonionic/cationic emulsifier ratio and cationic emulsifier/initiator (KOH) ratio on the kinetics, average particle size and distribution and on the average molecular weight and distribution were investigated and discussed. At the beginning of the polymerization, empty micelles, active micelles (polymer particles) and monomer droplets co-exist in emulsion. The transport of monomer from monomer droplets toward empty micelles was confirmed by monomer droplets and empty micelles disappearance and by formation of smaller particles. The transport of monomer from monomer droplets toward polymer particles was not confirmed, since the average polymer particle size did not increase during polymerization. It was proposed, that at lower conversions, monomer diffuses from polymer particle interior to particle surface, while at higher conversions, the monomer diffuses from larger to smaller polymer particles. Emulsifier concentration, nonionic/cationic emulsifier ratio and cationic emulsifier/KOH ratio have an evident effect on the kinetics and on the average molecular weight, thus demonstrating that cationic emulsifier participates to the initiation reaction.     

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     

Stability of carboxylated poly(butyl acrylate) latices during semibatch emulsion polymerization

The stability of latex particles in the semibatch emulsion polymerization of butyl acrylate (BA) in the presence of 0–10% acrylic acid (AA) was investigated. The amount of coagulum (i.e., large flocs caused by intensive coagulation) can be greatly reduced by an increase in the concentration of sodium lauryl sulfate (SLS) in the monomer emulsion feed. On the other hand, increasing the concentration of SLS in the initial reactor charge can result in an increase in the percentage of the particle volume change (i.e., a measure of the degree of limited flocculation) later in the process. Both the scrap and percentage of the particle volume change increase with an increase in the electrolyte concentration. Both the coagulation and secondary nucleation process can result in a significant deviation from the Novak model. Experimental data also show that latex particles comprising pure BA can lose their stability rapidly at higher total solids content because of the crowding effect. Incorporation of only 5% AA into the emulsion polymers greatly improves the latex stability. © 1996 John Wiley & Sons, Inc.     

Transitional emulsion polymerisation: Zero-one to pseudo-bulk

The transitional behaviours of emulsion polymerisation for styrene and butyl acrylate (BA) monomers from zero-one to pseudo-bulk regime were mechanistically investigated. A dynamic mathematical model, which incorporates cross-over mechanism from zero-one to pseudo-bulk kinetics was developed for emulsion polymerisation and compared with experimental data for conversion, particle size and molar mass. Particles smaller than cross-over size follow zero-one kinetics and particles greater than cross-over size, they follow pseudo-bulk kinetics. In our mechanistic approach, particles nucleated from micelles, grow until the cross-over size is attained, based on zero-one kinetics, and subsequently continue to grow based on pseudo-bulk kinetics. Key findings from our work are that the developed transitional model predictions agree reasonably with experimental data on process and product attributes such as conversion, average molecular weight, molecular weight distribution (MWD), average particle size and particle size distribution (PSD). Optimal strategies for semibatch operation was developed using reaction temperature and monomer feed rate as process variables with specified initial conditions.     

Particle coagulation at semicontinuous emulstion polymerization. I. Some factors affecting the process

The factors affecting the amount of coagulum appearing during the semicontinuous emulsion polymerization of acrylic monomers were studied. Monomers were added into the polymerization reactor in the form of emulsion. The stability of the polymerization system was greatly affected by the distribution ratio of a constant amount of emulsifier between the initial charge in the polymerization reactor and the monomer emulsion. The amount of arising coagulum was dependent also on the alkyl length of the alkyl acrylate and increased from ethyl acrylate to 2-ethylhexyl acrylate. The amount of appearing coagulum was essentially decreased by copolymerization with acrylic acid and sulfoethyl methacrylate, respectively. In the case of insufficient covering of particle surface by emulsifier, the colloid stability of polymerizing system was greatly increased by the presence of strong as well as weak acid groups chemically bound on the particle surface.