Modeling of semibatch styrene suspension polymerization processes

We developed a mathematical model to describe the behavior of semibatch styrene suspension polymerization processes, where the constituents of a typical emulsion polymerization process are added into the reaction vessel during the course of a typical suspension reaction. This technique was recently described for the production of core–shell polymer particles. The model assumes that the nucleated emulsion particles can agglomerate with the sticky and much bigger suspension particles and that the agglomeration rate constant is a function of the internal states of the suspended droplets. The proposed model presented good agreement with experimental conversion, average molecular weight, and molecular weight distribution data. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1950–1967, 2005     

Preparation of polystyrene/poly(methyl methacrylate) core‐shell composite particles by suspension‐emulsion combined polymerization

Suspension‐emulsion combined polymerization process, in which methyl methacrylate (MMA) emulsion polymerization constituents (EPC) were drop wise added to styrene (St) suspension polymerization system, was applied to prepare polystyrene/poly(methyl methacrylate) (PS/PMMA) composite particles. The influences of the feeding condition and the composition of EPC on the particle feature of the resulting composite polymer particles were investigated. It was found that PS/PMMA core‐shell composite particles with a narrow particle size distribution and a great size would be formed when the EPC was added at the viscous energy dominated particle formation stage of St suspension polymerization with a suitable feeding rate, whereas St‐MMA copolymer particles or PS/PMMA composite particles with imperfect core‐shell structure would be formed when the EPC was added at the earlier or later stage of St suspension polymerization, respectively. It was also showed that the EPC composition affected the composite particles formation process. The individual latex particles would exist in the final product when the concentrations of MMA monomer, sodium dodecyl sulfate emulsifier, and potassium persulfate initiator were great in the EPC. Considering the feature of St suspension polymerization and the morphology of PS/PMMA composite particles, the formation mechanism of PS/PMMA particles with core‐shell structure was proposed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Mechanism of particle formation in radical emulsion copolymerization of styrene with α-tert-butoxy-ω-vinylbenzyl-polyglycidol macromonomer

In the batch emulsion copolymerization of styrene and α-tert-butoxy-ω-vinylbenzyl-polyglycidol macromonomer, carried out at macromonomer concentrations exceeding the critical micelle concentration (c_mc), particles are formed by a two-step coagulative nucleation mechanism. This mechanism leaves its mark on morphology of particle interface, rate of polymerization and on molecular weight distribution of the obtained polymer. AFM studies revealed that the interface of particles is composed of objects with dimensions close to dimensions of the primary particles. Compartmentalization of styrene in the macromonomer micelles leads to the higher initial rate of styrene conversion than in the similar macromonomer free homopolymerization of styrene. The initial polymerization in the monomer-swollen macromonomer micelles, similar to the microemulsion polymerization, is responsible for the formation of the highest molecular weight component. In the mature particles there are two different polymerization loci: the interfacial layer and the core. This leads to bimodal molecular weight distribution of the formed polymer.     

Effects of mesoporous silica particles on the emulsion polymerization of methyl methacrylate

Rod‐like and spherical mesoporous SBA‐15 silica particles were synthesized as pure silicas and surface modified by organosilane coupling agents firstly, and then the effects of these mesoporous materials on the critical micelle concentration (CMC) of sodium dodecylsulfate (SDS), the stabilities of batch and semi‐continuous MMA emulsion polymerizations, and the molecular weights and molecular weight distributions of the polymer products were studied. The incorporation of both unmodified and silane‐modified forms of the mesoporous silica particles in the polymerization reaction increased the CMC of SDS. The presence of the unmodified mesoporous silica in the polymerization process led to instability in the batch emulsion polymerization process, as indicated by the formation of increased amounts of coagulum, and a decrease in the molecular weight of the polymer product. However, in comparison to the polymer formed in the absence of particle additives the molecular weight of the PMMA polymer increased with the amount of emulsifier and the addition of silane‐modified SBA‐15 particles, suggesting the growth of the polymer chains is facilitated at least in part by reaction in the pores of the particles. The improvement in molecular weight indicates that semi‐continuous MMA emulsion polymerization is best suited for the preparation of PMMA–mesoporous silica composites. POLYM. ENG. SCI., 54:2746–2752, 2014. © 2013 Society of Plastics Engineers     

The preparation of uniform polystyrene latices by true emulsion polymerization

Conventional emulsion polymerization of styrene produces some polydispersion in particle sizes in the latex. By carrying out a one-stage polymerization of finely emulsified monomer droplets of styrene formed in a mixture of methanol and water, it is possible to prepare stable latices of polystyrene in which the particles are perfectly uniform in size. The polymer has a relatively low molecular weight, but it is more stable to fragmentation by surfactant solutions than polystyrene prepared by conventional emulsion polymerization, the molecular weight of which is greater. The surface charge density of the particles is higher than that of particles produced by emulsion polymerization, and this probably accounts for the stability of the dispersion during polymerization and of the latex.     

Recalculation of the monomer reactivity and experimental differences in emulsion and microemulsion copolymerizations of partially water‐soluble monomers

On the basis of the copolymerization data for the emulsion and microemulsion polymerizations of ethyl acrylate and methyl methacrylate, the monomer concentrations at the copolymerization loci were calculated, with the assumption that the sum of their concentrations at the polymerization loci was equal to unity. The equivalency of the locus and feed concentrations, as for styrene, was invalid because of the partial water solubility of both the monomers. Consequently, the locus concentration rather than the initial feed concentration was used to recalculate the monomer reactivity at the actual site of polymerization, and this was called the true reactivity ratio. The apparent reactivity ratios for emulsion and bulk polymerizations were different, whereas those for microemulsion and bulk polymerizations were similar. This difference was attributed to the mode of polymerization in the emulsions and microemulsions, leading to different copolymer compositions for similar initial feed concentrations. This was verified experimentally from the thermal properties and particle size distribution measurements. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2802–2810, 2002     

In situ syntheses of a suspension agent based on a styrene–acrylic acid copolymer for the suspension polymerization of styrene

We carried out the suspension polymerization of styrene, initiated with benzoyl peroxide at 80°C, in the presence of the simultaneous polymerization of acrylic acid in the water phase, initiated by potassium peroxidisulfate (KPS) at the same temperature. The polymerization in the water phase was started at certain times after the beginning of the polymerization of styrene. Then, a continuous addition of KPS was carried out at a given landing rate and during variable feeding times. The water‐phase polymerization actually produced a copolymer of styrene and acrylic acid, which displayed surface‐active properties. The particle size distribution depended on the variables mentioned earlier (starting time, KPS feeding rate, and addition time), being controlled by the molecular weight, and on the composition of the copolymer produced and its availability at the increasing conversion of styrene. A second distribution of submicronic particles was produced. Both families of particles had about the same molecular weight. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3271–3285, 2002     

Preparation and characterization of monodisperse magnetic poly(styrene butyl acrylate methacrylic acid) microspheres in the presence of a polar solvent

Magnetic poly(styrene butyl acrylate methacrylic acid) [P(St–BA–MAA)] microspheres were prepared by emulsifier‐free emulsion polymerization in the presence of a polar solvent and a ferrofluid prepared by a coprecipitation method. The effects of some polymerization parameters, such as the medium polarity, reaction temperature, initiator content, and surfactant content in the ferrofluid, on the particle diameter and particle size distribution of magnetic P(St–BA–MAA) microspheres were examined in detail. The results showed that the electrostatic repulsion in the polymerization system significantly affected the monodispersity of the resulting magnetic polymer microspheres. The proper electrostatic repulsion, achieved through changes in the medium polarity and amount of surfactant in the polymerization system, improved the monodispersity, but a higher or lower repulsion led to a decrease in the monodispersity. Although the existence of surfactant and magnetite particles reduced the monodispersity more or less, the polymerization behavior of an emulsifier‐free emulsion polymerization in the presence of the ferrofluid was analogous to that of a conventional emulsifier‐free emulsion polymerization. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1733–1738, 2003     

Einfluß des stofftransportes bei der polymerisation von äthylen und 1-okten mit Ziegler-Katalysatoren

The polymerization of ethylene and 1-octene with supported Ziegler-catalysts was investigated with regard to the influence of mass transport of monomers on the kinetics, molecular weight and molecular weight distribution. In the case of the polymerization of ethylene, it was found that for certain conditions of reaction the mass transport of ethylene can influence the kinetics of polymerization respectively the catalyst efficiency strongly. The molecular weight and molecular weight distribution of the polyethylene formed are practically not affected by the conversion as well as particle size of catalyst and polymer. The molecular weight distribution however is affected by the concentration of the catalyst. The polymerization process of ethylene in suspension is distinguished by chemical and physical processes. A continuous chain initiation, for example, is based on the continuous reduction of the catalyst particles to small pieces during the course of polymerization. An apparent chain termination respectively catalyst deactivation can occur when catalyst particles are encapsulated within the growing polymer particles. The polymerization of 1 -octene for similar conditions of reaction gave polymers which were solved completely in the system used. The molecular weight distribution of the polymer formed nevertheless was very broad. This indicates that the mass transport of the monomers through the solid phase of polymer cannot be the main reason for the broad molecular weight distribution of the polymers which are produced by heterogeneous Ziegler-catalysts in suspension.     

Studies of water-soluble oligomers formed in emulsion copolymerization

A polymer chain transfer agent was synthesized by the reaction between poly(vinylbenzyl chloride) latex particles and 2-aminoethanethiol in a basic environment. In subsequent emulsion polymerization reactions, low molecular weight species were formed when waterborn oligomeric radicals diffused to the surface of these seed particles. These low molecular weight oligomers were separated by membrane filtration and their composition and molecular weight weight were analyzed by FTIR and mass spectroscopy. The measured composition results were compared with those that were calculated from the copolymerization equation. The molecular weights were compared with earlier experimental results that were obtained by isolation of oligomers formed when a water-soluble inhibitor was added to a reacting emulsion. Three seeded emulsion copolymerization systems, that is, styrene–acrylic acid, styrenemethacrylic acid, and styrene–methyl methacrylate, were investigated. The distribution of monomer in the water phase and in the copolymer particles was analyzed. The results show that the oligomer compositions for different copolymerization systems can be approximated reasonable well by the copolymerization equation, using the reactivity ratios obtained from bulk copolymerization. The length of the oligomer radicals formed depends on their composition and the properties of the polymer particles, such as surface charge, composition, size, and concentration. © 1994 John Wiley & Sons, Inc.     

Effects of styrene oligomers and polymers on the suspension polymerization behavior and properties of expandable polystyrene

Styrene oligomers are formed by a free‐radical mechanism during the thermal polymerization of styrene in storage. The effects of these compounds on the preparation of expandable polystyrene (EPS) were investigated with respect to suspension polymerization behavior and the properties of the impregnated polystyrene beads produced. Styrene dimers and trimers up to concentrations of 0.2 wt % did not affect the stability of the suspension during the polymerization and impregnation stages. Besides differentiated effects on the particle size distributions of the polymers and on the polymerization rate, no chain‐transfer activity of the oligomers was observed, and this confirmed the assignment of chain transfer to the Diels–Alder dimer in the literature. The investigation of the foaming behavior of the pentane‐impregnated EPS beads indicated a significant reduction of the prefoaming density caused by styrene dimers and trimers. This behavior resulted from a decrease in the glass‐transition temperatures of these polymers. The effects of high‐molecular‐weight polystyrene, formed in addition to oligomers during storage by the thermal polymerization of styrene, on the polymerization behavior and polymer properties of EPS were also investigated. The results showed a significant impact on the suspension stability that was dependent on the concentration of the high‐molecular‐weight polystyrene. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Study on emulsion and suspension in situ polymerization

A novel and simple method of emulsion and suspension in situ polymerization was designed for preparing a composite of polystyrene containing core–shell emulsion particles. The advantage of this method was that it did not need a complex process, such as emulsion breaking, washing, drying, and so on, during transforming from emulsion polymerization to suspension polymerization. First, the core–shell particles of poly(styrene/bisphenol A dimethyl methacrylate)/polystyrene [P(St/BPADA)/PS] with crosslinking structure were synthesized by emulsion polymerization. Then the latex was broken with electrolyte dripping and the emulsion particles became swollen and transformed into the monomer in the suspension polymerization system. Thus the emulsion and suspension in situ polymerization could be carried out successfully. The mechanism of the process was investigated in detail. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 404–412, 2005     

Core-shell structured latex particles. I. Copolymerization of styrene/benzyl methacrylate as a choice for shell material and characterization of poly(n-butyl acrylate) core latex particles

Composition, molecular weight, and microstructure of the “shell” polymer in core-shell structured latex particles, designed for toughening polycarbonate matrix, should be controlled for enhanced miscibility between the shell polymer and the matrix. Various “shell polymer” systems based on styrene (St) and benzyl methacrylate (BM) were synthesized. Reactivity ratios were determined for (St) and (BM). Chain transfer efficiency studies revealed the susceptibility of styrene to transfer to a chain transfer agent. Benzyl methacrylate was found to have steric and stability factors hindering its tendency to chain transfer with various chain transfer agent. Miscibility tests between P(St/BM) and polycarbonate (PC) indicated different degrees of miscibility, depending upon polymerization conditions. Factors other than molecular weight, such as branching and crosslinking, were found to play a role in the miscibility. Monodisperse poly(n-butyl acrylate) (PBA) seed latex particles of variable degree of crosslinking and particle size were successfully synthesized by batch emulsion polymerization. © 1995 John Wiley & Sons, Inc.     

Radiation-induced emulsion polymerization of vinyl acetate and styrene

Studies have been made of the γ-induced emulsion polymerization of styrene and comparisons made with chemically initiated emulsion polymerization. The polymerization proceeded smoothly to high conversions at 0 and 60°C, the reaction showing a high G (monomer) value. Complete conversions were obtained with total doses of less than 0.05 Mrad. In accordance with the behavior expected of systems having a constant rate of initiation, the molecular weight was found to decrease with decreasing temperature. The molecular weight and particle size distributions were narrower than those obtained in chemically initiated emulsion polymerizations at the same temperature. The radiation-induced emulsion polymerization of vinyl acetate proceeded smoothly at temperatures in the range 0–50°C to give polymers of much higher molecular weight than these obtained from chemically initiated polymerizations at the same temperature. Complete conversion was attained after a dose of 0.02 Mrad for latices approaching 50% solids. The elimination of ionic endgroups in the poly(vinyl acetate) radicals tends to drive the polymerization from the aqueous phase, resulting in faster rates and higher molecular weights than are obtained from chemically initiated systems. Rates of polymerization were found to be independent of temperature and the molecular weight of the polymer to be independent of dose rate. Latices of poly(vinyl acetate) of high solids content were evaluated for latex and film properties and found to have improvements over commercially available samples in both areas, especially in clarity of film and scrub resistance. A number of acrylate and maleate esters were copolymerized with vinyl acetate in a radiation-initiated emulsion system. High molecular weight copolymers were produced after low dose.     

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.     

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     

Power feed synthesis of pressure-sensitive latex adhesives

Latex particles with the same core composition of poly(MMA-co-ALMA) and different shell compositions of poly(BA-co-AA) were prepared by semibatch emulsion polymerization using ‘power feed’ monomer and chain transfer agent addition methods in the shell layers. The seed stage involved formation of seed particles of 111 nm in diameter with a batch process. After that, two growth stages formed the final particle diameter, d_z = 300 nm measured by dynamic light scattering. The gel content and the molecular parameters of the polymer were determined. The adhesive properties including loop tack, peel force and shear resistance were measured according to the FINAT test methods No. 9, 1 and 8. An evaluation was also made for the relationship between pressure-sensitive properties and molecular parameters. Introducing power feed to semibatch emulsion polymerization had no significant effect on the latex preparations and could improve the final conversion and the colloidal stability. The observed particles were grown without significant secondary nucleation. The power feed methods had no effect on the glass transfer temperature (T_g) of the shell layer also. Emulsion polymerization conducted by positive power feed resulted in the formation of longer primary polymer chains at the beginning than that conducted by negative power feed and standard uniform feed, which caused a very high gel fraction. As pressure-sensitive adhesives prepared by using the positive power feed had the highest gel content and strongest core–shell interaction, they exhibited the highest shear resistance, but the lowest tack and peel force.     

Precise control of polymer particle properties using droplets in the microchannel

In this study, we examined two types of oil–water, two-phase system polymerization by designing droplets of reaction space aiming precise control of polymer particle properties: (i) suspension polymerization using emulsion droplets, and (ii) slug polymerization using slugs of the segmented flow. For suspension polymerization, the particle size can be controlled up to a limited extend by varying the droplet size. And slug polymerization, which we proposed as a new polymerization method, enables continuous production of particles and independent control of polymer properties by separating the molecular control and precipitation processes. Our proposed method can be expected to contribute to precise control of polymerization reactions.     

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     

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.