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.     

Evidence for and against concentration gradients in polymerizing latex particles

A single-charge emulsion polymerization involving a monomer which is a good solvent for its polymer is considered. It is shown to be unlikely that within the polymerizing latex particles there are concentration gradients large enough measurably to affect the kinetics of the reaction. The average displacement of monomers due to Brownian motion within the latex particles and in the absence of concentration gradients is calculated. This diffusive mean free path, corresponding to an interval involving less than 1% change in conversion, is shown to be much longer than the radius of the latex particle. Consequently, loci where monomer concentration is perturbed by conversion to polymer are immediately swamped by unreacted monomer. Also, direct experimental evidence exists showing that the monomer concentration in latex particles is about the same when nonpolymerizing latex particles are saturated or during polymerization in the presence of monomer excess. The thermodynamics of saturation swelling preclude the possibility of the existence of large concentration gradients. The arguments that have been advocated in the literature for core–skin separation within polymerizing latex particles were based on conversion data which were thought to be linear with time, while a reexamination indicates that they were not. The observed core–skin separation obtained when butadiene or tritiated styrene were copolymerized with styrene in the presence of a polystyrene homopolymer seed latex has questionable relevance to single-charge homopolymerization. There are reasons to doubt that the distribution of co-monomers within latex particles can be frozen by their conversion to polymers in a two-stage emulsion polymerization.     

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.     

The mechanisms of latex particle formation and growth in the emulsion polymerization of styrene using the surfactant sodium dodecyl sulfate

A new method is presented that provides experimental information which is qualitatively and quantitatively sensitive to assumptions made as to the mechanisms of free radical entry and of latex particle formation in emulsion polymerization systems. The method consists of (1) obtaining (by electron microscopy) the full particle-size distributions (PSDs) at several different times soon after the cessation of latex particle nucleation, (2) using these PSDs to determine the volume dependences of the various rate coefficients governing particle growth by fitting the data to the appropriate evolution equations, and (3) employing these empirical rate coefficients to find that time dependence of the nucleation rate which fits the early-time PSD (again using the evolution equations). This method is quite sensitive to mechanistic assumptions: for example, one is able to determine whether or not the nucleation rate is an increasing or decreasing function of time. The technique is applied to a styrene nucleation system employing sodium dodecyl sulfate as surfactant at well above the critical micelle conventration. The data cannot be fitted even qualitatively by a simple one-step nucleation mechanis, whether it involes micellar entry or homogeneous nucleation. It is found, on the other hand, that the results can be accurately fitted by assuming that coagulation events between primary colloidal particles, perhaps formed by homogeneous nucleation, dominate both the nucleation process and the entry of free radicals into mature latex particles. In addition, the data indicate that the rate of free radical entry into the latex particles decreases with increasing particle size, at least for particles of unswollen radius less than ca. 40 nm.     

不同尺寸（0.02—0.5μm）单分散聚苯乙烯乳液微球的制备

通过对苯乙烯乳液聚合微观动力学以及聚合过程中胶粒直径及其分布随时间变化的理论分析,并通过实验验证,比较了不同乳化剂种类、不同反应温度和不同单体用量条件下,产物胶乳的粒径分布,发现乳液聚合最终产物的粒径分布与成核期长短没有直接联系,而是取决于自由基进入胶粒的速率常数、稳态增长时间、胶粒中的平均自由基数目和胶粒的体积增长速率,胶乳单分散性随这些参量的增大而提高,从而解释了采用高温、高引发剂浓度以及长时间反应的条件对最终的胶粒尺寸分布的影响。本文还通过实验,找到了在20～500nm范围内控制粒径大小及粒径分布的方法。在20～100nm的范围内,用一步法乳液聚合,通过改变单体用量和乳化剂浓度,制备了一系列粒径的单分散聚苯乙烯胶乳;在100～500nm的范围内,运用种子乳液聚合,通过改变溶胀单体与种子胶乳的用量比,也制得了不同粒径的单分散聚苯乙烯胶乳。     

The Effect of Nano-SiO2 Colloid on Soap-free Emulsion Polymerization of Methyl Methacrylate and Hydroxyethyl Methacrylate

Soap-free emulsion polymerization of methyl methacrylate (MMA) and hydroxyethyl methacrylate (HEMA) was carried out in the presence of colloidal nano-SiO₂ particles. The effect of nano-SiO₂ level on the monomer conversion, polymerization rate (Rp), and emulsion stability was investigated. The viscosity, particle size distribution of the emulsions, surface tension, and ionic conductivity of these systems were determined. Upon the introduction of the nano-SiO₂ particles into this system, the Rp and monomer conversion increased and the average particle size of the P(MMA-HEMA) emulsion decreased in comparison to emulsions formed in the absence of nano-SiO₂. However, the particle size distribution became broader to some degree. Scanning electron microscope observations demonstrated that the shape of these latex particles were uniformly spherical. The surface tension and ionic conductivity of the system increased significantly after polymerization, but the presence of nano-SiO₂ resulted in an increase in surface tension and a decrease in ionic conductivity in comparison to the particle–free system.     

Emulsion polymerization. VI. Concentration of monomers in latex particles

Nonpolymerizing latex particles surrounded by an aqueous phase saturated with monomer absorb only a finite amount of monomer, even if the monomer is a good solvent for the polymer, because the surface energy of each particle increases on swelling. At equilibrium the change in surface energy and the free energy of mixing exactly balance. Equations based on this thermodynamic principle predict with good accuracy the saturation swelling of crosslinked and uncrosslinked latex particles and the partitioning of monomer between the aqueous phase and latex particles at partial saturation. The available experimental data on swelling of latex polymers with monomers are reviewed. Earlier papers assumed that during emulsion polymerization the monomer concentration in the latex particles is independent of conversion as long as monomer droplets are present. This assumption is shown to be a justifiable approximation. The thermodynamics of the swelling of latex particles with a blend of two monomers is presented. The calculations indicate that copolymerization in emulsion should define reactivity ratios differing from those of homogeneous copolymerization by not more than 40% if the solubility of the comonomers in water is low. The reactivity ratio scheme is strictly applicable to emulsion copolymerization if the solvent properties of the two comonomers are identical.     

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.     

无乳化剂乳液聚合法合成单分散大粒径高分子微球的研究

无乳化剂乳液聚合法合成单分散大粒径高分子微球的研究朱世雄杜金环金熹高陈柳生（中国科学院化学研究所北京１０００８０）关键词无乳化剂乳液聚合，单分散，均相成核，低聚物胶束微米级大粒径单分散高分子微球在标准计量、情报信息、分析化学等许多领域都有广泛的...     

Dextran stabilized poly(methyl methacrylate) latex particles and their potential application for affinity purification of lectins

 Stable poly(methyl methacrylate) latex particles (220–360 nm in diameter) using dextran as the protective colloid were prepared and characterized in this study. Such an emulsion polymerization system follows Smith–Ewart Case III kinetics (i.e., the average number of free radicals per particle is greater than 0.5) due to the relatively large latex particle size. The carbohydrate content of these dextran modified emulsion polymers shows a maximum around 5% dextran based on total monomer weight. The latex stability during polymerization is closely related to the carbohydrate content of these latex particles, and it is controlled by the ratio of the thickness of the dextran adsorption layer to that of the electric double layer of the latex particles. The critical flocculation concentration (CFC) of the latex products correlates well with the latex stability during polymerization. The greater the total scrap produced during polymerization (i.e., the stronger the bridging flocculation), the lower is the CFC of the latex products. The affinity precipitation of concanavalin A (a model lectin used in this study) by the dextran modified PMMA latex particles is also illustrated in this study. The specifically adsorbed concanavalin A increases with the carbohydrate content of the dextran modified latex particles. Received: 9 December 1996 Accepted: 8 April 1997     

Study on controlling particle growth in seeded emulsion polymerization with regulated coagulation based on the electrostatic interactions

30wt% solid content, anionic seed copolymer latex P(methyl acrylate-co-methyl methacrylate) was prepared by conventional emulsion polymerization, and then the seeded emulsion polymerization was carried out accompanied with the electrostatic coagulation during the reaction in the presence of counter-ion species, such as cationic monomer and initiator. In this article, effects of cationic monomer (dimethyl aminoethyl methacrylate, DM) content, secondary monomer to seed polymer weight ratio, M/P and amount of emulsifier (polyoxyethylene nonylphenylether with 23 units of ethylene oxide, PEO23) were investigated on the effective particle growth and the stability of final latex. With 10wt% DM in monomer, M/P ratio at 2.0 were recommended. An optimal policy for handling the emulsifier content without the nucleation of secondary particles while achieving the controlled coagulative growth was proposed from the observations of polymer yield and particle size during the polymerization.     

Preparation of Bowl-Like Polymer Particles via Multi-Step Emulsion Polymerization and Alkali Post-Treatment

Summary : Monodisperse P(BA-MMA-MAA-EGDMA)/P(St-MAA-DVB) core/shell latex particles were first synthesized by a four-step emulsion polymerization, and a new kind of latex particles with “bowl-like” morphology were obtained by post-treating the resultant core/shell particles under alkali condition. Results indicated that the feeding rates of the monomer mixture and initiator aqueous solution were the key parameters to obtain monodisperse core/shell latex particles in the emulsion polymerization process, and the latex particles with “bowl-like” morphology could be generated only when the treatment temperature was equal or higher than 70 °C.     

Relaxation Studies of Emulsion Polymerization of Styrene Initiated by Ultraviolet Light (using α-sodium anthraquinone sulfonate/triethyl amine as photosensitizer)

Abstract

This paper presents the results of relaxation studies of the seeded emulsion polymerization of styrene initiated by UV-light with a water-soluble photosensitizer. The relaxation kinetic runs were performed at 45, 50, 55, and 60°C using a small diameter rotary dilatometer with an inner magnetic agitator. The entry rate coefficient of thermally induced free radicals into the latex particles, p ₀; the exit rate coefficient of free radicals from latex particles, k; and the average number of free radicals per particle in the thermally induced background polymerization, n _ss(thermal) were determined. The propagating rate coefficient kp was determined with the data of monomer concentration in a particle, C _M, obtained from experiments with chemical initiation. The Arrhenius formula with p ₀, k, and k_p was also obtained.     

Synthesis of iron oxide/poly(methyl methacrylate) composite latex particles: Nucleation mechanism and morphology

A magnetic poly(methyl methacrylate) (PMMA) composite latex was prepared by soapless emulsion polymerization in the presence of ferrofluid, and the ferrofluid was prepared by means of a coprecipitation method. The effects of various polymerization parameters, such as the monomer concentration, ferrofluid content, and initiator concentration, on the conversion curve and particle size of the magnetic composite latex particles were examined in detail. The results showed that two nucleation mechanisms were involved according to the polymerization conditions. In the monomer‐rich and less ferrofluid system, self‐nucleation of PMMA was dominant over the entire course of emulsion polymerization. In the ferrofluid‐rich system, seeded emulsion polymerization was the main course to form the magnetic composite latex particles. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5695–5705, 2004     

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.     

荧光探针法研究核壳结构有机硅-丙烯酸酯乳液的聚合行为

以芘为荧光探针,探讨了有机硅-丙烯酸酯核壳乳液聚合过程中,芘的第一振动峰(373 nm处)与第三振动峰(384 nm处)荧光强度的比值I1/I3与乳化剂、有机硅单体(D4)和引发剂(KPS)用量之间的关系,并结合聚合过程中探针芘的I1/I3峰值与单体转化率及乳胶粒形态演变之间的关系,研究了核壳结构有机硅-丙烯酸酯乳液的聚合行为.研究结果表明,探针芘的I1/I3峰值随乳化剂用量,D4用量,KPS用量不同发生相应的变化,随单体转化率的增加而增大.当乳化剂用量、D4用量、KPS与总单体的质量比依次为2 g、8 g、0.7%时,得到的乳液具有优良的综合性能.聚合反应过程中,当种子乳胶粒转变为核壳乳胶粒时,芘的I1/I3峰值仍呈现出明显的转变,说明有机硅-丙烯酸酯核壳乳液具有互穿聚合物网络结构.因此,荧光探针可用于研究有机硅-丙烯酸酯核壳乳液聚合反应进程.     

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.     

超声无皂乳液聚合制备BA/St/AM三元共聚物乳胶粒及其聚合机理研究

将超声技术引入到无皂乳液聚合方法中,在不加入任何引发剂和乳化剂的情况下,制备了丙烯酸丁酯(BA)/苯乙烯(St)/丙烯酰胺(AM)三元共聚纳米乳胶粒.研究了不同超声时间对单体转化率、乳胶粒粒径以及乳液粘度的影响.同时还探讨了超声无皂乳液聚合机理,认为AM在聚合过程中起到了引发和稳定的作用.TEM照片表明,乳胶粒直径大约在80nm左右,FTIR及DSC分析表明产物为三元共聚物,而不是共混物.     

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     

镶嵌型乳胶粒子的合成

以苯乙烯、甲基丙烯酸甲酯、丙烯腈等单体或它们的混合物为硬单体,天然胶乳为弹性组分,经多步种子乳液聚合法制得了在天然胶乳的粒子上镶嵌硬聚合物相的互穿网络型乳胶粒子.考察了十二烷基硫酸钠、十二烷基苯磺酸钠、壬基酚聚氧乙烯醚、油酸等乳化体系,过硫酸钾、过氧化苯甲酰热引发体系及异丙苯过氧化氢-四乙烯五胺、叔丁基过氧化氢-四乙烯五胺等氧化还原引发体系对聚合反应的影响.研究了交联剂用量对互穿结合率、溶胶含量的影响及溶胀时间、硬单体组成、乳化剂种类对乳胶粒子形态的影响,确定了适宜的聚合配方和工艺条件.透射电镜观察乳粒形态结果表明,单一使用极性或非极性单体,仅得到核-壳结构乳液,而采用不同极性单体复合、溶胀、互穿,得到的是镶嵌硬聚合物型乳粒结构.