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     

醋酸乙烯酯乳液聚合数学模型(Ⅱ) 阶段Ⅱ与阶段Ⅲ模型

研究了较大亲水性单体醋酸乙烯酯(VAc)乳液聚合动力学,着重剖析了自由基解吸的影响及水相中的聚合反应对总聚合反应速率的贡献,提出了阶段Ⅱ和阶段ⅢVAc乳液聚合数学模型,成功地预计了聚合反应速率、自由基在乳胶粒中的分布及乳胶粒中平均自由基数随转化率的变化规律.并将模型预计结果和实验数据进行了比较和讨论.     

Mass transfer and radical flux effects in dispersed‐phase polymerization of isooctyl acrylate

The kinetics of dispersed phase polymerization of a highly water‐insoluble monomer (isooctyl acrylate) were explored in emulsion, miniemulsion, and microsuspension polymerization. The effects of monomer water solubility and choice of initiator (oil‐ vs. water‐soluble) strongly impact the final product (particle size and molecular weight distribution). For emulsion polymerization, as the surfactant concentration was increased, there was a transition from homogenous to micellar nucleation near the CMC, then a drop in nucleation rate at high surfactant concentration due to insufficient radical flux to support more nucleation. For miniemulsion polymerization, a slow rate of growth of (droplet) nucleation with surfactant concentration was found, followed (at the CMC) by an increase in the rate of nucleation with added surfactant as the mode of nucleation switched to micellar. The conversion‐time kinetics of microsuspensions could be modeled with a bulk polymerization model. IOA is sufficiently insoluble in the aqueous phase that emulsion polymerization may or may not be reaction limited. The presence of a stabilizer such a PAA, the use of an oil‐soluble initiator such as BPO, and the insolubility of IOA in the aqueous phase all push the polymerization locus toward droplet (microsuspension) nucleation and bulk kinetics.© 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5649–5666, 2006     

乳液聚合导致一种新的转相过程

借助电导率仪、光学显微镜和亚微粒子分析仪等测试手段。研究了乳液聚合导致一种新的转相过程,并用于八甲基环四硅氧烷的聚合中。研究表明:体系以 W/O 相态开始,单体由连续相向水相(分散相)内的胶束中扩散并发生聚合反应,形成 O/W/O 复合乳液。反应过程中连续相体积不断减小,分散相(O/W 复相)体积不断增大,当达到某一临界相比时,体系发生转相,转相后乳液为 O/W。对本实验物系,转相点临界相比主要由初始水油比和乳化剂浓度决定。同常规的乳液聚合相比,伴有转相现象的乳液聚合有其自身的特点,转相使得聚合速率、聚合物粒径及分布、乳液稳定性等发生变化。     

High pressure semibatch emulsion and miniemulsion copolymerization of vinyl acetate and ethylene

This study presents the experimental study of semibatch emulsion and miniemulsion copolymerization of vinyl acetate (VAc) and ethylene to vinyl acetate-ethylene (VAE) copolymer at 60°C and 80–300 psig. In the miniemulsion copolymerization, a water-soluble initiator (K₂S₂O₈) is used and VAc miniemulsion is prepared in presence of surfactant and cosurfactant using a sonicator or a high-shear homogenizer. Then, ethylene gas is supplied to the reactor at constant partial pressure. In a miniemulsion process, the mass transfer limitations of VAc from monomer droplets to the aqueous phase, and to micelles or polymer latex particles that are present in conventional macro-emulsion polymerization can be eliminated and the transfer of ethylene dissolved in the aqueous phase to the miniemulsion droplets is the major ethylene transport process for the polymerization. The experimental data show that the amount of ethylene incorporation into the copolymer is higher in miniemulsion polymerization than in emulsion polymerization. The ethylene pressure has been found to have a strong impact on the ethylene incorporation into the copolymer phase in both emulsion and miniemulsion copolymerizations but the increase is more pronounced in miniemulsion case. The VAE copolymer latex particles prepared by miniemulsion polymerization exhibited higher storage stability than those prepared by macro-emulsion polymerization.     

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。     

Reaction kinetics of vinyl acetate emulsion polymerization

Transport of free radicals out of latex particles into the aqueous phase plays an important role in the emulsion polymerization of vinyl acetate. This so-called “desorption” process involves chain transfer to monomer which generates a mobile and rather stable monomer-unit free radical followed by the diffusion of this free radical out of the latex particle. A kinetic model is developed based on the reaction mechanisms of such an emulsion system. The experimental data available in the literature are used to test the model under various polymerization conditions. Reasonable agreement between the model predictions and experimental data is observed.     

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.     

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.     

RADICAL DESORPTION IN EMULSION POLYMERIZATION OF VINYL ACETATE

In the present paper a model equation for calculating the radical desorption rate constant,k_0,in the emulsion polymerization of vinyl acetate was suggested and the various parameters forevaluating k_0 were determined.Effects of reaction temperature,emulsifier concentration,initiator con-centration,monomer conversion and phase ratio on k_0 were studied.It indicates that the desorptionof radicals from latex particles to aqueous phase must be taken into account in the modelling ofemulsion polymerization for the monomers with higher hydrophilicity such as vinyl acetate.     

Combined single particle growth and population balance modeling in stereoregular polymerization of styrene

Modeling and experimental analysis for syndiospecific polymerization of styrene over silica-supported metallocene catalyst was carried out. A detail model was developed by coupling the single particle growth model (PGM) with particle population balance equation. The model was employed to predict the effects of intraparticle mass transfer limitations and the initial catalyst particle size on the rate of polymerization and the particle size distribution (PSD) of syndiotactic polystyrene (sPS). The single PGM, based on a modified polymeric multigrain model, was first utilized to calculate the single particle growth rate and polymerization rate under intraparticle mass transfer limitations and different initial catalyst particle sizes. Then, the model was solved simultaneously with particle population balance equation to estimate the PSD of sPS under the same limitations. The single PGM results showed a significant radial distribution of styrene concentration across polymer growth. It was further noticed that the diffusion resistance was most intense at the beginning of the polymerization reaction and the effects of polymerization rate were stronger. Moreover, it appeared that increasing the initial catalyst particle size led to lower rate of polymerization. The PSD simulation results revealed that the mass transfer limitation, as well as the initial catalyst particle size made a strong impact on the PSD of sPS. In addition, the simulation results obtained from this model showed good agreement results with experimental data of sPS.     

几种不可逆加成-断裂型链转移剂在苯乙烯乳液聚合中的研究

研究了基于不可逆加成-断裂链转移机理的3种分子质量调节剂对苯乙烯乳液聚合的影响.主要考察了3种链转移剂对乳液聚合速率、乳胶粒子大小以及聚苯乙烯数均相对分子质量的影响.链转移剂的内在动力学、扩散和自由基解吸附行为决定了其分子质量调节效率、对聚合速率的影响程度和乳胶粒子大小.链转移常数高的α-苯磺酰甲基丙烯酸乙酯使苯乙烯乳液聚合速率下降明显,乳胶粒子粒径分布较宽,且聚合后期不能有效调节聚苯乙烯分子质量 ;而链转移常数相对较小的2,3-二氯丙烯对聚合速率和乳胶粒子粒径的影响轻微,并能全程控制聚苯乙烯分子质量 ;分子质量较大的正十二烷基-2-苯基烯丙基硫则因在乳液体系中的扩散较慢,难以调节聚苯乙烯的分子质量.     

聚合釜釜型对偏氟乙烯乳液聚合的影响

偏氟乙烯(VDF)乳液聚合工艺的聚合效果关键是取决于VDF单体与水介质中助剂之间的传质效率。为研究较佳的聚合工艺参数,分别采用立式和卧式聚合釜,投入种类和规格相同的原料,在相同的温度和压力等操作条件下,研究较佳的VDF乳液聚合工艺参数。实验结果显示:釜型及搅拌桨形式在很大程度上影响了传质效率,采用卧式聚合釜能以较少的引发剂和乳化剂,得到较快的反应速率、较高的含固质量分数,且乳液稳定性更佳。因此可以认为卧式聚合釜是VDF乳液聚合较佳的聚合设备。     

醋酸乙烯酯乳液聚合数学模型(Ⅰ) 阶段Ⅰ模型

研究了较大亲水性单体醋酸乙烯酯(VAc)乳液聚合的乳胶粒生成和生长过程,提出了VAc乳液聚合阶段Ⅰ数学模型.该模型既考虑到胶束成核机理,又考虑到水相中低聚物沉淀成核机理.研究了自由基解吸与吸附在单体珠滴上的乳化剂对VAc乳液聚合阶段Ⅰ动力学的影响,并对模型预计结果与实验数据进行了比较和讨论.     

抗冲改性剂ACR/PVDF对PVC制品力学性能的影响

通过在ACR聚合过程中加入含氟单体,将氟引到ACR聚合物的骨架上,生产出了抗冲改性剂(丙烯酸酯类共聚物ACR/PVDF)。含氟单体分别选用四氟乙烯(HFE)、六氟丙烯(HFP)、偏氟乙烯(VDF),使用这种含氟ACR抗冲改性剂的可使聚氯乙烯(PVC)制品的力学性能,热稳定性,耐候性均得到提高。最佳反应条件为:含氟单体为偏氟乙烯,原料摩尔比m(VDF)∶m(甲基丙烯酸甲酯,MMA)∶m(丙烯酸丁酯,BA)为12∶40∶48。     

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     

Copolymer composition control by means of semicontinuous emulsion copolymerization

The effect of two different monomer addition strategies on the chemical composition distribution of the copolymer formed by the (seeded) semicontinuous emulsion copolymerization of styrene and methyl acrylate has been investigated. 1. The addition of a mixture of the monomers at a constant feed rate results in a homogeneous copolymer, provided that extremely long process times are used (starved conditions). When not starting from a seed latex, aqueous phase polymerization was observed at low feeding rates. When using a seed latex, aqueous phase polymerization appeared to be negligible. 2. In order to achieve an optimal monomer addition pattern, a pragmatic approach is presented. An optimal monomer addition profile was calculated from accurate monomer partitioning data using a short iteration procedure. Gradient high performance liquid chromatography (HPLC) was successfully applied as a rigorous test of the homogeneity of the copolymer formed. The information obtained contains much more detail than in the case of using differential scanning calorimetry of ¹H NMR. In contrast to ¹H NMR that provides only average cumulative chemical compositions, the complete chemical composition distribution can be obtained by means of HPLC.     

Kinetics of emulsion copolymerization with acrylic acids

A kinetic model is presented that describes the reaction behavior of emulsion copolymerization systems where significant polymerization occurs in both the particle and aqueous phases. Equations for predicting aqueous-phase free-radical concentrations and aqueous-phase and particle-phase reaction rates are developed. A method for estimating the radical entry rate coefficient is also presented. The model is applied to two seeded carboxylated emulsion copolymerization systems, acrylic acid-styrene and methacrylic acid-styrene. Both experimental and predicted results reveal that the reaction behavior is greatly affected by the type of acid monomer, partition of monomer between the various phases, and locus of polymerization. The mechanism for the acrylic acid-styrene system is more complicated than that for the methacrylic acid-styrene system. Evidence suggests that the primary reaction locus in the acrylic acid-styrene system shifts from the particles to the aqueous phase after the hydrophobic monomer, styrene, has been consumed.     

Online monitoring of emulsion polymerization using electrical impedance spectroscopy

A frequency‐dependent electrical monitoring technique was developed for characterizing emulsion polymerization online. High resolution electrical impedance spectroscopy (EIS) was conducted to study emulsion polymerization of styrene in terms of the key process parameters. Relationships between EIS data and process and product attributes such as monomer conversion and particle size were investigated. Electrical impedance values were measured at frequencies ranging from 1 Hz to 100 kHz. EIS parameters revealed changes in emulsion properties with time for both aqueous and organic phases during polymerization. At relatively higher frequencies (≥1 kHz) EIS data were found to be dominated by events in the continuous phase showing transitions in polymerization rates and intervals, while changes in monomer droplet and polymer particle sizes were dominant at lower frequencies (1 Hz). The EIS data were found to correlate well with polymerization rate, monomer conversion and particle size profiles at the appropriate frequencies in real time. © 2014 Society of Chemical Industry     

Behavior of free radical transfer between aqueous phase and latex particles in emulsion polymerization

The free radical transfer between aqueous phase and latex particles was investigated in the seeded emulsion polymerization using potassium persulfate (KPS) as an initiator. The effects of seed particle size, initiator concentration and polymerization temperature on the radical entry into and/or exit from the particles were emphatically examined. The results suggest that the aqueous-phase radical entry into the particles should be a competitive process, i.e. the competition between radical diffusion from the bulk aqueous phase to the interface of particles and its reactions in the aqueous phase determines whether it may be adsorbed into the particles or not. This implies that the reactions and properties of radicals in the aqueous phase play an essential role in particle nucleation in the emulsion polymerization.