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     

乳液聚合中成核机理的研究进展

主要介绍了在乳液聚合反应中,各种成核过程的机理及其对乳液聚合反应和性能的影响;分析了胶束成核、均相成核、液滴成核的产生条件与影响因素;介绍了成核机理的最新研究进展.     

Kinetics of particle nucleation and growth in the emulsion polymerization of acrylic monomers

The rates of particle formation and growth during the earliest stages of the emulsion polymerization of several acrylic monomers have been studied as a function of surfactant concentration by means of the time-dependence of light scattering from the reaction mixtures. Investigated were methyl methacrylate, and methyl, ethyl and butyl acrylates at concentrations of SDS surfactant from 0 to several times the CMC. Under continuous photoinitiation the Rayleigh scattering intensities rose rapidly with slopes that increased with decreasing SDS concentration. The more water-soluble the monomer, the more slowly was the rate of increase in scattering intensity. Computer modeling, using HUFT theory, could be used to obtain values for the various parameters involved for MMA. The Fuchs stability factor, W, was found to be 1 for [SDS] = 0 and infinity for [SDS] = CMC or grester. The partition coefficient for J-mer oligomers between the aqueous and organic phases must rise exponentially with J. Electrostatic effects on radical capture by particles are considered to be negligible, but very important as they affect coagulation kinetics.     

w(MMA)对MMA乳液聚合成核的影响

以甲基丙烯酸甲酯(MMA)为单体,在c(乳化剂)=2mmol/L下制备乳液,研究不同w(MMA)对MMA乳液聚合成核的影响,并分析了不同w(MMA)对乳胶粒粒径的影响规律。实验结果表明:当w(MMA)≤10%,随着w(MMA)的增加转化率逐渐增大,乳胶粒的生成速率也逐渐增大;当w(MMA)≥10%时,转化率可以达到70%以上,w(MMA)对乳胶粒的生成速率的影响不大,多余的单体用于乳胶粒粒径的增长;在w(MMA)=10%时基本能够满足c(乳化剂)=2mmol/L时的成核要求。当5%≤w(MMA)≤30%,在乳化剂的自调节作用下,使得最终形成的乳胶粒数目相差不大。     

Synthesis and nucleation mechanism of inverse emulsion polymerization of acrylamide by RAFT polymerization: A comparative study

Well-defined poly (acrylamide) is synthesized by RAFT inverse emulsion polymerization using hydrophilic and lipophilic initiators. The kinetic behavior observed for RAFT inverse emulsion polymerization is similar to that for RAFT inverse miniemulsion polymerization. The nucleation mechanism of inverse emulsion polymerization of acrylamide is firstly investigated by RAFT polymerization and verified by GPC and SEM measurements. Droplet nucleation is found to be the primary mechanism in the inverse emulsion polymerization of acrylamide. However, polymerization occurring in the continuous phase is not negligible when lipophilic initiator is used.     

乙烯基硅氧烷改性丙烯酸酯乳液聚合的动力学及成核机理分析

用种子乳液聚合法研究了硅氧烷改性丙烯酸酯的乳液聚合,对影响种子乳液聚合动力学的因素进行讨论,并分析了乳液聚合的成核机理.实验结果表明：反应温度、引发剂浓度、乳化剂浓度和有机硅氧烷用量对有机硅改性丙烯酸酯乳液聚合动力学有较大的影响.反应温度越高,引发剂浓度越高、乳化剂浓度越高、有机硅氧烷用量相对较小,乳液聚合反应的转化率越高;此外,体系的pH值在6～8之间时也有利于反应的进行.种子乳液聚合中R_P∝［E］^0.72,R_P∝［I］^0.56,表观活化能E_a为143.92 kJ•mol^-1.种子乳液聚合初期,反应主要是单体液滴成核;进入壳层反应时,反应成核主要是以胶束成核为主.     

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     

Identification of nucleation loci in emulsion polymerization processes. I. New information from spectroscopy studies

Particle nucleation is the forcing function in emulsion polymerization reactions and as such it plays a significant role in the development of most of the properties of the final latex. The locus of nucleation in emulsion polymerization remains a contentious issue. Recent developments in the spectroscopy of emulsions strongly suggest that the locus of particle nucleation is a population of small nano‐droplets of size range between 30–100 nanometers in diameter. These nano‐droplets are generated independently of the rate of initiator decomposition and appear to be functions only of the emulsification conditions. In this paper the simulation studies leading to the identification of the nano‐droplet population are described. The theoretical evidence suggesting that the nano‐droplets are the main loci of particle nucleation is presented and along with the recommendations for the experimental work. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2847–2857, 2006     

Crosslinking kinetics in emulsion polymerization

Network formation in free-radical polymerization is investigated both from experimental and theoretical points of view. In a bulk free-radical crosslinking copolymerization, the radical concentration increases significantly due to a decrease in the bimolecular termination rate. Some fraction of radicals is trapped during the course of network formation, and the reactivity of the radicals in liquid state is completely different from that in solid state (trapped radicals) in terms of both propagation and termination. In emulsion crosslinking polymerization, the crosslinking density tends to be fairly high even from the start of the polymerization. The crosslinking density development is substantially different from that in bulk and solution polymerizations, in which the crosslinking density increases with time, at least in the earlier stages of polymerization. Due to the elastic contribution of free energy change, the monomer concentration in the polymer particles is lower than for linear emulsion polymerizations as long as the monomer droplets exist, resulting in an enhanced tendency toward crosslinking reactions.     

Emulsification in batch emulsion polymerization

Dispersion of liquid–liquid systems is often applied in industrial processes such as extraction, suspension, and emulsion polymerization. The influence of emulsification of the monomer in the aqueous phase on the course and outcome of the batch emulsion polymerization of styrene has been studied. A visual criterion was applied for determining the lowest impeller speed for sufficient emulsification (N*). It appeared that in polymerization experiments under the same conditions, N* was the critical value above which no further increase in polymerization rate was observed. Using a turbine impeller instead of a pitched blade impeller as well as using a larger impeller diameter provides better emulsification at constant power input. The results indicate that scale‐up with constant impeller tip speed is most appropriate in case of a turbine impeller. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3225–3241, 1999     

Inifer surfactants in emulsion polymerization

Thiol-ended non-ionic surfactants, used in combination with t-butyl hydroperoxide are components of a redox system able to initiate the emulsion polymerization of styrene, as well as control the molecular weight by transfer. Most of the surfactants remain as side products in the water phase, while multimodal molecular weight distributions of polymer are observed depending on the structure of the surfactant, the conversion of the monomer and the process used for feeding the reactor. The maximum incorporation yield of these reactive surfactants in the polymer is around 40%.     

Robust nucleation in polymer-stabilized miniemulsion polymerization

The addition of a monomer soluble polymer to an emulsion was found to slow the effects of Ostwald ripening and impart diffusional stability to the droplets. Droplet nucleation was found to be the dominant nucleation mechanism in the polymerization of these polymer-stabilized miniemulsions (as distinguished from true miniemulsions). As a result these nucleations were more robust, and the polymerizations were less sensitive to variations in the recipe or contaminants levels. This was evident in the rates of polymerization and in the particle numbers. The miniemulsion polymerizations were subjected to changes in initiator concentration, a water-phase retarder, an oil-phase inhibitor, and agitation. Particle number was found to vary with each of these factors to the powers of 0.002, 0.02, 0.0031, and −0.026, respectively. The corresponding exponents for conventional emulsion were one to two orders of magnitude greater. These results demonstrate the potential of miniemulsion polymerization to greatly reduce the variability in particle number found in conventional emulsion polymerizations. © 1996 John Wiley & Sons, Inc.     

Silicone-stabilized nonaqueous emulsion polymerization

Stable dispersions are prepared by free-radical polymerization of methyl methacrylate in aliphatic hydrocarbons containing poly(dimethylsiloxane) modified with mercaptoalkyl side groups. The particles are pictured as being stabilized by a protective layer of solvated poly(dimethylsiloxane). Some important features of the polymerization are described.     

乳液聚合方法研究进展

乳液聚合方法具有各方面的优点和广泛的应用范围,因此,受到人们的广泛关注。本文介绍了乳液聚合的优缺点,并着重介绍了一些新的乳液聚合方法及其原理、特点、应用以及中外最新的一些研究成果。     

Particle nucleation in emulsion copolymerization containing multifunctional monomers

Characteristic features of particle nucleation and growth in the emulsion copolymerization of styrene and multifunctional monomers such as ethylene glycol dimethacrylate and divinylbenzene were investigated. It was found that in these emulsion copolymerization systems the rate of polymerization per particle decreased drastically with an increase in the content of the multifunctional monomer in the initial monomer feed, and the number of polymer particles produced, on the other hand, increased corresponding to the decrease in the rate of polymerization per particle. The increase in the number of polymer particles produced was explained on the basis of Smith-Ewart theory, which predicts that the number of polymer particles produced would increase inversely proportional to the 0.4 power of the volumetric growth rate per particle, that is the rate of polymerization per particle during the interval of particle formation (Interval I). It was pointed out that the decrease in the rate of polymerization per particle in Interval I would be due mainly to a decrease in the monomer concentration in the polymer particles which was caused by crosslinking networks of the resultant polymer.     

Particle nucleation rates in continuous emulsion polymerisation reactors

The design of a continuous, stirred emulsion polymerisation reactor requires a detailed characterisation of the particle nucleation rate. Here, consideration is given to systems which use micelle-forming surfactants and water-insoluble monomers. The surfactant micelles will be considered to participate in two competing rate processes; the nucleation of polymer particles and dissolution into the aqueous phase. When the reactor operates in a steady state it is possible to obtain a size distribution function for the particles. This distribution function is used in the development of a number of diffusion equations and conservation equations. By making various sets of assumptions concerning the nucleation process, these equations are then used to obtain expressions for the particle number. By comparing the different models with experimental results it can be seen that satisfactory predictions for the particle number can be obtained without assuming that the polymer particles are always saturated with surfactant. The models also show that the radical absorption processes are not controlled by diffusion in the aqueous phase. In some cases the particle number does not reach a steady state but oscillates with time. The nature of these oscillations is described by the solution of nonlinear differential equations. Boundary conditions for these equations depend on the reaction conditions.     

Initial droplet size distribution in miniemulsion polymerization

The initial droplet size distribution of miniemulsions has not yet been measured. It is deduced from previous experimental results that the distribution is broad. Furthermore, the small fraction of the distribution, depending on the nonideality of the cosurfactant–monomer system, may not be stable. This may lead to a rearrangement of the distribution leading to a bimodal distribution. The stability criterion is based on the phenomenon of molecular diffusion or Ostwald ripening. Experimental proof in support of the conclusion regarding the bimodal distribution is cited. The practical significance of the conclusion for making emulsion polymers with high solid contents is given. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3058–3065, 2003     

无皂乳液聚合的最新研究进展

简单阐述了无皂乳液聚合的定义及其常见的聚合方法,介绍了无皂乳液聚合方法在活性可控自由基聚合(CRP)领域中的应用,对其在原子转移自由基聚合(ATRP)领域和在可逆加成-断裂链转移聚合(RAFT)领域的应用机理进行阐述.简要分析了提高乳液稳定性的方法,最后结合无皂乳液聚合技术的应用进展对其发展趋势做出展望.     

Computationally efficient solution of population balance models incorporating nucleation, growth and coagulation: application to emulsion polymerization

A computationally efficient solution technique is presented for population balance models accounting for nucleation, growth and coagulation (aggregation) (with extensions for breakage). In contrast to earlier techniques, this technique is not based on approximating the population balance equation, but is based on employing individual rates of nucleation, growth and coagulation to update the PSD in a hierarchical framework. The method is comprised of two steps. The first step is the calculation of the rates of nucleation, growth and coagulation by solving an appropriate system of equations. This information is then used in the second step to update the PSD. The method effectively decomposes the fast and the slow kinetics, thereby eliminating the stiffness in the solution. In solving the coagulation kernel, a semi-analytical solution strategy is adapted, which substantially reduces the computational requirement, but also ensures the consistency of properties such as the number and mass of particles.