Modeling of the styrene microemulsion polymerization

A mathematical model was developed to simulate the polymerization kinetics of styrene oil-in-water microemulsions. Nucleation of particles in microemulsion droplets was assumed to account for the number of particles generated. It was found that the entry rate coefficient of radicals into microemulsion droplets is much smaller than the entry rate coefficient into monomer-swollen particles. All particles contain at most one growing radical. Various radical entry mechanisms were evaluated using the simulation. The possibility of flocculation between particles during the later stages of the polymerization and the high desorption rate of monomeric radicals was suggested by the simulation results. The likelihood of re-entry of desorbed radicals was den onstrated.     

Effect of dose rate on emulsion and microemulsion polymerization of styrene

Emulsion and microemulsion polymerization of styrene were initiated with a gamma ray to study the effect of dose rate on polymerization. In both systems, there is an apparent plateau of polymerization rate in the curve of reaction rate vs. conversion. It was shown that emulsion polymerization conformed to the Smith–Ewart theory very well. Changing the dose rate in interval 2 had no great influence on polymerization rate, but it changed the average lifetime of radicals in polymer particles and affected the molecular weight of polymer produced. For microemulsion polymerization it was assumed that in the plateau it is the number of growing polymer particles being kept constant, not the number of polymer particles. When the dose rate was changed while the polymerization came into the constant period, the polymerization rate and the molecular weight of the polymer varied with the dose rate. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 257–262, 1998     

Micellar nucleation differential microemulsion polymerization

Polymer nanoparticles within the range of 2–5 nm with a solid content of more than 13 wt.% and a narrow molecular weight polydispersity (Mw/Mn ∼ 1.1) were for the first time prepared using a micellar nucleation differential microemulsion polymerization system emulsified by sodium dodecyl sulfate (SDS), with SDS/monomer (methyl methacrylate) and SDS/H₂O weight ratios of up to 1:16 and 1:100, respectively. It was found that for benzoyl peroxide (BPO), micellar nucleation is more favorable for the synthesis of smaller polymer nanoparticles than ammonium persulfate (APS) which gives rise to homogeneous nucleation and 2,2′-azobisisobutyronitrile (AIBN) which involves partially heterogeneous nucleation. In the polymerization process, there exists a critical stability concentration (CSC) of SDS, above which the size of the nanoparticles is to be minimized and stabilized. With an increase in the monomer addition rate, the polymerization system changes from a microemulsion system to an emulsion system. A mechanism was proposed to describe the micellar nucleation process of differential microemulsion polymerization. This study may contribute to the development of fine polymer nanoparticles for drug delivery systems.     

Dispersion polymerization of styrene in ethanol–water media: Monomer partitioning behavior and locus of polymerization

A simulation model has been developed to predict the partitioning behavior of styrene in dispersion polymerization in ethanol–water mixtures. The composition of both the continuous phase and the dispersed phase are quantitatively estimated throughout the polymerization process. The presence of water in the system causes a considerable increase of the styrene partitioning in favor of the particles. Thus, at 70°C and for an initial composition of ethanol/water/styrene = 63.3/26.9/9.8, the concentration of styrene in the particles is about 4.8 times higher than that in the serum instead of about one in pure ethanol. The higher the polymerization temperature, the lower the styrene concentration in the particles; the higher the initial styrene concentration, the higher the styrene concentration in the particles, whereas the partition coefficient is not largely effected. In contrast, neither the interfacial tension nor the final particle size do significantly alter the simulation results. The predicted data from this model have been successfully applied to clarify the mechanisms involved in dispersion polymerization, in terms of stabilization and of kinetic events. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36 : 325–335, 1998     

光散射法研究丙烯酸十八酯和苯乙烯微乳液 共聚机理

在十六烷基溴化吡啶/叔丁醇/15%丙烯酸十八酯和苯乙烯/水体系的O/W微乳液中,使用动态光散射法,研究其中两种单体共聚反应的成核机理。结果表明,聚合过程中乳胶粒成核位置主要在增溶胶囊的单体微珠中,乳胶粒主要依靠单体微珠不断提供单体而长大。     

Kinetics of the microemulsion polymerization of styrene with short‐chain alcohols as the cosurfactant

The kinetics of styrene microemulsion polymerization stabilized by sodium dodecyl sulfate (SDS) and a series of short‐chain alcohols (n‐C_iH_2i+1OH, abbreviated as C_iOH, where i = 4, 5, or 6) at 60 °C was investigated. Sodium persulfate was used as the initiator. The microemulsion polymerization process can be divided into two intervals: the polymerization rate (R_p) first increases to a maximum at about a 20% conversion (interval I) and thereafter continues to decrease toward the end of the polymerization (interval II). For all the SDS/C_iOH‐stabilized polymerization systems, R_p increases when the initiator or monomer concentration increases. The average number of free radicals per particle is smaller than 0.5. The molecular weight of the polymer produced is primarily controlled by the chain‐transfer reaction. In general, the reaction kinetics for the polymerization system with C₄OH as the cosurfactant behaves quite differently from the kinetics of the C₅OH and C₆OH counterparts. This is closely related to the different water solubilities of these short‐chain alcohols and the different concentrations of the cosurfactants used in the preparation of the microemulsion. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 898–912, 2001     

Modeling inverse microemulsion polymerization

A mathematical model for inverse microemulsion polymerization has been developed. The model has been used to fit experimental results of the effect of initiator concentration, light intensity, emulsifier concentration, and dispersed phase weight fraction on the monomer conversion evolution, particle size, and polymer molecular weight in the inverse microemulsion polymerization of 2-methacryloyl oxyethyl trimethyl ammonium chloride (MADQUAT) initiated by UV light in the presence of AIBN. A good fitting of the experimental data was achieved. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2167–2178, 1999     

Comparison of oil-soluble and water-soluble initiation of styrene polymerization in a three-component microemulsion

The polymerization of styrene in three-component oil-in-water microemulsions made with the cationic surfactant dodecyltrimethylammonium bromide is studied by dilatometry and quasielastic light scattering as a function of type and concentration of initiator. Fast polymerization rates, high conversions, and high molecular weight polymers are achieved with both oil-soluble (AIBN) and water-soluble (potassium persulfate) initiators. The rate of polymerization shows initiation and termination intervals, but no constant-rate interval is observed. Stable monodisperse microlatexes are obtained with both types of initiators. For both AIBN and potassium persulfate, polystyrene molecular weight is proportional to initiator concentration [I]^–0.4 and particle radii decrease as [I]^–0.2. Polymerization initiation occurs in or at the microemulsion droplets, and polymer particles grow by recruiting monomer and surfactant from uninitiated swollen micelles.     

Microemulsion polymerization of styrene stabilized by sodium dodecyl sulfate and short‐chain alcohols

Styrene microemulsion polymerizations with different short‐chain alcohols [n‐C_iH_2i+1OH (C_iOH), where i = 4, 5, or 6] as the cosurfactant were investigated. Sodium dodecyl sulfate and sodium persulfate (SPS) were used as the surfactant and initiator, respectively. The desorption of free radicals out of latex particles played an important role in the polymerization kinetics. An Arrhenius expression for the radical desorption rate coefficient was obtained from the polymerizations at temperatures of 50–70 °C. The polymerization kinetics were not very sensitive to the alkyl chain length of alcohols compared with the temperature effect. The maximal polymerization rate in decreasing order was C₆OH > C₄OH > C₅OH. This was related to the differences in the water solubility of C_iOH and the structure of the oil–water interface. The feasibility of using a water‐insoluble dye to study the particle nucleation mechanisms was also evaluated. The parameters chosen for the study of the particle nucleation mechanisms include the cosurfactant type (C_iOH), the SPS concentration, and the initiator type (oil‐soluble 2,2′‐azobisisobutyronitrile versus water‐soluble SPS). © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3199–3210, 2001     

Monodisperse ultrafine polystyrene nanoparticles prepared by a semicontinuous microemulsion polymerization

Monodisperse ultrafine polystyrene nanoparticles have been successfully prepared under low levels of surfactant through a novel semicontinuous microemulsion polymerization, in which the first part of monomer (St₁) is added dropwise while the subsequent supply to the polymerizing system is delivered in one potion. Polystyrene nanoparticles with number‐average diameter of 17.4 nm and polydispersity index of 1.06 were obtained using low level of surfactant/monomer weight ratio of 0.20. Influencing of parameters including amount of St₁, solid content, initiator, reaction temperature, and cosurfactant on the resultant particle size and size distribution were investigated. The mechanism of nucleation and particle growth was discussed as well. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4522–4528, 2008     

Effect of short-chain alcohols on the oil-in-water microemulsion polymerization of styrene

The influence of short-chain alcohols, 1-butanol (C₄OH), 2-pentanol (C₅OH) and 1-hexanol (C₆OH), on the formation of oil-in-water styrene microemulsions and the subsequent free-radical polymerization was studied. Sodium dodecyl sulfate was used as the surfactant. The overall performance of C₄OH as the cosurfactant is quite different from C₅OH and C₆OH. The range of the microemulsion region in decreasing order is C₄OH > C₅OH > C₆OH. The primary parameters selected for the microemulsion polymerization study were the concentrations of cosurfactant and styrene. Only a small fraction of microemulsion droplets initially present in the reaction system can be successfully transformed into latex particles and the remaining droplets serve as a reservoir to supply the growing particles with monomer. Limited flocculation of latex particles also occurs during polymerization and the degree of flocculation is most significant for the C₄OH system. Received: 24 August 1999/Accepted in revised form: 22 October 1999     

Particle formation in interval III of the emulsion polymerization of styrene with aerosol‐MA as an emulsifier

Particle nucleation in the seeded emulsion polymerization of styrene in the presence of Aerosol‐MA emulsifier micelles and in the absence of monomer droplets (interval III) was investigated. The seed particles were swollen with different amounts of the styrene monomer before the experiments. A larger number of polymer particles formed in interval III than in the corresponding seeded batch operation in the presence of monomer droplets. The increase in the number of particles could be attributed to the reduced rate of growth of new particles, which retarded the depletion of emulsifier micelles. The number of secondary particles initially increased with the initial polymer weight ratio in the seed particles (w_p0) but decreased at a higher range of w_p0, after reaching a maximum at w_p0 = 0.60, and eventually was reduced to zero. At high values of w_p0 (>0.75), polymerization occurred in the seed particles, whereas few or no new particles were formed despite the presence of micelles. The cessation of particle formation at high conversions was ascertained with a semibatch process in which the neat monomer feed was added to the reaction vessel containing the seed particles and emulsifier micelles. For w_p0 > 0.85, the emulsifier micelles were disintegrated to stabilize the seed particles with no secondary particle formation. The possible reasons for the cessation of particle formation at high w_p0 were examined. The size distribution of secondary particles showed a positive skewness in terms of volume because of the declining rate of growth for particles, together with a low rate of growth for small particles. The distribution breadth of new particles sharpened with increasing w_p0. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1652–1663, 2002     

Radiation-induced polymerization of methyl methacrylate in microemulsion with high monomer content

γ-Ray-induced polymerization of methyl methacrylate was conducted in a microemulsion stabilized by a mixture of sodium of 12-acryloxy-9-octadecenoic acid (AOA) and sodium dodecyl sulfate (SDS) with various weight ratios at room temperature. The experimental data showed that the mixture of AOA and SDS with a weight ratio 2 was an efficient surfactant system for the microemulsion containing 38.6 wt% MMA and 5.5 wt% surfactant. The effects of MMA concentration and dose rate on the polymerization kinetics and particle size are discussed.     

Catalytic‐chain‐transfer polymerization of styrene revisited: The importance of monomer purification and polymerization conditions

The cobaloxime‐mediated catalytic‐chain‐transfer polymerization of styrene at 60 °C was studied with an emphasis on the effects of monomer purification and polymerization conditions. Commonly used purification methods, such as column chromatography and simple vacuum distillation, were not adequate for obtaining kinetic data to be used in mechanistic modeling. A purification regime involving inhibitor removal with basic alumina, followed by polymerization of the styrene in the presence of the cobaloxime and subsequent vacuum distillation, was found to be essential to this end. It was then possible to quantitatively investigate effects such as the initiator concentration and conversion dependencies of the apparent chain‐transfer constant that resulted from the occurrence of cobalt–carbon bond formation. A value of about 9 × 10³ was found for the true chain‐transfer constant to cobaloxime boron fluoride, that is, its value in the absence of cobalt–carbon bond formation. Furthermore, previous predictions were confirmed: the measured chain‐transfer constant decreased with increasing initiator concentration and conversion. Finally, it was confirmed that the presence of light increased the amount of free Co(II) catalyst in agreement with other studies. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 752–765, 2003     

Polymerization of butyl acrylate in anionic microemulsion

Butyl acrylate was initiated with KPS or BPO to polymerize at high monomer concentration in the microemulsions with SBOA (sodium 12-butinoyloxy-9-octadecenate) as emulsifier. The microemulsion remained clear or reddish. It was found that the constant polymerization period appeared in most microemulsions and the length of it varied with the concentration of monomer and the initiating rate. When microemulsions were initiated with KPS, the overall polymerization rate increased with the emulsifier concentration; while initiator was BPO, it showed the inverse tendency. It was attributed to the difference between the initiating mechanism of the two initiators. © 1996 John Wiley & Sons, Inc.     

Cosurfactant effects on the microemulsion polymerization of styrene

The polymerization of styrene in o/w microemulsions stabilized with dodecyltrimethylammonium bromide (DTAB) with or without cosurfactant (n-butanol, n-hexanol or n-octanol) is examined here. The addition of a cosurfactant enhances the one-phase region in the order: n-butanol > n-hexanol > n-octanol. The kinetics of polymerization slows down in the presence of the alcohol. With the alcohol, the molar masses increase, but no particular trend was noticed on particle size of the lattices. However, by changing the surfactant counter-ion to chloride, alcohol effects on the kinetics almost vanish. Possible explanations to these results are given here. To cite this article: J.E. Puig et al., C. R. Chimie 6 (2003).     

W/O型微乳法制备淀粉基纳米粒

在正己烷、Span-60和NaOH水溶液的W／O型淀粉微乳液中,进行淀粉与环氧氯丙烷交联反应制备淀粉微球,用质量分数为1％的淀粉水浆液制备出微球的流体力学半径Rb为7．08—113nm,其中粒径不超过100nm的纳米粒在整个微粒体系中占69％,平均粒径为92．2nm。TEM和DLS结果表明,制得的微粒呈圆球形,且微粒的流体力学半径随淀粉水浆液浓度的增加而增大并分布变宽,淀粉水浆液的浓度低有利于淀粉基纳米粒的形成。     

W/O microemulsions of styrene monomer and dimer

The reason for the lower water solubility in W/O microemulsions of the styrene dimer, trans, trans-1,4-diphenyl-1,3-butadiene, in comparison with the monomer was investigated by determining the phase equilibria in the microemulsion system with pentanol as the cosurfactant and sodium dodecyl sulfate as the surfactant. The main factor for the low tolerance for water in the system was the incompatibility of the dimer with the cosurfactant and surfactant.     

Microemulsion polymerization of acrylamide and styrene: Effect of the structures of reaction media

Isothermal phase diagrams of the system cetyltrimethylammonium bromide (CTAB)/n‐butanol/n‐octane/water were constructed, and the effect of the oil (n‐octane) contents on the microemulsions was studied at 40 °C. We determined the microemulsion structures of two systems, CTAB/n‐butanol/10% n‐octane/water and sodium dodecyl sulfonate (As)/n‐butanol/20% styrene/water, by conductivity measurements to investigate the polymerization of acrylamide and styrene in the two microemulsion systems. The polymerization kinetics of the water‐soluble monomer acrylamide in CTAB micelles and the different CTAB/n‐butanol/10% n‐octane/water microemulsion media [water‐in‐oil (W/O), bicontinuous (BC), and oil‐in‐water (O/W)] were studied with water‐soluble sodium bisulfite as the initiator. The maximum polymerization rate in CTAB micelles was found at the second critical micelle concentration. A mechanism of polyacrylamide formation and growth was proposed. A connection between the structures of the microemulsions and the polymerization rates was observed; the maximum polymerization rate occurred at two transition points, from W/O to BC and from BC to O/W, and the polyacrylamide molecular weights, which depended on the structures of the microemulsions, were also found. A square‐root dependence of the polymerization rates on the initiator concentrations was obtained in CTAB micelles and O/W microemulsion media. The polymerization of the oil‐soluble monomer styrene in different As/n‐butanol/20% styrene/water microemulsion media (W/O, BC, and O/W) was also investigated with different initiators: water‐soluble potassium persulfate and oil‐soluble azobisisobutyronitrile. A similar connection between the structures of the microemulsions and the conversions of styrene in CTAB/n‐butanol/10% n‐octane/water for the polymerization of acrylamide was observed again. The structures of the microemulsions had an important role in the molecular weights and sizes of polystyrene. The polystyrene particles were 10–20 nm in diameter in BC microemulsion media and 30–60 nm in diameter in O/W microemulsion media according to transmission electron microscopy. We determined the solubilization site of styrene in O/W microemulsion drops by ¹H NMR spectra to analyze the results of the microemulsion polymerization of styrene. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3320–3334, 2001