聚合过程中原位生成助稳定剂的细乳液聚合

以甲基丙烯酸十二氟庚酯(DFMA)、甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)为共聚单体,不加任何传统的助稳定剂进行细乳液聚合.在共聚体系中,由于DFMA在初期反应生成的聚合物中占有较高比例,初期形成的少量低聚物可以起到助稳定剂作用,因此DFMA作为反应单体的同时,又可以原位生成助稳定剂,维持单体液滴或乳胶粒子的稳定,以细乳液聚合的方式进行聚合.分别采用油溶性引发剂(AIBN)和水溶性引发剂(KPS)引发聚合,考察细乳液聚合过程中乳胶粒子粒径的变化规律,粒径由初始时刻的400nm左右减少到80nm左右,最终与使用传统的助稳定剂得到的粒径相当.提出了原位生成助稳定剂的细乳液聚合机理,并使用交联剂验证了提出的原位生成助稳定剂的细乳液聚合机理.     

Kinetics and mechanism of emulsifier-free emulsion copolymerization: Styrene-methyl methacrylate-acrylic acid system

The emulsifier-free emulsion copolymerization of styrene (St) and methyl methacrylate (MMA) in the presence of functional monomer acrylic acid (AA) was carried out in batch process. The kinetics was investigated in detail using model function, Integrated Gamma Function. The morphology and size of particles were monitored continuously by TEM all along the polymerization. It was found that the nucleation, polymerization rate increase with increasing concentration of the functional monomer AA, initiator ammonium persulfate (APS), and polymerization temperature T, and APS plays a predominant role in the particle nucleation process. The particle nucleation stage ceased at about 10% conversion and the steady stage can be extended to about 70% conversion. The particle nucleation is likely to yield primary particle via the mechanism of homogeneous coagulative nucleation and coagulation of the primary particle to yield uniform particles. The particle growth in the postnucleation stage is via a shell growth mechanism. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2649–2656, 1999     

Polymerization of vinyl chloride at reduced monomer accessibility. III. Polymerization kinetics and molecular structure using PVC latex as seed

Vinyl chloride was polymerized at 53–97% of the saturation pressure in a water-suspended system at 55°C with an emulsion PVC latex as seed. A water-soluble initiator was used in various concentrations. The monomer was continuously charged as vapor from a storage vessel kept at lower temperature. Characterization included determination of molecular weight distribution and degree of long-chain branching by gel chromatography and viscometry and by thermal dehydrochlorination. To avoid diffusion control intense agitation was necessary. At a certain conversion, aggregation of primary particles resulted in restricted polymerization rate. Before aggregation, formation of new particles did not occur as the number of particles was high enough to ensure capture of all oligoradicals. The kinetic equation accepted for ordinary emulsion polymerization of vinyl chloride was qualitatively found to be valid after the pressure drop as well. Decreased termination rate may result in increased polymerization rate at reduced monomer concentration, i.e., a gel effect, especially at low particle numbers and high polymer contents. The molecular weight decreased with decreasing monomer concentration. This is in accordance with the new mechanism suggested for chain transfer to monomer starting with occasional head-to-head additions.     

Semicontinuous Emulsion Polymerization of Vinyl Acetate. Part I. Homopolymerization with Poly-(Vinyl Alcohol) and Nonionic Coemulsifier

The semicontinuous emulsion polymerization of vinyl acetate has been studied. Poly(vinyl alcohol) as a protective colloid and ethoxylated cetyl alcohol as a coemulsifier were used. The conversion and particle diameter were affected by the stirring speed and the coemulsifier distribution between initial reactor charge and continuously introduced monomer. The amount of unreacted monomer oscillates with time.     

Sterically stabilized emulsion polymerization of styrene: Pseudo‐semicontinuous approach

The sterically stabilized emulsion polymerization of styrene initiated by a water‐soluble initiator at different temperatures has been investigated. The rate of polymerization (R_p) versus conversion curve shows the two non‐stationary‐rate intervals typical for the polymerization proceeding under non‐stationary‐state conditions. The shape of the R_p versus conversion curve results from two opposite effects—the increased number of particles and the decreased monomer concentration at reaction loci as the polymerization advances. At elevated temperatures the monomer emulsion equilibrates to a two‐phase or three‐phase system. The upper phase is transparent (monomer), and the lower one is blue colored, typical for microemulsion. After stirring such a multiphase system and initiation of polymerization, the initial coarse polymer emulsion was formed. The average size of monomer/polymer particles strongly decreased up to about 40% conversion and then leveled off. The initial large particles are assumed to be highly monomer‐swollen particles formed by the heteroagglomeration of unstable polymer particles and monomer droplets. The size of the “highly monomer” swollen particles continuously decreases with conversion, and they merge with the growing particles at about 40–50% conversion. The monomer droplets and/or large highly monomer‐swollen polymer particles also serve as a reservoir of monomer and emulsifier. The continuous release of nonionic (hydrophobic) emulsifier from the monomer phase increases the colloidal stability of primary particles and the number of polymer particles, that is, the particle nucleation is shifted to the higher conversion region. Variations of the square and cube of the mean droplet radius with aging time indicate that neither the coalescence nor the Ostwald ripening is the main driving force for the droplet instability. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 804–820, 2003     

Prediction of polymer composition in batch emulsion copolymerization

Monomer partitioning in emulsion copolymerization plays a key role in determining composition drift and polymerization rates. The combination of recently developed thermodynamically based monomer partitioning relationships with mass balance equations, makes predictions of monomer partitioning in emulsion copolymerizations possible in terms of monomer mole fractions and monomer concentrations in the particle and aqueous phases. Using this approach, the effects of monomer to water ratios and polymer volumes on the monomer mole fraction within the polymer particle phase in a nonpolymerizing system at thermodynamic equilibrium can be determined. Comparison of these monomer partitioning predictions with experiments for the monomer system methyl acrylate—vinyl acetate shows good agreement. Furthermore, composition drift occurring in a polymerizing system as a function of conversion can be predicted if the assumption is made that equilibrium is maintained during reaction. Comparison of predictions with experimental results for emulsion copolymerizations of the monomer systems methyl acrylate—vinyl acetate and methyl acrylate—indene shows good agreement. © 1994 John Wiley & Sons, Inc.     

Application of Molecular Weight and Particle Growth Measurements in Continuously Uniform Latices to Kinetic Studies of Styrene Emulsion Polymerization

It is possible to generate, in specially formulated styrene emulsion polymerizations, latices in which the monomer—polymer particles are uniform through all stages of growth. These latices are kinetically similar to their polydispersed counterparts and can therefore be used as model systems in generalized kinetic studies of emulsion polymerization. The most important feature of these systems is the fact that the particles are uniform throughout the reaction with regard to all intrinsic properties and rate processes, and the particles can be characterized by this complete, continuous uniformity. Certain remarkably simple, but precise, relationships exist between the overall, measurable kinetic parameters and the individual particle kinetic parameters, thereby resulting in a heretofore unrealized analytic accessibility. Molecular weight kinetic analyses are an order of magnitude more accurate than in non-uniform systems. Application of these continuously uniform systems in actual kinetic studies indicates an inconsistency in the current concepts of emulsion polymerization, i.e., the generation of polymer at a constant molecular weight is predicted while an increase of several fold is observed. Before the situation can be clarified, further studies with continuously uniform systems are needed to evaluate molecular weight development, molecular weight distribution, and molecular structure and also to re-evaluate the rate and diffusion processes which control these structural features.     

Polymerization of oil (styrene and methylmethacrylate)-in-water microemulsions

 The polymerization of styrene-in-water and methylmeth-acrylate-in-water microemulsions stabilized by nonionic surfactants was investigated using different initiation techniques. Thermally induced initiation was carried out using potassium persulfate (water soluble) and azobisiso-butyronitrile (AIBN) (oil soluble) at 60° and 50°C, respectively. When the monomer concentration was kept below a certain limit, the particle size of the nanolatex was similar to the droplet size of the microemulsion precursor. At higher monomer concentrations, the latex produced was significantly larger than the microemulsion droplets, as a result of the possible coalescence of the microemulsion droplets during polymerization. By using chemically induced polymerization (hydrogen peroxide+ascorbic acid) at temperatures below the cloud point temperature of the microemulsion or by photochemically induced initiation at room temperature, it was possible to obtain nanolatex particles with similar size to the droplets up to 10% monomer content. In all cases, the particle size was determined using photon correlation spectroscopy (PCS). Electron micrographs of the microlatex particles were taken and these confirmed the measurements obtained by PCS. The molecular weight of the polymers produced was determined by gel permeation chromatography. The average number of polymer molecules per particle was calculated. It was shown in some cases that the nanolatex contained one polymer chain per particle. A mechanism was suggested for polymerization and particle growth. Received: 29 May 1997 Accepted: 28 May 1998     

An experimental study of ideal and nonideal behavior in styrene emulsion polymerization

An experimental investigation was conducted to relate the average number of radicals per particle, n? to the dimensionless parameter α, as suggested by Stockmayer. Seed emulsion polymerizations of polystyrene were run over a wide range of particle sizes and initiator levels in the 50?70°C temperature range. The seed polymerization technique removed the question of particle formation behavior and allowed a straightforward determination of n?. Alpha was varied more than three orders of magnitude and resulted in measured values of n? in the range 0.5?1.3. These data are in good agreement with Stockmayer's relationship as long as the value of the termination rate constant is taken at the monomer/polymer ratios found in emulsion polymerization. For polystyrene at a monomer/polymer ratio of 60/40 this value is an order of magnitude lower than that found for infinitely dilute polystyrene solutions.     

Mathematical modeling of styrene and butyl acrylate homopolymerization via the reversible addition-fragmentation mechanism

A mathematical model is suggested for the kinetics of the controlled free-radical polymerization of two monomers—styrene and butyl acrylate—via the reversible addition-fragmentation chain transfer (RAFT) mechanism (with 2,2′-azobisisobutyronitrile as the initiator and dibenzyl trithiocarbonate as the RAFT agent). A comparison of experimental molecular weight characteristics of polystyrene and poly(butyl acrylate) with those calculated using the model indicates that the model is valid. The effects of the process control parameters (temperature and the initial concentrations of the initiator, monomer, and RAFT agent) have been elucidated by a computational experiment.     

Particle nucleation and monomer partitioning in styrene O/W microemulsion polymerization

Particle nucleation in the polymerization of styrene microemulsions was found to take place throughout the polymerization as indicated by measurements of the particle number as a function of conversion. A mechanism based on the nucleation in the microemulsion droplets was proposed to explain the experimental findings although homogeneous nucleation and coagulation during polymerization were not completely ruled out. A thermodynamic model was developed to simulate the partitioning of monomer in the different phases during polymerization. The model predicts that the oil cores of the microemulsion droplets were depleted early in the polymerization (4% conversion). Due to the high monomer/polymer swelling ratio of the polymer particles, most of the monomer resides in the polymer particles during polymerization. The termination of chain growth inside the polymer particles was attributed to the chain transfer reaction to monomer. The low n? (less than 0.5) of the microemulsion system was attributed to the fast exit of monomeric radicals.     

Synthesis of monodisperse polymer suspensions with a narrow particle size distribution in the presence of water-insoluble triple block copolymers of polypropylene oxide and polyethylene oxide (pluronics)

The colloidal chemical properties of triple block copolymers of polypropylene oxide and polyethylene oxide (pluronics of various structures) were studied in comparison. All of them are shown to be surfactants but differ in interfacial tension, surface activity, surface area occupied in the adsorption layer, and adsorption layer thickness. The kinetic regularities of polymerization of styrene and methyl methacrylate were studied. The particle diameters and their size distribution were determined. Distinctions in the kinetic regularities of polymerization are shown: the shape of the conversion—time curves (for the duration of the initial and stationary stages of polymerization) and the dependences of the diameter on the surfactant concentration and monomer to water volume ratio. In the presence of the water-insoluble pluronics, the mechanism of formation of polymer—monomer particles and interfacial layer on the surface differs from that when using water-soluble surfactants, which makes it possible to distinguish these processes into an independent type of heterophase polymerization.

     

Core–shell and gradient morphology polymer particles analyzed by X‐ray photoelectron spectroscopy: Effect of monomer feed order

The synthesis of composite latex particles possessing core–shell and gradient morphologies, respectively, using seeded starve‐fed semibatch emulsion polymerization of styrene (St) and methyl methacrylate (MMA) is presented. The focus is on the effect of the monomer feed order on the particle morphology development. The particle morphology is assessed using a novel approach which entails comparing the experimental surface composition as a function of polymerization time (particle growth) obtained by X‐ray photoelectron spectroscopy with the predicted surface composition using a mass balance mathematical model. Both types of composite latexes (core–shell and gradient) feature changes with polymerization time in the oxygen/carbon surface composition which enables one to track the morphology development. Differential scanning calorimetry is also implemented to analyze the extent of phase separation. The monomer feed order is shown to play a crucial role—under the present conditions, gradient and core–shell particles are obtained if the feed order is St/MMA (St fed first), but not if the feed order is reversed. These findings illustrate that thermodynamic factors are important, given that thermodynamically it is more favorable for MMA‐rich chains to occupy the oil–water interface to reduce the interfacial tension. Systems where St is the second stage monomer lead to mixed structures rather than the targeted core–shell or gradient morphology with St‐rich chains at the particle surface. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2513–2526     

Semi-continuous emulsion polymerization of styrene in the presence of poly(methyl methacrylate) seed particles. Polymerization conditions giving core-shell particles

This work reports the morphology of two-phase latex particles prepared by semi-continuous seed emulsion polymerization of styrene in the presence of polar poly(methyl methacrylate), PMMA, seed particles, using different conditions of non-polar styrene feed rate, rate of initiation, seed particle concentration and temperature of polymerization.The expected latex particle morphology at thermodynamic equilibrium is an inverted core-shell structure where the non-polar polystyrene would form the core. However, depending on the set of process conditions used the morphology of the resulting two-phase particles varied from that of a pure core-shell structure, over intermediate structures in which a shell of PS surrounded a PMMA core containing an increasing number of PS phase domains, to a structure in which the entire PS phase was present as discrete PS phase domain, more or less evenly distributed in a matrix of PMMA.By the use of a caloirimetric reactor system the monomer concentration in the particles during the different polymerization experiments could be calculated by comparing the integral of the polymerization rate curve with the integral of the monomer feed rate. A comparison between particle morphology and the calculated concentration of plasticizing monomer in the polymerizing particles strongly suggested that the diffusivity of the entering oligo radicals determined by the difference between polymerization temperature and the glass transition temperature of the monomer-swollen core polymer is a key factor determining the morphology of two-phase particles prepared by semi-continuous seed emulsion polymerization.Two-phase particles with a true core-shell structure were obtained in experiments where the estimated glass transition temperature of the PMMA phase was only a few degrees below the polymerization temperature. The results show that such particles can be obtained under conditions of high as well as low styrene feed rates, provided that the rate of initiation is properly adjusted.     

Miniemulsion copolymerization of styrene–methyl methacrylate

Miniemulsion copolymerization of 50 : 50 weight fraction of styrene–methyl methacrylate monomer, using hexadecane as the cosurfactant, was carried out in both unseeded and seeded polymerizations. Effects of the hexadecane concentration and the ultrasonification time on the conversion–time curves and particle size of the final latex were investigated for unseeded polymerization. The kinetic and particle size distribution results showed that an increase in hexadecane concentration and ultrasonification time cause faster polymerization rate and smaller particle size. The mechanism of mass transport from miniemulsion droplets to polymer particles was also investigated for seeded polymerization. For this purpose a monomer miniemulsion was mixed with a fraction of a previously prepared miniemulsion latex particles prior to initiation of polymerization, using residual oil-soluble initiator in the seed latex. The concentration of hexadecane and a water-insoluble inhibitor (2,5 di-tert-butyl hydroquinone) in the miniemulsions were the main variables. Seeded polymerizations were also carried out in the presence of miniemulsion droplets containing a water-insoluble inhibitor and water-soluble initiator. The inhibitor concentration and the agitation speed during the course of polymerization were the experimental variables. The kinetic and particle size results from these seeded experiments suggested that collision between miniemulsion droplets and polymer particles may play a major role in the transport of highly water-insoluble compounds.     

The synthesis of polymer suspension with narrow particle size distribution for immunochemical investigations

 Heterophase polymerization of styrene in the presence of di-p-tolyl-o-carbalkoxyphenylcarbinol (DTC) soluble in monomer and insoluble in water, as stabilizer, was investigated. The factors affecting polymer particle diameter, their size distribution and stability were investigated. It was suggested that polymer particles are formed from monomer droplets. The polystyrene suspension with narrow particle size distribution synthesized in the presence of DTC, was used for immunochemical research. Received: 10 March 1998 Accepted: 8 June 1998     

Kinetic modeling of two-step RAFT process for the production of novel fluorosilicone triblock copolymers

Well-defined poly(dimethylsiloxane)-b-poly(2,2,3,3,4,4,4-heptafluorobutylmethacryl-ate-b-poly(styrene) (PDMS-b-PHFBMA-b-PS) triblock copolymers were prepared by two-step reversible addition-fragmentation chain transfer (RAFT) polymerization. A comprehensive mathematical model for the two-step RAFT polymerization in a batch reactor was presented using the method of moments. The model described molecular weight, monomer conversion and polydispersity index as a function of polymerization time. Good agreements in the polymerization kinetics were achieved for fitting the kinetic profiles with the suggested model. In addition, the model was used to predict the effects of initiator concentration, chain transfer agent concentration and monomer concentration on the two-step RAFT polymerization kinetics. The simulated results showed that for the two-step RAFT polymerizations, the effects initiator concentration, chain transfer agent concentration and monomer concentration are identical and the influence degrees are different yet.     

Particle formation under monomer‐starved conditions in the semibatch emulsion polymerization of styrene. I. Experimental

Particle formation and particle growth compete in the course of an emulsion polymerization reaction. Any variation in the rate of particle growth, therefore, will result in an opposite effect on the rate of particle formation. The particle formation in a semibatch emulsion polymerization of styrene under monomer‐starved conditions was studied. The semibatch emulsion polymerization reactions were started by the monomer being fed at a low rate to a reaction vessel containing deionized water, an emulsifier, and an initiator. The number of polymer particles increased with a decreasing monomer feed rate. A much larger number of particles (within 1–2 orders of magnitude) than that generally expected from a conventional batch emulsion polymerization was obtained. The results showed a higher dependence of the number of polymer particles on the emulsifier and initiator concentrations compared with that for a batch emulsion polymerization. The size distribution of the particles was characterized by a positive skewness due to the declining rate of the growth of particles during the nucleation stage. A routine for monomer partitioning among the polymer phase, the aqueous phase, and micelles was developed. The results showed that particle formation most likely occurred under monomer‐starved conditions. A small average radical number was obtained because of the formation of a large number of polymer particles, so the kinetics of the system could be explained by a zero–one system. The particle size distribution of the latexes broadened with time as a result of stochastic broadening associated with zero–one systems. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3940–3952, 2001     

A Study of Emulsion Polymerization Kinetics by the Method of Continuous Monomer Addition

The differences in the kinetics of emulsion polymerization between nonswelling and swellable latex particles were explored in an attempt to define the locus of polymerization. The systems studied included vinylidene chloride, which forms a nonswelling particle, and mixtures of vinylidene chloride and butyl acrylate, which copolymerize to form a swellable particle. The basic experiment involved growing a seed latex by adding monomer at a constant rate. At low feed rates the rate of polymerization R_p was controlled by the rate of monomer addition R_a. The data fit the equation R_p?KR_a where the proportionality constant had an average value of 0.91. K was not dependent on monomer composition and appears to be a constant characteristic of the monomer addition process. In the range where this relationship holds, the reaction runs starved, i.e., monomer is consumed almost as fast as it enters the reactor. At higher rates of addition the reaction floods and excess monomer in the form of droplets can be detected. In this condition the rate starts out at a lower value but increases with conversion.' R_p is not controlled by R_a but does depend on monomer composition. No major differences were found between the behavior of swelling and nonswelling systems. Neither followed che kinetics expected if the Smith-Ewart theory were applicable. The results argue strongly that polymerization takes place at the particle-water interface or in a surface layer on the polymer particle.     

Kinetics and mechanism of emulsifier-free emulsion polymerization. III. Styrene/nonionic comonomer (2-hydroxyethyl methacrylate) system

The emulsifier-free emulsion polymerizations of styrene in the presence of about 0.33–2.7% (relative to styrene) of the water soluble comonomer, 2-hydroxyethyl methacrylate (HEMA), and of the initiator, potassium persulfate (KPS), were carried out. It was found that KPS plays a predominant role in the particle nucleation process, since the number density of polymer particles (N_p) was dependent on the 0.97-power of [KPS]. The nucleation ability of HEMA was weak, since N_p was dependent only on the 0.17-power of [HEMA]. The particle nucleation stage ceased quite early before 1% conversion, leading to nearly monodispersed polymer particles. The nucleation is suggested to be via the homogeneous nucleation mechanism. The particles grow via the core-shell structure mechanism (shell region polymerization), since the particle size is rather large—from 1500 to 6000 Å. The amount of HEMA can affect the shell thickness and physical properties of the shell, such as the monomer swelling capacity and monomer diffusion rate.