Styrene emulsion polymerization: Kinetics and particle size distributions in highly swollen latex systems

The results are reported of studies on the kinetics and the time evolution of the particle size distribution in seeded styrene emulsion polymerization systems wherein the seed latex particles were highly swollen with monomer as a result of prior swelling by dodecane. Conditions were such that no new latex particles were formed nor was a significant number of monomer droplets present (“Interval III”). The data were fitted to obtain values for the rate coefficients for entry and exit (desorption) of free radicals. It was found that, during the early part of the polymerization (when the polymer:monomer ratio in the latex particles is considerably less then in an equivalent emulsion polymerization system without dodecane), the entry rate coefficient was much smaller than that measured in systems without dodecane. This effect is consistent with an entry mechanism wherein entering free radicals must displace surfactant molecules from the latex particles.     

On the kinetics of styrene emulsion polymerization above CMC. I. A mathematical model

A detailed mathematical model of the kinetics of styrene emulsion polymerization has been proposed. Its main features/assumptions are compartmentalization, micellar and homogeneous nucleation, particle formation by both initiator‐derived and desorbed radicals, dependence on the particle size of the rate coefficients, thermodynamic considerations, and aqueous phase kinetics. The model predicts that micellar nucleation dominates over homogeneous nucleation and that the evolution of the nucleation rate reaches a maximum, where desorbed radicals have an important contribution. Initiator‐derived radicals with only one monomeric unit have also a significant contribution on the rate of capture in particles. The results suggest that the correctness of the instantaneous termination approach depends not only on the size of the particle, but also on the type of entering radical (initiator‐derived or monomeric). © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2201–2218, 2000     

Free radical exit in emulsion polymerization. I. Theoretical model

The exit or desorption of free radicals from latex particles is an important kinetic process in an emulsion polymerization. This article unites a successful theory of radical absorption (i.e., initiator efficiency), based on propagation in the aqueous phase being the rate determining step for entry of charged free radicals, with a detailed model of radical desorption. The result is a kinetic scheme applicable to true “zero-one” systems (i.e., where entry of a radical into a latex particle already containing a radical results in instantaneous termination), which is still, with a number of generally applicable assumptions, relatively simple. Indeed, in many physically reasonable limits, the kinetic representation reduces to a single rate equation. Specific experimental techniques of particular significance and methods of analysis of kinetic data are detailed and discussed. A methodology for both assessing the applicability of the model and its more probable limits, via use of known rate coefficients and theoretical predictions, is outlined and then applied to the representative monomers, styrene and methyl methacrylate. A detailed application of the theory and illustration of the methodology of model discrimination via experiment is contained in the second article of this series. © 1994 John Wiley & Sons, Inc.     

无皂乳液聚合中单分散粒子的形成过程

在少量双官能团水溶性共单体(磺化丁二酸-聚乙二醇-烯丙基缩水甘油醚酯)存在下进行MMA/BA无皂乳液聚合,用CoulterLS230激光粒径分析仪研究了乳胶粒子的成核机理和单分散粒子的形成过程.乳胶粒子的成粒过程属多步成粒机理:先均相成核,形成不稳定的初始粒子,然后凝聚成稳定乳胶粒,其粒径分布经历了先变宽后变窄的过程,这是聚合过程中成核-凝聚-增长共同作用,相互竞争的结果.它还导致聚合初期出现周期成核的现象.     

Grafting of dodecyl methacrylate onto hydroxylated polybutadiene by miniemulsion polymerization

Homogeneous copolymer latex particles of dodecyl methacrylate (DMA) and low‐molecular‐weight hydroxy‐terminated polybutadiene (HTPB) oligomers were prepared by free‐radical polymerization using miniemulsion methods. Rate data and latex characteristics were consistent with the classical miniemulsion mechanism where nucleation of monomer droplets is the predominant pathway of particle formation. There is essentially no particle formation by secondary nucleation in the water phase. Characterization of the copolymer latex particles using transmission electron microscopy and modulated differential scanning calorimetry suggested that there is a significant amount of grafted poly(DMA)/HTPB polymer contributing to the miscibility of the HTPB and poly(DMA) phases. Particles were more homogeneous at increased HTPB composition, of relatively narrow polydispersity, and could be prepared reproducibly using a number of different initiation systems. The observed trends can all be rationalized in terms of conventional understanding of miniemulsion polymerization systems. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3404–3416, 2004     

Particle formation mechanism and kinetic model of ultrasonically initiated emulsion polymerization

A general kinetic model of particle formation in an ultrasonically initiated emulsion polymerization system is presented. This model takes into account homogeneous, micelle entry, and monomer droplet nucleation mechanism. The effects of the ultrasound in producing free radical, degrading free radical and influencing the fashion of the nucleation are also considered. Moreover, chain transfer to monomer and termination in the aqueous phase, capture of oligomer radicals by particles, and coagulation of particles are also considered. An analytical solution is obtained for the initial particle stage consideration. This model predicts that, if the desorption of radical from particles can be neglected, the concentration of the total radical in the aqueous phase is directly proportional to the cavitation concentration. Model predictions are in good agreement with experimental data obtained from the literature.     

Molecular weight distribution in emulsion polymerizations

A mathematical formulation is given which describes the evolution of the number distribution of the molecular weight (MWD) of linear polymer chains that grow in emulsion polymerization systems. The resulting set of coupled ordinary differential equations takes into account the microscopic events of free radical entry, exit, chain annihilation, bimolecular termination (by combination and disproportionation), and chain transfer in a mono- or polydisperse system. Simple analytic solutions are presented for systems in which the number of particles, as well as the average number of free radicals per particle, is constant and in which the rate coefficients are size independent. These solutions indicate that compartmentalization of the free radicals in the latex particles results in a significant increase in the polydispersity of the polymer produced by emulsion polymerization, compared with that in bulk systems. The theory shows that significant mechanistic information may be obtained from experimental MWDs and that, in principle, experimental conditions may be prescribed to grow a desired MWD. The MWDs are presented in a novel manner that facilitates the comparison of theory with experiment.     

Free radical entry in emulsion polymerizations

Measurements of the rate coefficients characterising the entry of free radicals into seed particles in styrene emulsion polymerizations has allowed the rate determining step for entry to be identified. This was found to be the rate of production of oligomeric species in the aqueous phase by monomer addition to the primary free radicals. Once formed the subsequent diffusion of these species to the latex particles (and their incorporation within these particles) is relatively fast, contrary to the assumptions of the previous diffusion controlled theories. The experimental results imply that the entering free radicals contain only two or three monomer units. Thermodynamic considerations show that such species should be both water soluble and surface active. Similar conclusions have been reached for other sparingly water soluble monomers, such as butyl acrylate and butyl methacrylate.     

Emulsion polymerization. I. Recalculation and extension of the Smith-Ewart theory

The most important assumptions underlying the Smith-Ewart theory are that the locus of chain propagation is the monomer-swollen latex particle, polymeric chains are initiated by radicals entering from the water phase into the particles, chain termination is an instantaneous reaction between two radicals within one particle, and particles are nucleated by radicals absorbed into monomer-swollen soap micelles. Right or wrong, these and other assumptions used by Smith and Ewart are retained in this paper. The newly derived and experimentally verifiable equations contain only such parameters which can be determined by experiments not involving emulsion polymerization. The proportionality constant between the particle number and the appropriate powers of soap and initiator concentrations is defined in terms of these independent parameters. Absolute rate equations are presented for the intervals before and after the completion of particle nucleation. To calculate these rates it is not necessary to have prior knowledge of the experimental particle number. The conversion at which particle nucleation is complete is calculated. The molecular weight is defined in terms of independent parameters. Predictions are made for the particle size distribution. It is shown that the validity of the theory is confined to specifiable intervals of conversion, to a certain range of monomer/water ratio, and to soap concentrations whose upper and lower limits are given.     

Conditions for secondary particle formation in emulsion polymerization systems

A simple means is deduced for determining conditions for secondary particle formation in emulsion polymerization systems in systems where the amount of added surfactant is below the cmc. A new radical formed from initiator in the aqueous phase will undergo some polymerization with aqueous-phase monomer, but must have three possible eventual fates: aqueous-phase termination, entry into a preexisting particle, or creation of a new particle. The means for determining the onset and extent of secondary nucleation is to modify HUFT theory to take into account a successful model for entry [ Macromolecules, 24, 1629 (1991)] which states that entry occurs if and only if the aqueous-phase radical has achieved a critical degree of polymerization z. Particle formation below the cmc is by homogeneous/coagulative nucleation which (if coagulation is ignored) gives an upper bound to the rate of formation of precursor particles; these are of a degree of polymerization J_crit > z. The resulting equations are readily solved, and require only a knowledge of the aqueous-phase propagation and termination rate coefficients (the latter is very high: ca. 10⁹ dm³ mol⁻¹ s⁻¹ for termination between the very small radicals), z and j_crit. Easily applied means are given for estimating all these quantities. The treatment gives good accord with experimentally observed conditions for the onset of secondary nucleation in low-surfactant systems (including taking in situ micellization into account).     

表面活性单体存在下的MMA／BA乳液共聚合（Ⅱ）：聚合动力？…

研究了表面活性单体「磺化－十二醇－烯丙基甘油－丁二酸酯钠盐（ＺＣ－Ｌ）」的用量对ＭＭＡ／ＢＡ／ＺＣ－Ｌ乳液聚合速率和粒径的影响,用Ｃｏｒｌｔｉｒ ＬＳ２３０型激光粒径分析仪测定聚合过程中乳液的粒径和粒径分布变化,并与ＭＭＡ／ＢＡ无皂乳液聚合及十二烷基苯磺酸钠存在下的ＭＭＡ／ＢＡ乳液聚合作了比较。「ＺＣ－Ｌ」〈ＣＭＣ时,成核机理为均相成核机理,乳胶粒需依靠粒子间的凝聚来提高表面电荷密度而稳定;「ＺＣ     

表面活性单体存在下的MMA/BA乳液共聚合(Ⅱ)聚合动力学及机理

研究了表面活性单体[磺化-十二醇-烯丙基甘油-丁二酸酯钠盐(ZC-L)]的用量对MMA/BA/ZC-L乳液聚合速率和粒径的影响,用CoulterLS230型激光粒径分析仪测定聚合过程中乳液的粒径和粒径分布变化,并与MMA/BA无皂乳液聚合及十二烷基苯磺酸钠存在下的MMA/BA乳液聚合作了比较.[ZC-L]CMC时,成核机理包括均相成核和胶束成核机理,生成的粒子因吸收体系中的表面活性单体而稳定存在.     

The peculiarities of homogeneous nucleation of reactive Cu0 colloidal particles in the presence of functional oligoperoxides

A method is proposed that combines the stage of formation of colloidal metal and metal-oxide particles with the stage of their surface modification by functional surface-active oligoperoxides (FSAP), which are sorbed irreversibly. Investigation of copper particle homogeneous nucleation kinetics witnesses the significant influence of supermolecular micelle-like structures formed by FSAP in solution on the reduction rate of Cu2+ cations caused by a phenomenon analogous to micellar catalysis. The rate constants of copper reduction in different local zones of the process have been determined. Particle homogeneous nucleation kinetics in the presence of surface-active oligoperoxides has been found to correspond to the main regularities of the Michaelis-Menten equation describing micellar catalysis. The carrying out of copper particle formation in distinct zones correlates well with the particle size distribution. The presence of reactive ditertiary peroxidic fragments on the particle surface as a result of FSAP sorption confers reliable protection from oxidation, hydrophobicity, and ability to form free radicals and participate in elementary stages of radical processes.     

The kinetics and compartmentalization of seeded emulsion polymerization of styrene with a series of seeds of different size

The Interval II kinetics and compartmentalization effect of emulsion polymerization of styrene with the seeds of five radii (r=40.2, 51.3, 76.5, 99.7 and 252.0 nm) have been studied. The kinetic parameters, i.e., the rate coefficients ρ, K and C which refer, respectively, to the entry of free radicals into latex particles, the exit of free radicals from the particles and the bimolecular termination of free radicals within the particles; n_ss and n_ss(thermal), the average number of free radicals per particle in the steady state and in the thermally induced background polymerization, respectively, are obtained. The propagating rate coefficient k_p, the termination rate coefficient k_t, as far as possible, are calculated in the runs. From this work, it can be concluded that the kinetic behavior, the kinetic parameters and the compartmentalization effect of emulsion polymerization are greatly influenced by the latex particle size.     

Styrene emulsion polymerization: Particle-size distributions

Data are presented on the time evolution of particle-size distributions (PSDs) in seeded and ab initio styrene emulsion polymerization systems. Initiation was by chemical reagent (potassium persulfate) or γ-radiation. The unswollen PSDs at various times during interval II of the polymerization were obtained by direct measurement of calibrated electron micrographs. Experimental results were fitted with the equations that describe the time evolution of an initial PSD. Analytic solutions to these equations that allow for entry, exit, and propagation of free radicals were obtained. The values of the rate coefficients for these processes used to fit the experimental data were in excellent agreement with those obtained from dilatometric kinetics experiments.     

Synthesis of Bimodal PVC Latexes by Emulsion Polymerization: An Experimental and Modeling Study

The onset and extent of secondary particle formation in the seeded emulsion polymerization of vinyl chloride were investigated by performing a series of seeded polymerizations at different concentrations of seed latex and surfactant. It was found that, in general, both the onset and the extent of secondary particle formation are determined not only by the rate of homogeneous nucleation, but also by the rates of particle coagulation. A comparison of methods to compute the evolution of the particle size distribution in vinyl chloride emulsion polymerization was also carried out. For growth processes, the widely-used pseudo-bulk model gives correct answers. For processes involving particle formation, on the other hand, this model cannot be used because it neglects, among others, the effects of nucleation and coagulation on the radical number distribution. To surmount this problem, we propose to use the zero-one-two model, for which the full population balance equations are given here.     

STUDY ON THE FORMATION MECHANISM OF MONODISPERSE PARTICLES IN THE EMULSIFIER-FREE EMULSION POLYMEAIZATION OF METHYL METHACRYLATE AND BUTYL ACRYLATE

The formation mechanism of monodisperse polymer latex particles in the emulsifier-free emulsion polymerizationof methyl methacrylate and butyl acrylate with potassium persulfate as initiator was investigated. A multi-step formationmechanism for the monodisperse polymer particles was proposed. The nucleation mechanism is considered to be thecoagulation of the precursor particles by homogeneous nucleation when the primary particles reach a critical size with highsurface charge density and sufficient stability. It had been proved by a special experiment that the early latex particles formedby the coagulation were stable. The primary particles grow by absorbing monomers and radicals in the polymerization systemand then become colloidally unstable again due to the understandable decrease of particle surface charge density, which leadsto the aggregation of the growing particles and the formation of larger latex pedicles therefrom. Aner the nucleation period,the preferential aggregation of the smaller particles in the propagation process leads to the change of the particles towards auniform size and narrower particle size distribution. The coexistence and competition of homogeneous nucleation,coagulation, propagation and aggregation result in the increase of the polydispersity index (U = D_(43)/D_(10)) in the first Stage,then its decrease in the later stage because of the competition of propagation and aggregation, and the gradual formation ofthe monodisperse particles.     

聚硅氧烷/丙烯酸酯核/壳复合胶乳的粒径分布与成核机理

通过种子乳液法合成出具有高有机硅含量核 壳结构的聚硅氧烷 丙烯酸酯复合粒子 .研究了聚合方法、乳化剂浓度、引发剂浓度、单体滴加速度等工艺条件对复合乳液粒径尺寸、分布与形态的影响 ,并对复合乳液的成核机理进行了探讨 .研究表明 ,乳化剂浓度对乳液粒子的粒径分布和形态、结构有显著影响 ,引发剂浓度增加将使粒子粒径减小 ;相对一次投料法 ,种子乳液法生成的粒子分布窄 ,具有明显核壳结构 ,通过壳层单体滴加速度可以控制粒子的粒径尺寸和分布 ;而壳层丙烯酸酯聚合物主要是在聚硅氧烷种子表面的“过渡层”聚合、富集而成 .     

Radical entry in emulsion polymerization: propagation at latex particles/water interfaces

In emulsion polymerization, complete entry of an initiator-derived, surface-active radical may involve its adsorption onto latex particles/water interfaces and subsequently its propagation with one more monomer molecule therein. However, all publications to date have defined this propagation step as a three-dimensional bulk reaction between a surface-active entry radical and a monomer molecule. This is incorrect conceptually. It is proposed that the rate of the propagation of surface-active entry radicals with monomer at latex particles/water interfaces be expressed as [Formula: see text] . In this equation, A is the interfacial area between water and latex particles; [M](P) and [Formula: see text] are the mean concentrations of monomer in the particle phase and entry radicals in the aqueous phase, respectively; k(I) is the radical propagation constant at the interfaces, and may be estimated via transition state theory. For seeded styrene polymerization by Hawkett et al. (J. Chem. Soc. Faraday Trans. 1 76 (1980) 1323), k(I) approximately approximately 4.2x10(-9)k(p) (mol(-1)dm(4)s(-1)) is estimated. Here k(p) is the propagation rate coefficient in bulk polymerization. This alternative approach should be useful for one to simulate radical entry rate in emulsion polymerization where the propagation step may be rate-determining, such as under monomer-starved conditions.