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     

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     

叔碳酸乙烯酯改性醋丙乳液的制备与性能研究

采用半连续种子乳液聚合,以丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)、乙酸乙烯酯(VAc)为主单体,丙烯酸(AA)为功能单体,叔碳酸乙烯酯(VeoVa10)为改性单体,合成了核壳型丙烯酸酯乳液。探讨了聚合温度、乳化剂、引发剂及功能单体与乳液性能的关系。通过单因素实验探讨了乳化剂用量、配比,改性单体用量等与乳液性能的关系。FT-IR和DSC测试结果表明,各单体之间发生了自由基共聚反应,乳液粒子为核壳结构。     

Dynamic optimization of semibatch vinyl acetate/acrylic acid suspension copolymerizations

This work performs the dynamic optimization of semibatch vinyl acetate (VAc)/acrylic acid (AA) suspension copolymerizations. The proposed dynamic optimization strategy is based on a direct search Complex algorithm and is used to control the copolymer composition along the batch. First, a sequential optimization procedure is used to determine the optimum AA concentration and feed rate profiles, required to provide the specified copolymer composition. In the second step, a sequential optimization procedure is coupled with a predictive controller to guarantee that the manipulation of feed flow rates can allow for attainment of the desired copolymer compositions. The optimization strategy is validated through simulation, by assuming that reactions are subject to perturbations of the reaction temperature, initiator, and VAc concentrations. It is shown that the proposed optimization strategy can be used successfully both for design of monomer feed rate profiles and removal of process disturbances during semibatch suspension copolymerizations, to keep the copolymer composition constant throughout the batch. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

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     

Seeded emulsion polymerization of n-butyl acrylate utilizing miniemulsions

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

醋丙乳液型纸塑覆膜胶的研制

以醋酸乙烯(VAc)为硬单体,丙烯酸丁酯(BA)、丙烯酸异辛酯(EHA)为软单体,丙烯酸(AA)、叔碳酸乙烯酯(VV-10)、丙烯酸羟丙酯(HPA)为功能单体,采用乳液聚合方法制备醋丙共聚乳液覆膜胶。讨论了玻璃化温度、功能单体、乳化剂以及引发剂的用量等因素对乳液性能的影响。实验结果表明,当玻璃化温度为23.14℃、w(功能单体)=10%、w(乳化剂)=2%、w(引发剂)=0.4%时,乳液的各项性能良好。     

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     

Optimal operations of semibatch solution polymerization of acrylamide with molecular distribution as constraints

In this work, optimal control profiles of a semibatch solution polymerization of an acrylamide system are investigated for the first time. The control variables are the monomer and initiator feed rates. The objective function is the operating time of each batch. One of the operating constraints is the maximum of the polymerization rate of the reaction, which is important due to the limitation of the heat-removal equipment. The expected number-average molecular weight and molecular weight distribution are also included as constraints in order to guarantee the quality of the products. A nonlinear programming approach developed by Jang and Yang is used for solving the equations. Several simulation and experimental runs show that the operation of this semibatch system is very smooth and conversions are fitted well by the model. The molecular weights and molecular weight distributions of the polymer products are also well controlled. © 1993 John Wiley & Sons, Inc.     

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.     

Graft polymerization of vinyl acetate onto silica

A method is reported for the surface grafting of polyvinyl acetate (PVAc) onto modified, nonporous silica. The silica surface was modified by silylation with vinyl(triethoxy) silane followed by graft polymerization of vinyl acetate. The graft yield was measured by thermogravimetric analysis and the monomer conversion was monitored by UV spectral analysis. The rate of the graft polymerization and the graft yield were proportional to the initial monomer concentration. Vinyl acetate conversion followed first-order kinetics and displayed a trend of increasing initial rate with increasing monomer concentration.     

Polymer chain extension in semibatch emulsion polymerization with RAFT‐based transfer agent: The influence of reaction conditions on polymerization rate and product properties

A mathematical model was developed for batch and semiemulsion polymerizations of styrene in the presence of a xanthate‐based RAFT agent. Zero–one kinetics was employed along with population balance equations to predict monomer conversion, molecular weight (MWD), and particle size (PSD) distributions in the presence of xanthate‐based RAFT agents. The effects of the transfer agent (AR), surfactant, initiator, and temperature were investigated. Monomer conversion, MWD, and PSD were found to be strongly affected by monomer feed rate. The polymerization rate (Rp), number average molecular weight (Mn) and particle size (r) decreased with increasing AR. With increases in surfactant and initiator concentrations Rp increased, whereas with increase in temperature Mn decreased, Rp increased and r increased. In semibatch mode, Mn and r increased with increase in monomer flow rate. By feeding the RAFT agent along with the monomer (F_M/F_AR = N_Mo/N_ARo = 100), Mn attained a constant value proportional to monomer/RAFT molar ratio. The observed retardation in polymerization and growth rates is due to the exit and re‐entry of small radicals. Thus, chain extension was successfully achieved in semibatch mode. The simulations compared well with our experimental data, and the model was able to accurately predict monomer conversion, Mn, MWD, and PSD of polymer products. Our simulations and experimental results show that monomer feed rate is suitable for controlling the PSD, and the initial concentration and the feed rate of AR for controlling the MWD and PSD. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Graft polymerization of vinyl acetate onto silica

The free‐radical graft polymerization of vinyl acetate onto nonporous silica particles was studied experimentally. The grafting procedure consisted of surface activation with vinyltrimethoxysilane, followed by free‐radical graft polymerization of vinyl acetate in ethyl acetate with 2,2′‐azobis(2,4‐dimethylpentanenitrile) initiator. Initial monomer concentration was varied from 10 to 40% by volume and the reaction was spanned from 50 to 70°C. The resulting grafted polymer, which was stable over a wide range of pH levels, consisted of polymer chains that are terminally and covalently bonded to the silica substrate. The experimental polymerization rate order, with respect to monomer concentration, ranged from 1.61 to 2.00, consistent with the kinetic order for the high polymerization regime. The corresponding rate order for polymer grafting varied from 1.24 to 1.43. The polymer graft yield increased with both initial monomer concentration and reaction temperature, and the polymer‐grafted surface became more hydrophobic with increasing polymer graft yield. The present study suggests that a denser grafted polymer phase of shorter chains was created upon increasing temperature. On the other hand, both polymer chain length and polymer graft density increased with initial monomer concentration. Atomic force microscopy–determined topology of the polymer‐grafted surface revealed a distribution of surface clusters and surface elevations consistent with the expected broad molecular‐weight distribution for free‐radical polymerization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 300–310, 2003     

Modeling poly(vinyl alcohol)-stabilized vinyl acetate emulsion polymerization. II. Comparison with experiment

The mathematical model presented in Part I, accommodating the emulsion polymerization of vinyl acetate stabilized with poly(vinyl alcohol), predicts experimental conversion and particle size data with reasonable accuracy. Model predictions of measurable variables exhibit sensitivity to variables affecting either primary ungrafted particle nucleation of flocculation kinetics, but are relatively insensitive to variables affecting poly(vinyl alcohol) grafting reactions and the resulting primary grafted particle concentration. Semibatch simulations indicate that independent increases in the vinyl acetate, poly(vinyl alcohol), and initiator levels of all increase the primary grafted particle population. It is unlikely, however, that this population exceeds the ungrafted counterpart under most commercial polymerization conditions. This relative insignificance of grafting during particle nucleation is also noted in literature data simulations where, with appropriate parameter adjustments, the model predictions agree well with the batch, thermal initiation data. © 1993 John Wiley & Sons, Inc.     

Loop polymerization of vinyl acetate

The emulsion polymerization of vinyl acetate was studied using a loop reactor. The results were compared with some earlier work done in a batch reactor. A parallel was drawn with the results obtained with a tubular loop reactor and with a continuous reactor using styrene as monomer. The same phenomena of the optimum conversion peak with styrene at the laminar turbulent flow transition zone also occurred for the vinyl acetate. The peak obtained in this case was, however, broader and in the lower turbulent zone. The effect of the surfactant concentration on the broadness of the peak is discussed.     

An investigation of the emulsion terpolymerization of 2-ethylhexylacrylate–vinyl acetate–acrylic acid

An investigation of the emulsion polymerization of 2-ethylhexylacrylate (EHA)—vinyl acetate (VAc)—acrylic acid (AA) has been done. It was found that the polymerization rate depends on the AA level and that particle nucleation occurs throughout the entire conversion range. At the 5% AA level, there is significant coagulation. The number of particles depends on the balance between nucleation and coagulation. Addition of a small amount of water-soluble comonomer has no significant effect on the course of polymerization, but the viscosity of the latex can increase significantly. The dependence of latex viscosity on pH on neutralization has been studied. The maximum viscosity reached on neutralization depends on the acrylic acid level and the semibatch policy used in the latex synthesis. Addition of salt is a simple and effective way to control viscosity buildup during neutralization.     

An experimental study of multiobjective dynamic optimization of a semibatch copolymerization process

Optimal open loop control strategies are developed for a semibatch free radical copolymerization of methyl methacrylate and vinyl acetate using the multiobjective dynamic optimization method. A detailed kinetic model is validated through experimentation and used for the design of optimal controls. Both monomer feed rate and reactor temperature are varied to produce the copolymer of desired composition and molecular weight. The open loop control policies are implemented in a process control computer and tested on an experimental stirred tank polymerization system. Excellent agreement between the model predictions and the experimental data have been obtained.     

Semibatch emulsion polymerization of butyl acrylate. II. Effects of emulsifier distribution

The effects of emulsifier distribution ratio between the initial charge and the feed on particle formation and kinetics of butyl acrylate emulsion polymerization, using sodium lauryl sulfate as emulsifier and potassium persulfate as initiator, were investigated. The number of particles increased with initial emulsifier concentration in the reactor charge. It was shown that traditional ranking, in terms of number of particles produced, of semibatch emulsion polymerization with monomer emulsion feed is not always justified and a semibatch emulsion polymerization can produce far more particles than a conventional batch emulsion polymerization. The number of polymer particles was found to be practically independent of the emulsifier distribution ratio between the charge and the feed for a high overall emulsifier concentration, while for a low overall emulsifier concentration, the number of particles increased with initial loading of the emulsifier. The polydispersity index (PDI) of the final latexes showed a minimum with emulsifier distribution. A bimodal particle size distribution, and a latex with a large PDI, was obtained when there was no emulsifier in the charge. As the initial emulsifier charge increased, a unimodal PSD with a smaller PDI was obtained. With higher proportions of emulsifier in the initial charge, the PDI rose again due to particle nucleation at monomer‐starved conditions, and a skewed unimodal PSD was obtained. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 582–597, 2001     

乙烯基硅氧烷改性丙烯酸酯乳液聚合的动力学及成核机理分析

用种子乳液聚合法研究了硅氧烷改性丙烯酸酯的乳液聚合,对影响种子乳液聚合动力学的因素进行讨论,并分析了乳液聚合的成核机理.实验结果表明：反应温度、引发剂浓度、乳化剂浓度和有机硅氧烷用量对有机硅改性丙烯酸酯乳液聚合动力学有较大的影响.反应温度越高,引发剂浓度越高、乳化剂浓度越高、有机硅氧烷用量相对较小,乳液聚合反应的转化率越高;此外,体系的pH值在6～8之间时也有利于反应的进行.种子乳液聚合中R_P∝［E］^0.72,R_P∝［I］^0.56,表观活化能E_a为143.92 kJ•mol^-1.种子乳液聚合初期,反应主要是单体液滴成核;进入壳层反应时,反应成核主要是以胶束成核为主.     

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