Diffusion-controlled semibatch emulsion polymerization of styrene

Semibatch emulsion polymerization of styrene under the monomer-starved condition is strongly affected by the gel effect. A mechanistic model based on diffusion-controlled reaction mechanisms is developed to predict the kinetics of semibatch emulsion polymerization. Experimental data available in the literature are employed to assess the proposed model. Reasonable agreement between the model predictions and experimental data is observed. The simulation results suggest that the reaction system approaches Smith–Ewart case II kinetics (n? = 0.5) when the concentration of monomer in the particles is close to the saturation value, whereas the reaction system under the monomer-starved condition is characterized by diffusion-limited reaction mechanisms (n?≥0.5). © 1995 John Wiley & Sons, Inc.     

溴化苯乙烯/苯乙烯/丙烯腈乳液聚合试验条件探索

以过硫酸钾为引发剂,十二烷基硫酸钠为乳化剂,叔十二烷基硫醇为链转移剂,通过乳液法对溴化苯乙烯、苯乙烯、丙烯腈进行共聚得到溴化苯乙烯-丙烯腈共聚物.考察了引发剂、乳化剂、链转移剂的添加量,反应温度,反应时间,水和单体比例等对聚合反应收率的影响.研究表明：较适宜的反应条件为反应温度80℃,反应时间6h,水与单体质量比4∶1,引发剂质量为单体总质量的0.4％,乳化剂质量为单体总质量的4％,叔十二烷基硫醇为单体总物质的量的2％;上述条件下的产物收率高,相对分子质量4万左右,热分解温度高于350℃.     

Continuous flow operation in emulsion polymerization of styrene

The kinetics of continuous emulsion polymerization of styrene were studied theoretically on the basis of the authors' batch reaction model, and a new reaction model was proposed for continuous operation. The validity of the model was tested by experiments conducted with stirred tank reactors in series. The characteristics of the first reactor used to generate polymer particles were studied in particular detail. It was found that there was an optimum residence time for the first reactor, the value of which was quantitatively predictable from the operating variables. The most suitable combinations of several types of reactors for continuous emulsion polymerization are also discussed.     

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.     

Emulsifier‐free emulsion polymerization of styrene

Polystyrene latex particles in an emulsifier‐free emulsion were prepared by purified styrene (St) as monomer and 2,2′‐azobis (2‐amidino propane) dihydrochloride (ABA, 2HCl) as initiator. The optimized condition of polymerization of styrene was obtained by using the various parameters such as different amounts of monomer (0.009, 0.051, and 0.071 mol styrene/mol Water), different amounts of initiator (6.02, 4.62, 2.41, and 1.00 weight percent of initiator relative to styrene), and pH (range 1–7). Quantitative and qualitative analyses of prepared polymer were performed by Scanning Electron Microscopy (SEM), Differential Scanning Calorimetry (DSC), Gel Permeation Chromatography (GPC), and ¹H‐NMR and FT‐IR spectroscopy, that were used, respectively, to show the morphology of particles, the glass transition temperature (T_g), the average molecular weight, and the structure of the prepared polymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1898–1904, 2004     

A study of the soap-free emulsion polymerization of styrene

A study on the soap-free emulsion polymerization of styrene has been accomplished in this work. The polymerization reaction was carried out in a batch reactor under isothermal condition. Potassium persulfate was used as an initiator. In our experiments, the effects of agitation speed, monomer concentration, and initiator concentration on the number and size of polymer particles, on the conversion of monomer and molecular weight of polymers were investigated. In addition, the systems in the presence of emulsifier or CaSO₃ were investigated and discussed in comparison with a system free of them.     

Comparison of chemical and enzymatic emulsion polymerization of styrene

For the reasonable comparison of chemical and enzymatic polymerization, manganese(III) acetate and manganese peroxidase (MnP)‐catalyzed synthesis of polystyrenes were chosen and studied with respect to the yield and the polydispersity of polymer particles. MnP allowed the production of polystyrene in a higher yield and higher polydispersity (82.34% and 2.61) than manganese(III) acetate (77.90% and 1.75). This is believed to be due to a gradual supply of initiator radicals via a catalytic cycle in MnP‐catalyzed polymerization, whereas radicals are generated all at once in Mn(III)‐mediated polymerization. NMR spectroscopy revealed that atactic polystyrene was produced by emulsion polymerization using Mn(III) or MnP. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of stirring on the emulsion polymerization of styrene

The purpose of this paper is to clarify the effect of stirring on the course of emulsion polymerization of, for example, styrene. It establishes the existence of an optimum range of stirring speed and three important factors which must be considered in carrying out emulsion polymerization. (1) Stirring significantly affects the course of reaction in the presence of an imperfectly purified nitrogen atmosphere. Consequently, the number of polymer particles produced and the polymerization rate per particle will be affected. (2) At higher stirring speeds, polymer particles coagulate and coalesce. At lower stirring speeds, the reaction rate is controlled by the monomer transport rate from monomer droplets to the aqueous phase. (3) Stirring contributes to the reduction of the number of micelles because emulsifier molecules are adsorbed onto the surfaces of monomer droplets finely dispersed by the stirring. At low emulsifier concentrations near the critical micelle concentration, this effect cannot be neglected.     

α-甲基苯乙烯和苯乙烯共聚物乳液的合成及性能研究

在不通N2的条件下,采用半连续法,在85℃、乳化剂用量为总量的7.53%时合成出了不同单体配比的α-甲基苯乙烯-苯乙烯共聚物[P(AMS-St)]乳液,其中AMS单体含量最高可达70%以上。用红外、核磁对共聚物结构进行了表征,讨论了加料方式、反应温度、乳化剂用量、单体配比对乳液转化率及稳定性的影响和单体组成与乳液流变性、乳胶粒径大小之间的关系。结果表明随单体中AMS含量的增加,乳液黏度逐渐变大,乳胶粒径逐渐变小,乳胶粒具有均一的尺寸。     

Surfactant-enhanced free radical polymerization of styrene in emulsion gels

The presence of a surfactant (such as hexadecyltrimethylammonium bromide, CTAB) enhanced the rate of polymerization of styrene in emulsion gels with and without silica. The emulsion gels consisted of styrene, azobisisobutyronitrile (AIBN), surfactant, water, and, in some cases, fumed silica. Polymerization of the emulsions was carried out at room temperature in one or several days depending on the composition of the emulsion. The conversion of monomer to polymer could exceed 90% in a couple of days. In contrast, very little polymerization occurred in the absence of surfactant. A simple model, incorporating a surfactant-initiator complex and standard free radical polymerization, successfully fits the experimental kinetics data. This analysis suggests that the initiator is complexed with approximately three surfactant molecules.     

Effect of 1-pentanol on the styrene emulsion polymerization

The influence of 1-pentanol (C₅OH) on the ST emulsion polymerization mechanisms and kinetics is investigated. The CMC of the ST emulsions first decreases rapidly and then levels off when the C₅OH concentration ([C₅OH]) increases from 0 to 72 mM. The effect of C₅OH increases to a maximum and then decreases when the SDS concentration ([SDS]) increases from 2 to 18 mM. At [SDS]=2 mM, homogeneous nucleation controls the polymerization kinetics regardless of [C₅OH]. At [SDS]=4 mM, the effect of [C₅OH] appears due to the transition from homogeneous nucleation to a mixed mode of particle nucleation (homogeneous nucleation and micellar nucleation) occurs when [C₅OH] increases from 0 to 72 mM. The effect of [C₅OH] is the strongest at [SDS]=6 mM since the particle nucleation mechanisms span homogeneous nucleation (low [C₅OH]), a mixed mode of particle nucleation (homogeneous nucleation and micellar nucleation) (medium [C₅OH]) and micellar nucleation (high [C₅OH]). At [SDS] >6 mM, in which micellar nucleation controls the polymerization kinetics, the effect of [C₅OH] decreases rapidly with increasing [SDS].     

Ionomer synthesis by emulsion polymerization of styrene and sodium acrylate

The emulsion copolymerization of styrene and sodium acrylate is reported using either a water-soluble initiator (potassium persulfate, or KPS), or an oil-soluble one [2,2-azoisobutyronitrile (AIBN)]. Reaction rates are fast with both KPS and AIBN. With KPS, conversions >90% are achieved in 50 min, with AIBN, conversions reach 85% in 100 min. Particle size, measured by quasielectric light scattering (QLS), increases with conversion. Particle size in final latices is ∼ 70–80 nm. Copolymer formation is confirmed by infrared (IR) spectroscopy, plasma emission spectroscopy (PES), and scanning electron microscopy (SEM). IR and PES indicate that mainly sodium acrylate reacts at the beginning of the reaction and then styrene is incorporated in the copolymer backbone. The copolymer produced with KPS contains more sodium acrylate than the one made with AIBN. These differences can be explained in terms of the reactivities and partitioning (local concentrations) of the monomers and of the type of initiator used. Thermomechanical analysis (TMA) of the copolymers reveals two transitions: one at ∼ 100°C, which is due to the glass transition temperature (T_g) of polystyrene blocky segments in the copolymer, and another one at higher temperatures, which is associated to the T_g of segments composed of alternated sodium acrylate and styrene units. The higher-temperature transition shifts to lower values as the reaction proceeds because these segments become richer in styrene. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 879–889, 1997     

Effects of short chain alcohols on the styrene emulsion polymerization

The effects of a series of short chain alcohols, 1‐butanol (C₄OH), 1‐pentanol (C₅OH), and 1‐hexanol (C₆OH), on the styrene (ST) emulsion polymerization mechanisms and kinetics were investigated. The CMC of the ST emulsions stabilized by sodium dodecyl sulfate (SDS) first decreases rapidly and then levels off when the C_iOH (i = 4, 5, or 6) concentration ([C_iOH]) increases from 0 to 72 mM. Furthermore, at constant [C_iOH], the CMC data in decreasing order is CMC (C₄OH) > CMC (C₅OH) > CMC (C₆OH). The effects of C_iOH (i = 4, 5, and 6) on the ST emulsion polymerization stabilized by 6 mM SDS are significant. This is attributed to the reduction in CMC by C_iOH, the different oil–water interfacial properties, the different concentrations of monomer within latex particles, and the different effectiveness of SDS/C_iOH in stabilizing latex particles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4406–4411, 2006     

On the fine emulsion polymerization of styrene with non-ionic emulsifier

Summary The fine emulsion polymerizations of styrene initiated by a redox system ammonium peroxodisulfate/sodium thiosulfite stabilized by a non-ionic emulsifier were kinetically investigated. The dependence of the rate of polymerization on conversion or the emulsifier concentration was described by a curve with maximum at medium conversion. The maximum rate of polymerization is proportional to the − 0.45^th and 1.5^th power of initiator and emulsifier concentration, the number of particles to the 0.32^nd and 1.3^rd power of initiator and emulsifier concentration and the molecular weight to the − 0.62^th and −0.97^th power of initiator and emulsifier concentration, respectively. The results show a strong decrease in turbidity at around 20% conversion when emulsion turns into translucent latex. Deviation from the micellar nucleation model was attributed to the solubility of emulsifier in monomer, high level of nonmicellar aggregates, thick interfacial layer and transfer emulsion to microemulsion. The strong decrease of molecular weight with increasing emulsifier concentration is attributed to chain transfer events promoted by the high level of emulsifier at the reaction loci. Received: 16 November 1998/Revised version: 25 May, 10 October 1999/Accepted: 10 October 1999     

Kinetics of styrene emulsion polymerization with a stable monomer radical

We have analyzed the electrical conductivity of a linear high charge density polyelectrolyte aqueous solution, finding that the counterion association order follows the same pattern as that described for a cyclic monomeric polyelectrolyte, i.e. NO > Br^? > Cl^? > F^?. However, these counterions interact in a very different manner with this polyion, making Eisenberg's relationship inapplicable in this system. Consequently, an alternative method is proposed for treating data.     

Entry and exit rate coefficients in emulsion polymerization of styrene

The rate coefficient for entry of radicals into the polymer particles and the radical exit rate coefficient were estimated in seeded emulsion polymerization of styrene. The dependence of both coefficients on the particle size was used in an attempt to discriminate between the models proposed for these coefficients. The results obtained were found to be consistent with a model in which the entry of radicals into the polymer particles occurs by the propagational mechanism and the radicals desorb from the polymer particles by diffusion. A comparison between the estimated values of the coefficients and those calculated theoretically using the equations derived from the corresponding mechanisms was performed.     

Aspects of coagulation during emulsion polymerization of styrene and vinyl acetate

The influence of recipe and process conditions on the coagulation behavior of polystyrene (PS) and polyvinyl acetate (PVAc) latices has been studied. Seeded batch experiments reveal a significant influence of electrolyte concentration on the coagulation behavior of both PS and PVAc latices. Within the experimental error, no dependency of the coagulation behavior on process conditions, in terms of energy dissipation, reactor scale, impeller type, and impeller diameter, has been observed for the reactor scales investigated. These results indicate that intrinsic chemical influences such as electrolyte concentration dominate the coagulation behavior during emulsion polymerization and also in the absence of polymerization over the process conditions. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2409–2421, 1998     

The stabilization effect of mixed-surfactants in the emulsion polymerization of styrene

Summary The emulsion polymerization of styrene was performed at 50°C with a mixture of anionic and nonionic surfactants using different surfactant concentrations. In the single-surfactant systems, a proportional relationship was observed between the total particle surface area per cm³ of aqueous solution at 90% conversion (TS) and the amount of surfactant used for each polymerization. For mixed-surfactant systems an additivity was established between the TS value and surfactant composition. The study of the particle size data from low to high conversion showed that the particle number changed with conversion.     

Efficiency of initiation by azodiisobutyronitrile in the emulsion polymerization of styrene

Oil-soluble initiators can produce rates of emulsion polymerization similar to those obtained with the water-soluble initiators which are normally used. Although radicals are generated in pairs in the oil phase, escape of a radical to the aqueous phase leaves an isolated radical in the oil phase: this is the essential condition for an emulsion polymerization. A concentration of azodiisobutyronitrile was found which produced the same number of latex particles in the emulsion polymerization of styrene as was obtained with a typical concentration of potassium peroxydisulphate. The rate of nucleation of latex particles can then be equated to that obtained with the known rate of decomposition of peroxydisulphate. Comparison with the rate of decomposition of azodiisobutyronitrile shows its efficiency to be only 4% in emulsion polymerization in contrast with the efficiency of ～50% obtained in bulk or solution polymerization.     

The effects of electrolyte concentration in the emulsion polymerization of styrene

Using concentrations below that required to coagulate the latex, the effects of the addition of potassium chloride on the emulsion polymerization of styrene have been investigated. When potassium decanoate (an emulsifier with a high critical micelle concentration (c.m.c.)) is used the increase in the concentration of micellar emulsifier and the decrease in the area occupied by an emulsifier molecule at the polymer/water interface are significant. When this is taken into account Gardon's equation for latex particle size reproduces the trend of the experimental results at the lower electrolyte concentrations. The agreement can be made quantitative by choosing alternative values for the propagation rate constant of styrene and the rate of radical formation from persulphate. With potassium octadecanoate (which has a low c.m.c.) and with potassium decanoate at the higher electrolyte concentrations these factors cannot account for the results observed.