The preparation of small polystyrene latex particles

The effects of several variables in the preparation of small-sized polystyrene latex particles are described. A semicontinuous preparation using microlatexes obtained by microemulsion polymerization as a seed is compared with a batchwise preparation employing the same ingredients. The particles in the batch products prove to be slightly larger in size but are more narrowly distributed. Furthermore, the effects of both the surfactant type and the ionic strength on the particle size in the batchwise emulision polymerization of styrene are reported. The systems do not obey the linear Smith–Ewart relationship with respect to the micellar surfactant concentration, although in the microemulsion polymerization of styrene the Smith–Ewart relationship is found to be valid with respect to the initiator concentration. Surfactants with a low critical micelle concentration increasingly promote the formation of smaller particle sizes. Salt is found to decrease the particle size when using a strong adsorbing surfactant. However, in the case of a weak adsorbing surfactant, an increase in particle size has been observed above a certain salt concentration.     

Ultrasonically initiated free radical‐catalyzed emulsion polymerization of methyl methacrylate (i)

The emulsion polymerization of methyl methacrylate initiated by ultrasound has been studied at ambient temperature using sodium lauryl sulfate as the surfactant. The investigation includes the: (1) nature and source of the free radical for the initiation process; (2) effects of different types of cavitation; and (3) dependence of the polymerization rate, polymer particle number generated, and the polymer molecular weight on acoustic intensity, argon gas flow rate, surfactant concentration, and initial monomer concentration. It was found that the polymerization could be initiated by ultrasound in the emulsion systems containing methyl methacrylate, water, and sodium lauryl sulfate at ambient temperature in the absence of a conventional initiator. The source of the free radical for the initiation process was found to come from the degradation of the sodium lauryl sulfate, presumably in the aqueous phase. The weight average molecular weight of the poly(methyl methacrylate) obtained varied from 2,500,000 to 3,500,000 g mol⁻¹, and the conversion for polymerization was up to 70%. Deviations from the Smith–Ewart kinetics were observed. The polymerization rate was found to be proportional to the acoustic intensity to the 0.98 power; to the argon gas flow rate to the 0.086 power; to the surfactant concentration to the 0.08 power, with the 0.035M–0.139M surfactant concentration range; and to the surfactant concentration to the 0.58 power, with the 0.139M–0.243M surfactant concentration range. The polymerization rate was found to increase with increasing initial monomer concentration up to a point where it became independent of initial monomer concentration. The polymer particle number generated per milliliter of water was found to be proportional to the acoustic intensity to the 1.23 power; to the argon gas flow rate to the 0.16 power; to the surfactant concentration to the 0.3 power, with the 0.035M–0.139M surfactant concentration range; and to the surfactant concentration to the 1.87 power, with the 0.139M–0.243M surfactant concentration range. The polymer weight average molecular weight was found to be proportional to the acoustic intensity to the 0.21 power, and to the argon gas flow rate to the 0.02 power. It was found to be inversely proportional to the surfactant concentration to the 0.12 and 0.34 power, with the 0.035M–0.139M and the 0.139M–0.243M surfactant concentration ranges, respectively. The polymer yield and polymerization rate were found to be much larger than those obtained from an ultrasonically initiated bulk polymerization method. The polymerization rates obtained at ambient temperature were found to be similar to or higher than those obtained from the conventional higher temperature thermal emulsion polymerization method. This investigation demonstrated the capability of ultrasound to both initiate and accelerate polymerization in the emulsion system, and to do this at a lower temperature that could offer substantial energy savings. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 797–825, 1999     

Toward a better understanding of the emulsion polymerization of butadiene. I. Continuous conductivity measurements

Continuous conductivity measurements were performed during the batch emulsion polymerization of butadiene along with kinetic and particle size measurements. The critical monomer conversion was obtained around 55% and the rate of polymerization was correlated to the surfactant concentration with an exponent of 0.35 which was not in agreement with the exponent offered by Smith and Ewart. In addition, the evolution of some particle‐related quantities such as particle size and number of particles during the three intervals of the emulsion polymerization and their agreements with Smith‐Ewart mechanism were investigated. The behavior of conductivity in the emulsion polymerization of butadiene normally containing a buffering agent was found to be completely different from the unbuffered one. Comparison of the conductivity profiles with the kinetic and particle‐related quantities represented that the conductivity of the reaction mixture is very sensitive to the changes in the particle size so that any small change in the forms of nucleation, growth, and coagulation is clearly observed in the conductivity profiles. Furthermore, the conductimetric data are capable of determining some important points during the polymerization such as the beginning of the reaction that can be important from the industrial process control point of view. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45262.     

Styrene miniemulsion polymerization stabilized by carboxylated polyurethane. II. Kinetics

A styrene miniemulsion was prepared using carboxylated polyurethane as the sole costabilizer and sodium dodecyl sulfate as the surfactant. The effects of the amount of carboxylated polyurethane, the amount of the initiator and surfactant, the presence of a water‐phase inhibitor (sodium nitrite), and the reaction temperature on the kinetics of the miniemulsion polymerization were investigated. The evolution of the particle size during the polymerization was measured. The results show that the polymerization rate was proportional to the 0.21 power of the surfactant concentration and the 0.30 power of azobisisobutyronitrile. The droplet nucleation and homogeneous nucleation were found to be coexistent in the polymerization. The hydrophility of the particle surface plays a key role in the nucleation of the particle and, therefore, has an important effect on the kinetics of the polymerization. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1941–1947, 2003     

Emulsion copolymerization of alpha-methylstyrene and styrene

Fast copolymerizations of styrene and alpha-methylstyrene can be achieved in emulsion systems where free-radical reactions in the bulk or solution are inefficient. The Smith–Ewart–Gardon theory of emulsion polymerization was developed for homopolymerizations but should extend to this copolymerization since the particular comonomers meet the basic assumptions of this model. Sodium lauryl sulfate surfactant provided faster initial polymerization rates, but steady-state conversions were faster with potassium laurate, especially at higher alpha-methylstyrene contents. This is ascribed to acceleration of potassium persulfate decomposition by the former soap. Monomer concentration in the polymerizing particles was constant during steady reaction rates. The rate of volume growth of particles during this interval was generally as predicted by theory. The number of particles and particle sizes could be predicted well if allowance was made for initiator wastage reactions. The observed average number of radicals per particle appeared to be 0.5. Analysis of the composition of monomer droplets and proton NMR analyses of copolymer compositions provided independent confirmations that the present emulsion copolymerization was consistent with the terminal copolymerization model.     

Polystyrene latex particles bearing primary amine groups via soap‐free emulsion polymerization

Polystyrene latexes were prepared in the presence of an amino‐containing functional comonomer, N‐(3‐aminopropyl)methacrylamide hydrochloride (APMH), via soap‐free batch emulsion polymerization initiated by the cationic initiator 2,2′‐azobis(2‐amidinopropane) dihydrochloride. These latexes were characterized by studying the influence of the ionic comonomers on the polymerization kinetics, particle size, surface charge density and colloidal properties. The synthesized latexes were monodisperse with a final size between 100 and 600 nm depending on the APMH concentration. The initial polymerization rate and the particle number increased in accordance with the Smith–Ewart theory for soap‐free styrene emulsion polymerization with a hydrophilic functional comonomer. The final functionalization rate of the particles has been particularly studied with the intention of fitting the prepared latexes to be used in the immobilization of biological molecules for biological sample preparation and diagnostic applications. © 2020 Society of Chemical Industry     

Influence of disproportionated rosin acid soap on the emulsion polymerization kinetics of styrene

The effect of disproportionated rosin acid soap (DRAS) on the emulsion polymerization kinetics of styrene has been studied. Batch experiments reveal a significant influence of chain transfer and limited particle coagulation on the polymerization process. For the recipes studied, the number of growing chains in the emulsion and consequently the polymerization rate were found to be independent of the particle number during the interval of coagulation. However, for relatively large particles (d_p ≈ 100 nm), the polymerization rate was proportional to the particle number, indicating Smith–Ewart case II kinetics. These effects have been shown to be well predicted by model calculations using a radical population balance over the particles. Since DRAS is derived from naturally occurring constituents found in pine trees, its performance, and with that the properties of the product latex, may vary significantly. However, if the performance of DRAS is known, the recipe and process conditions can be optimized. For this reason a procedure has been developed to quantify the performance of DRAS from the simple batch experiments discussed in this paper, the polymerization kinetics, and the information obtained about the coagulation process. © 1995 John Wiley & Sons, Inc.     

A kinetic study of vinyl acetate polymerization in aqueous media in the absence of emulsifier

In the absence of emulsifying agents, vinyl acetate polymerization in aqueous media was carried out at 50°C over a wide range of initial initiator and monomer concentrations to clarify the effect of reaction conditions on the kinetic behavior of the polymerization system. It was shown that the rate of polymerization was proportional to reaction time and initiator concentration and independent of the number of polymer particles present. The rate could also be successfully explained by the Smith and Ewart theory for emulsion polymerization when the dissolved monomer in water and the Trommsdorff effect were taken into consideration. A set of equations which could account for the effect of dissolved monomer in water on the rate of polymerization is proposed.     

Miniemulsion and conventional emulsion copolymerization of styrene and butadiene: A comparative kinetic study

The kinetics of conventional and miniemulsion copolymerizations of styrene and butadiene were compared using the Mettler RC1 calorimeter. A two‐step homogenization procedure was applied to obtain miniemulsions of these monomers with hexadecane as the costabilizer. The results indicated that the miniemulsion polymerizations proceeded mainly by nucleation in the monomer droplets, while in the conventional emulsion polymerizations, particle formation occurred by a combination of micellar and homogeneous nucleation. The overall rate of miniemulsion polymerization was faster than the corresponding conventional emulsion system if the surfactant concentration was below the critical micelle concentration (cmc) and slower if the surfactant concentration was above the cmc. The homogenization process is important for making stable miniemulsion systems, but had no effect on the conventional emulsion system (without hexadecane), most likely because of the second stage addition of the butadiene monomer. The dependencies of the rate of polymerization (heat of reaction) and number of particles on the surfactant concentration differed for the two types of polymerization systems. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2304–2312, 2006     

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     

Particle nucleation mechanism for the emulsion polymerization of styrene with a novel polyester emulsifier

The particle nucleation mechanism in emulsion polymerization of styrene with a novel polyester emulsifier, 5‐sulfoisophthalic acid dimethyl ester sodium salt‐modified tetracarboxylic acid‐terminated polyester (SMTAPE), was investigated. The consumption of SMTAPE micelles was monitored by the measurement of surface tension during the emulsion polymerization. Kinetic studies and emulsifier consumption clearly showed that a continuous nucleation mechanism without Smith–Ewart interval II was characteristic of this system. It was attributed to the high concentration of SMTAPE emulsifier in the polymerization, which led to a large surface area and a vast number of micelles around 10 nm in size that served as the major locus of particle nucleation. A broad particle size distribution was observed throughout the reaction, and the nucleation period lasted well into the reaction until the disappearance of the micelles or the disappearance of monomer droplets. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1061–1070, 2001     

Acrylic latices stabilized by polymerizable non-ionic surfactant

The final latex particle size is controlled by the concentration of polymerizable non-ionic surfactant NE-40 in the emulsion copolymerization of methyl methacrylate (MMA) and butyl acrylate (BA). The particle size decreases with increasing NE-40 concentration and increases with increasing persulphate initiator concentration. The dependence of particle size on the initiator concentration does not follow conventional Smith–Ewart theory, which is attributed to the bridging flocculation process during the particle nucleation period. The differences in the particle nucleation and growth stages and colloidal stability observed in the NE-40 and nonyl phenol-40 mol ethylene oxide adduct (NP-40) stabilized systems can be attributed to the different distribution patterns of surfactant molecules in the particles. Experimental data also indicate that the particle size decreases with increasing electrolyte concentration, or agitation speed. The total scrap, presumably caused by the bridging flocculation process, increases rapidly with increase in the NaCl concentration The amount of large flocs formed during polymerization is generally greater for the run operated at higher agitation speed. As expected, the latex products stabilized by non-ionic surfactants show excellent stability toward added sodium salt.     

Isothermal emulsion polymerization of n‐butyl methacrylate with KPS and redox initiators: Kinetic study at different surfactant/initiator concentrations and reaction temperature

Thermal initiators, although widely used in emulsion polymerization, are limited to high reaction temperatures due to their high activation energy. Redox initiators have low activation energies indicating that emulsion polymerization could be conducted at lower temperatures to save energy. In the present study, a redox initiator system comprised of hydrogen peroxide (H₂O₂) and ascorbic acid (AA) in conjunction with a Fe²⁺ ion catalyst is compared with a potassium persulfate (KPS) thermal initiator in an emulsion polymerization system consisting of n‐butyl methacrylate (BMA), sodium lauryl sulfate (SLS) and water. The dependence of particle number on surfactant and initiator concentrations shows that redox‐ and KPS‐initiated systems both follow the Smith‐Ewart theory. However, the high radical flux generated from the redox initiator results in the formation of much smaller latex particles and higher reaction rate with lower molecular weights. Latex particle size and molecular weight could also be influenced by reaction temperature. By using redox initiator, small monodisperse particles (diameter < 50 nm) can be achieved without using a large amount of surfactant. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43037.     

Rate coefficient for radical desorption in emulsion polymerization

Investigators have proposed the rate coefficient for radical desorption from polymer particles to explain the kinetic deviation of the emulsion polymerization of water-soluble monomers such as vinyl acetate and vinyl chloride from the classical Smith and Ewart theory.⁶ In this article, the rate coefficient for radical desorption is theoretically derived by a different approach, and its applicability to vinyl acetate and vinyl chloride emulsion polymerization is examined in detail using experimental data available in the literature. The theory developed here predicts the average number of radicals per polymer particle in the emulsion polymerization of vinyl acetate and vinyl chloride.     

Emulsion polymerization of styrene with amphiphilic random copolymer as surfactant: Predominant droplet nucleation

Amphiphilic random copolymer consisting of monomeric units of poly (butyl acrylate) and poly (maleic acid salt) was synthesized and characterized. The emulsion polymerization kinetics of styrene stabilized by this copolymer was investigated. The influencing factors, including polymeric surfactant concentration, initiator concentration and polymerization temperature, were systematically studied. The kinetic data show that the polymerization rate (R_P) increased with the increase of the polymeric surfactant concentration ([S]) and polymerization temperature (T). At the higher [S], droplets nucleation and micelle nucleation coexisted in the polymerization system; at the lower [S], only the droplets nucleation process existed. The polymerization did not follow Smith‐Ewart Case II kinetics. Dynamic light scatter and transmission electron microscope were utilized to measure the sizes and shapes of the particles, respectively. It would be speculated that a kind of large heterogeneous particles with multiple‐active‐sites was formed in the polymerization system. The increasing of R_P with increasing initiator concentration ([KPS]) was rapid at a medium [KPS], but the slowly increasing was observed at a lower or higher [KPS]. It was attributed to the barrier effect of the polymeric surfactant around the monomer droplets. The polymerization activation energy was 60.29 kJ/mol. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Kinetics of the emulsion copolymerization of MMA/BA in the presence of sodium montmorillonite

The kinetics of the emulsion copolymerization of methyl methacrylate/butyl acrylate (MMA/BA = 50/50) in the presence of sodium montmorillonite (Na-MMT) was investigated. Sodium laurylsulfate was used as surfactant at different concentrations and potassium persulfate as initiator. Two series of experiments were carried out at 30% and 10% solids content and varying the amount of surfactant and sodium montmorillonite. The effect of surfactant and sodium montmorillonite content on the stability of the final latices was assessed. The effect on particle nucleation, polymerization kinetics and molar mass distribution was also discussed, and compared with the predictions of the Smith–Ewart theory.     

Zur kinetik und teilchenbildung der fällungspolymerisation von acrylsäure in gegenwart von polystyrol-block-polyethylenoxid-copolymeren

A surfactant system containing polystyrene-block-poly(oxyethylene) and water was used for the free radical precipitation polymerization of acrylic acid in toluene. The use of this stabilizing system makes it possible to produce poly(acrylic acid) dispersions with a particle diameter ranging from 50 to 300 nm and solid contents up to 40 wt.-%, which remain stable for months. The rate of polymerization, which was measured on-line in a reaction calorimeter shows a strong autocatalytic behavior. The maximum of the polymerization rate and the corresponding time of appearance depend strongly on the water content. The influence of the composition of the surfactant (block length), its concentration and the concentration of initiator and monomer on the polymerization rate and the particle diameter were studied. Especially by varying the block length of the copolymer, the number of particles, respectively the particle diameter, can be controlled. To describe the course of the polymerization process, a model based on the theory of homogeneous particle nucleation is suggested. The influence of water on the swelling equilibrium of the poly(acrylic acid) particles is taken into account.     

Emulsion polymerization of ethylene. V. Kinetics and mechanism

The solubility of ethylene was measured in water, water–tert-butyl alcohol, water-emulsifier, water-tert-butyl alcohol-emulsifier, and water–tert-butyl alcohol–emulsifier–polyethylene. The polymerization of ethylene in an emulsion system differs from that of other vinyl monomers in several ways: the rate of polymer formation is inversely proportional to the emulsifier concentration and to the number of particles, the molecular weight of the polymer increases as the particle size increases, the polymer contains bound emulsifier whose concentration depends inversely on the particle diameter. These peculiarities are attributed to a transfer reaction between polymer radicals and emulsifier adsorbed on the surface of the polymer particle. In the presence of a fatty-acid soap, the transfer probably occurs primarily at the carbon α to the carboxyl group.     

Synthesis of well‐defined,functionalized polymer latex particles through semicontinuous emulsion polymerization processes

The design of a semicontinuous emulsion polymerization process, primarily based on theoretical calculations, has been carried out with the objective of achieving overall independent control over the latex particle size, the monodispersity in the particle size distribution, the homogeneous copolymer composition, the concentration of functional groups (e.g., carboxyl groups), and the glass‐transition temperature with n‐butyl methacrylate/n‐butyl acrylate/methacrylic acid as a model system. The surfactant coverage on the latex particles is very important for maintaining a constant particle number throughout the feed process, and this results in the formation of monodisperse latex particles. A model has been set up to calculate the surfactant coverage from the monomer feed rate, surfactant feed rate, desired solid content, and particle size. This model also leads to an equation correlating the polymerization rate to the instantaneous conversion of the monomer or comonomer mixture. This equation can be used to determine the maximum polymerization rate, only below or at which monomer‐starved conditions can be achieved. The maximum polymerization rate provides guidance for selecting the monomer feed rate in the semicontinuous emulsion polymerization process. The glass‐transition temperature of the resulting carboxylated poly(n‐butyl methacrylate‐co‐n‐butyl acrylate) copolymer can be adjusted through variations in the compositions of the copolymers with the linear Pochan equation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 30–41, 2003     

Kinetics of emulsion polymerization of styrene using the reactive surfactant HITENOL BC20

The effect of the reactive surfactant HITENOL BC20 (polyoxyethylene alkylphenyl ether ammonium sulfate; 20 U of ethylene oxide (EO)) on the emulsion polymerization of styrene was studied via reaction calorimetry (Mettler RC1; 70°C). For polymerizations carried out above the cmc of BC20, the reaction kinetics and evolution of the number of particles (N_p) resembled those reported using the conventional surfactant sodium lauryl sulfate, indicating that nucleation proceeded by a combination of micellar and homogenous nucleation (Interval I and Stage 2). The reaction rate (R_p) not only increased with increasing initiator (K₂S₂O₈) and surfactant concentrations, as expected, but the increase in rate in Stage 2 was dependent on the initiator concentration and independent of the surfactant concentration. This is consistent with the proposed nucleation mechanisms. The molecular weight increased with increasing surfactant concentration and decreasing initiator concentration as would also be expected for a conventional surfactant. The dependencies of R_p and N_p on the BC20 and initiator concentrations, however, were lower than the classical Smith‐Ewart values (R_p ∝ [E]^0.47–0.52; R_p ∝ [I]^0.21–0.25) although R_p was found to be directly proportional to N_p. Chain transfer to the reactive surfactant is considered a likely source of divergence. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008