Calculation of the particle size distribution in suspension polymerization using a compartment-mixing model

A modelling strategy for effective estimation of the particle size distribution (PSD) in suspension polymerization is presented. The strategy consists of coupling a population balance equation (PBE) and a compartment-mixing (CM) model to account for the non-homogeneous mixing in the tank reactor. The values for the rate of energy dissipation of each compartment are estimated from Computational Fluid Dynamics (CFD) calculations and experimental reports on systems with the same agitator and geometric characteristics. Model predictions using the CM model are compared with predictions that assume homogeneous mixing and experimental data on PSD from styrene and divinylbenzene pilot-plant suspension polymerization reactors of 1 and 5 L with Rushton and PBT impellers.     

In-line evaluation of average particle size in styrene suspension polymerizations using near-infrared spectroscopy

The main objective of this article is evaluating the influence of average polystyrene particle size upon the near-infrared (NIR) spectra collected during suspension polymerization experiments and observing whether NIR spectroscopy may be used for in-line monitoring and control of average particle size. It is shown that NIR spectra are sensitive to changes of the average particle size, and that standard empirical models (PLS—partial least squares—and NN—neural networks) may be built to correlate average particle size and light absorbance at certain wavelengths fairly well. Finally, it is shown that these models allow the in-line evaluation of average particle size in styrene suspension polymerizations with NIR spectroscopy. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1737–1745, 1998     

Batch emulsion polymerization of vinyl chloride: Application of experimental design to investigate the effects of operating variables on particle size and particle size distribution

In this article, the influences of operating variables on the particle size (PS) and particle size distribution (PSD) of emulsion poly(vinyl chloride) in batch reactor were investigated using Taguchi experimental design approach. The variables were temperature (T), water to monomer weight ratio (R), concentrations of initiator ([I]) and emulsifier ([E]), and agitation speed (S). Scanning electron microscope was used together with image analysis software to determine the PS and PSD. Statistical analysis of results revealed that the PS of emulsion poly(vinyl chloride) strongly depends on emulsifier and initiator concentrations, respectively, whereas the other factors have no significant effects in the range of levels investigated in this study. Except initiator concentration, all factors have important influence on the PSD (significance sequence: S > R > T > [E]). It is implied from the greater influence of agitation speed relative to temperature on PSD that the shear coagulation predominates the Brownian coagulation in this system. The relative optimum condition for a typical paste application was also determined using overall evaluation criteria. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Seeding as a means of controlling particle size in dispersion polymerization

Two distinctively different seeded dispersion polymerization processes employing micron and submicron size seed particles, respectively, have been used to gain a better mechanistic understanding of the dispersion polymerization process. Using monodisperse micron-size PMMA particles as seed, it was found that when low monomer/polymer ratios (M/P < 2.50) were used in methyl methacrylate (MMA) seeded dispersion polymerizations, particle growth dominates and the number of particles remains unchanged (i.e., narrow distributions are preserved). However, when higher M/P ratios (>2.50) were applied, bimodal or trimodal particle size distributions were produced, which is considered to result from the competition between particle growth and secondary nucleation. When small amounts of submicron seeds were used with the initial intention of gaining a better understanding of the nucleation process, it was surprisingly found that the final number of micron size particles was nearly the same as the initial number of submicron seed particles over a relatively wide range of reaction conditions, including seed, initiator, stabilizer, and monomer concentrations, and the medium composition. These results indicate that within certain limits seeded dispersion polymerization can be a more robust means of controlling particle size than ab initio dispersion polymerization in terms of reproducibly producing a target particle size. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

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     

高转化率乳聚丁苯橡胶聚合过程中乳液相对分子质量分布与粒径分布考察

采用中石油吉化分公司乳聚丁苯橡胶高转化率大生产配方,考察了实验室聚合反应釜聚合反应单体转化率随反应时间的变化,采用激光粒度分析仪和凝胶渗透色谱仪测定了聚合反应不同单体转化率的胶乳的粒径分布与分子质量分布,结果表明：胶乳粒径呈正态分布,粒径主要集中分布在0.1μm附近,胶乳的平均粒径随反应时间的延长逐渐增大,但是增加的幅度越来越小;聚合反应时间在11 h前（即转化率小于72%）,胶乳的重均分子质量、Z均分子质量一直增大,而数均分子质量变化无明显规律;而分子质量分布宽度指数随反应的进行变小,表明调整的高转化率配方合成的丁苯橡胶可有效改善聚合生成的胶乳粒径分布。     

Measurement methods of particle size distribution in emulsion polymerization

The particle size distribution of polymer always develops in emulsion polymerization systems, and certain key phenomena/mechanisms as well as properties of the final product are significantly affected by this distribution. This review mainly focuses on the measurement methods of particle size distribution rather than average particle size during the emulsion polymerization process, including the existing off-line, on-line, and in-line measurement methods. Moreover, the principle, resolution, performance, advantages, and drawbacks of various methods for evaluating particle size distribution are contrasted and illustrated. Besides, several possible development directions or solutions of the in-line measurement technology are explored     

Formation of monodisperse polyacrylamide particles by dispersion polymerization: particle size and size distribution

Highly monodisperse polyacrylamide microparticles were directly prepared by dispersion polymerization in aqueous alcoholic media initiated by 2,2′‐azobisisobutyronitrile using poly(N‐vinylpyrrolidone) as a steric stabilizer. Monomer conversion was studied dilatometrically and polymer molecular weight was determined viscometrically. The hydrodynamic diameter of polymer particles and its distribution were measured with a dynamic laser light scattering spectrometer. The number of the nuclei produced in the early stage of the polymerization was found to be constant during the remainder of the polymerization. The influences of various polymerization parameters, such as initiator concentration, monomer concentration, stabilizer content, medium polarity, and polymerization temperature on the particle size and size distribution were systematically investigated. Copyright © 2003 Society of Chemical Industry     

Measurement based modeling and control of bimodal particle size distribution in batch emulsion polymerization

In this article, a novel modeling approach is proposed for bimodal Particle Size Distribution (PSD) control in batch emulsion polymerization. The modeling approach is based on a behavioral model structure that captures the dynamics of PSD. The parameters of the resulting model can be easily identified using a limited number of experiments. The resulting model can then be incorporated in a simple learning scheme to produce a desired bimodal PSD while compensating for model mismatch and/or physical parameters variations using very simple updating rules. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

Unsteady stirring method used in suspension polymerization of styrene

An unsteady stirring method, that is, coreverse rotation with different periodic intervals, was adopted to the suspension polymerization of styrene. Experiments were carried out in a 0.5‐L flat‐bottom flask with a six‐blade Rushton turbine. Parameters affecting the final particle size and the particle size distribution under the unsteady stirring conditions, such as the agitation speed and the periodic interval, had been studied in detail, and the results were compared with those under a steady stirring one. The experimental results showed that the average particle size decreased and the uniformity final particle size distribution could be significantly improved when unsteady stirring approach is used. These were explained as the result of the decrease of the coalescence rate during the suspension polymerization when the unsteady stirring method was used. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1431–1438, 2000     

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.     

酵母悬浮液进料时膨胀床空隙率和粒径分布的动态变化

引言 膨胀床吸附技术可以直接从细胞破碎液(未澄清液)中提取目标产物[1-3],而无需预先进行固液分离操作,具有快速、高效和集成化的特点.在实际应用中,料液中细胞(碎片)的存在将会影响到膨胀床的床层稳定性和操作性能[4-6].     

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.     

非均相聚合反应中乳化剂用量及搅拌状况对粒径大小的影响

以釜径为74mm,无挡板的玻璃搅拌釜为反应釜,恒温水浴为热源;自来水为冷却水组成了一套冷模的聚合反应实验装置,同时采用蜂蜡为分散相,去离子水为连续相,Span-80及Tween-60为乳化剂,以二叶平桨、二叶斜桨直边、二叶斜桨圆边及三叶后掠式搅拌桨叶为基准,分别研究了乳化剂用量及不同搅拌状况对粒径大小的影响。结果表明：在低转速下,三叶后掠式搅拌桨的搅拌效果最好;在一定范围内,同一转速下的树脂的平均粒径随乳化剂用量的增加而减小。     

悬浮聚合法制备微球状压敏胶的研究

以丙烯酸-2-乙基己酯(2-EHA)、丙烯酸甲酯(MA)和丙烯酸(AA)为共聚单体,聚乙烯醇(PVA)为分散剂,过氧化苯甲酰(BPO)为引发剂,采用悬浮聚合法制备了可重复粘贴的微球状PSA(压敏胶).研究了水油比(即水与主单体质量比)、软硬单体质量比、分散剂种类和搅拌速率等对聚合物粒径及PSA性能的影响.结果表明:当水...     

Synthesis of a latex with bimodal particle size distribution for coating applications using acrylic monomers

Multipart emulsion polymerization of methyl methacrylate (MMA) and butyl acrylate (BA) was carried out in this work. The target was to achieve stability during the polymerization and to determine the proper hydrophilic–lipophilic balance (HLB) value for the stable system, using different types of non-ionic emulsifiers, sodium lauryl sulphate and their combinations. After determination of proper value of HLB (36.2), the best emulsifier combination on the basis of minimization of coagulum level was determined. This combination was 20 wt.% of KENON30 to SLS. The effect of monomer feed composition on the dry latex film properties was investigated to approach a monomer feed composition dealt with a proper T_g. The prepared latex showed a bimodal particle size distribution, due to the proper feeding policy in semibatch emulsion copolymerization process. The monomer feed composition of 45 wt.% MMA and 55 wt.% BA with a proper T_g was selected for the final improvement of coating properties such as UV resistance and adhesion. Adding acrylic acid (AA) and N-methylol acrylamide (NMA) to the reaction mixture improved the UV resistance and adhesion property of dry latex film. The flow and leveling, gloss, adhesion, UV resistance and water resistance of the produced bimodal latex showed good quality in comparison with the similar commercial resins used in coating applications.     

纳米级碳酸钙悬浊液粒度分布的有效测定

利用超声衰减法对纳米级碳酸钙悬浊液中颗粒粒度分布进行了分析，为纳米颗粒悬浊液粒度分布的测量提供了新方向。实验结果表明，表面改性能够很好地改善纳米级碳酸钙在水中的润湿性及分散性，是实现纳米级碳酸钙悬浊液粒度分布有效测定的关键因素。另外，样品透射电镜分析结果表明，基于声衰减原理的声波粒度仪较好地反映了纳米级碳酸钙悬浊液中颗粒粒度分布情况。     

聚合条件对丁苯胶乳粒径的影响

通过乳液聚合方法合成了适用于聚氯乙烯(PVC)改性甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物(MBS)的种子胶乳,利用一步法工艺获得一定粒径的丁苯胶乳,研究了乳化剂加入量、加入方式,聚合温度,聚合反应时间对粒径的影响,合成了粒径在200～300nm的丁苯胶乳。     

Influence of the geometric factors of the experimental device used in suspension polymerization on the properties of poly(styrene‐co‐divinylbenzene) microparticles

The prediction of the final particle size for reactive systems such as the reactions of suspension polymerization is a complex matter. Thus, the preparation of very small microparticles is specially challenging, probably because of the coalescence of the polymeric beads taking place during the later stages of the polymerization. In this work, very small gel‐type styrene‐co‐divinylbenzene beads were synthesized by using a previously determined set of experimental synthesis conditions in which the stabilization of the dispersion of the monomeric droplets was ensured, and, under these conditions, the factors related to the geometry of the experimental device were modified to determine their actual effect on the final size of the microparticles. From the experimental results, a very simple and useful model was obtained that was able to predict the final size of the microparticles as a function of the values of the geometric factors of the reactor. This model indicates that the most influential factors in the final size of the microparticles are the liquid depth inside the reactor and the stirrer diameter; thus, an increase in the liquid depth produces larger particles, and, conversely, the particle size decreases when using larger stirrer diameters. Additionally, the model permits the design of polymerization experiments aimed at obtaining microparticles with a diameter smaller than 50 μm. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012