Equilibrium encapsulation of polystyrene latex particles

We have performed a series of seeded styrene emulsion polymerizations in which the second stage of growth was initiated only after the second-stage monomer charge had achieved equilibrium saturation with the seed particles. The final particles were observed in the electron microscope by using two means of distinguishing between the first- and second-generation polymer: (a) butadiene tagging and osmium tetroxide staining coupled with ultramicrotomy and (b) tritiated-styrene tagging coupled with autoradiographic detection. We find that the first- and second-generation polymer chains are not uniformly mixed throughout the final latex product; rather, the second-generation polymer overcoats the seed polymer in a core–shell fashion. In order to explain these results, we present the viewpoint that monomer actually concentrates at the periphery of the swollen particle to form a monomer-encapsulated structure, rather than swelling the particle uniformly as has always been envisioned. We believe the encapsulation phenomena to be governed by the microscopic thermodynamic environment of the latex particles which has, in turn, a profound effect upon the conformational behavior of the long-chain polymer molecules as they interact with the particle–water interface.     

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.     

Simulation of the latex particle morphology

A model is presented for the simulation of the structuration of polymer particles under conditions in which the new polymer chains are compatible with the polymer previously formed. The model involves the calculation of the monomer concentration gradients within the particles due to discrepancies in thermodynamic interactions between the monomer and the different polymers present in each part of the polymer particle. In addition, the distribution of free radicals in the latex particle is taken into account. This distribution results from the anchoring of the hydrophilic end-group of the growing polymer chain on the surface of the particle. The model was applied to the simulation of the polymerization of vinyl acetate on a butyl acrylate–vinyl acetate copolymer seed. It was found that the development of the particle morphology was mainly due to the profile of concentration of radicals in the particle. On the other hand, the effect of the monomer–polymer thermodynamic interactions on the particle morphology was found to be negligible. However, it has to be pointed out that this is because, for the system studied, the interaction parameters of vinyl acetate with polyvinyl acetate and polybutyl acrylate are nearly identical.     

Effect of Monomer Feeding Mode on thePreparation of Hollow Latexes with High MAA Content in the Core Latex Preparation简

In order to prepare hollow latex particles with optimum morphology based on osmotic swelling principle, three- layer core/shell latex particles with 40 wt% MAA in the core were first prepared via multistep seeded emulsion copolymerization, in which monomers were added by a semi-continuous process with monomer addition under two different forms： pure monomers＇ mixture （monomer addition）, and pre-emulsified monomers （pre-emulsion addition）. Then, the hollow latex particles with different morphologies were obtained after alkali post-treatment. Influences of the monomer feeding mode on the emulsion polymerization and the particle morphology were investigated. Results showed that the pre- emulsion addition could significantly improve the polymerization stability in each step, and greatly enhance the uniformity of shell encapsulation. The sizes of the core and core/shell latex particles obtained by the pre-emulsion addition were smaller and more uniform than those synthesized by the monomer addition, and the hollow latex particles with intact morphology were generated by alkali post-treating of the core/shell latexes prepared from the pre-emulsion addition. As the core size increased, the morphology of the post-treated particles underwent evolution from hollow to collapse. Moreover, the mechanism of the particle morphological evolution was proposed.     

Application of peroxide macroinitiators in core-shell technology for coating improvements

New approach to synthesis of core-shell latices is proposed in the presented work. The method is based on the peroxide macroinitiators utilization for formation of the seed particles with tethered to their surface peroxide moieties. As a result, initiation and chain-growing reactions of polymerization of the shell-forming monomer are localized precisely at the seed latex interface. That allows to diminish consumption of this monomer required for complete encapsulation of a core polymer. The advantages of this new method over the conventional core-shell technology are reflected in improving the properties of polymer coating derived from such latices.     

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.     

超浓乳液聚合制备PU/PS的SIPN粉状树脂研究

将聚氨酯予聚体 (PU ) 苯乙烯 (St)的复合体系 ,用超浓乳液聚合方法制备了半互穿聚合物网络(SIPN)复合聚合物 ,得到了用聚氨酯予聚体改性的聚苯乙烯 (PU/PS)SIPN粉状树脂 .研究了分散相的比例(α)和聚合温度对聚合稳定性及聚合转化率 -时间的关系 ;测定了聚合物胶乳粒子的大小、形态 ,玻璃化温度 ,动态力学性能等 .结果表明 ,超浓乳液聚合较之本体聚合具有较高的聚合速率 ,容易控制所制备的胶乳粒径 ,能够制得PU/PS复合聚合物的SIPN粉状树脂 .该粉状树脂便于加工 ,具有良好的强韧性 ,有利于扩大应用     

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.     

Hollow latex particles: synthesis and applications

One of the major developments in emulsion polymerization over the last two decades has been the ability to make hollow latex particles. This has contributed many fundamental insights into the synthesis and the development of structure in particles. Hollow latex particles also enhance the performance of industrial coatings and potentially are useful in other technologies such as microencapsulation and controlled release. Ever since the publication of the initial process patents describing these particles, there has been a global R&D effort to extend the synthetic techniques and applications. One prominent synthetic approach to hollow particles is based on osmotic swelling. This dominates the literature, and usually starts with the synthesis of a structured latex particle containing an ionizable core that is subsequently expanded with the addition of base. Fundamental to this approach are a sophisticated control of transport phenomena, chemical reactivity within the particle, and the thermoplastic properties of the polymer shell. Hydrocarbon encapsulation technology has also been employed to make hollow latex particles. One approach involves a dispersed ternary system that balances transport, conversion kinetics, and phase separation variables to achieve the hollow morphology. Other techniques, including the use of blowing agents, are also present in the literature. The broad range of approaches that affords particles with a hollow structure demonstrates the unique flexibility of the emulsion polymerization process.     

Measuring the extent of phase separation during polymerization of composite latex particles using modulated temperature DSC

The morphological features of composite latex particles predominantly develop during the polymerization process and depend upon a significant number of variables. In this study, we have concentrated on the relative polarities of the two polymers in the particles and the rate at which we added the monomers during semibatch reactions containing the seed polymer latex. Our particular interest was to develop data that could reveal the extent of polymer phase separation as a function of the amount of monomer fed, and to characterize the morphology resulting from it. While TEM is the most common analytical technique employed, we show in this paper that modulated temperature DSC can generate data that allows us to follow the phase separation process as the monomer feed progresses. By considering the possibilities of having “phases” within the particles of pure polymer, homogeneously mixed (but nonequilibrium) polymers, gradient and interfacial polymer, we have been able to quite successfully simulate the DSC data. This results in quantitative estimates of the relative amounts of these “phases” and their polymer compositions. Combining these results with TEM photos showing the spatial characteristics of the morphology, we can achieve a much greater understanding of the physical structure of the composite latex particles. In many cases we find that phase separation is far from complete at the end of the reaction process. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2790–2806, 2005     

丙烯酸2-乙基己酯/丙烯酸辐射乳液聚合——乳胶中羧基的分布

本文用辐射法引发丙烯酸2-乙基己酯/丙烯酸(EHA/AA)乳液共聚合,用酸碱反滴定法研究了剂量率、剂量、乳化剂浓度、固含量、共聚物分子量、丙烯酸浓度、丙烯酸加料方式及丙烯酸预先中和程度等反应条件对乳胶中羧酸可滴定百分比的影响。并对聚合机理作了初步探讨。     

Encapsulation of non-chemically modified montmorillonite clay platelets via emulsion polymerization

This paper demonstrates that a covalent bonding between clay platelets and polymer chains is not necessary for a successful encapsulation of the inorganic compounds through emulsion polymerization. In the work described in this paper, the chemical modification of clay was performed using two kinds of titanate coupling agents: titanium IV, (2-propanolato)tris(2-propanoata-O), 2-(2-methoxyethoxy) ethanol and titanium IV, 2-propanolato,tris(isooctadecanoato-O), where the former is saturated and the second has unsaturated alkyl groups. The hydrolytic stability of the organoclays thus synthesized was thereafter investigated. It was found that the titanate modifiers were highly sensitive towards hydrolysis as evidenced by Fourier transform infrared and thermal gravimetry analyses. The effect of a chemical modification step on clay encapsulation was studied by comparing the results obtained between reactions using the synthesized organoclays and the ones using native clay platelets. It was found that the incorporation of polymerizable double bonds on clay platelets was unnecessary to achieve successful encapsulation and that, surprisingly, the chemical modification step could be omitted for the synthesis of clay-containing latex particles. The effects of monomer feed composition, i.e., monomer mixtures consisting of different weight ratios methyl methacrylate/butyl acrylate, and process types on clay encapsulation were also investigated. Both parameters were found to have a strong influence on clay encapsulation. Finally, the surfactant concentration and the surfactant type were statistically found to have a significant effect on the clay/polymer interaction as evidenced by the results of glass transition temperatures of dried latex/clay nanocomposites powders.     

St/交联剂乳液共聚包覆硬脂酸改性碳酸钙颗粒的研究

在硬脂酸改性的纳米碳酸钙存在下,通过苯乙烯(St)与多乙烯基单体的乳液共聚合,制备了以纳米碳酸钙为核,以交联聚苯乙烯(PS)为壳的交联型PS/碳酸钙复合纳米粒子.研究了多乙烯基单体的种类和用量以及碳酸钙的用量对聚合反应以及包覆的影响.结果表明,多乙烯基单体以及碳酸钙的引入会使聚合反应速率有不同程度的降低;使用1%~5%的TMPTMA或DVB,可实现PS对碳酸钙颗粒的牢固包覆,不可抽提的PS达94%以上;当碳酸钙用量改变时,需要适当调整乳化剂和多乙烯基单体的用量;IR和TGA的结果表明,随着碳酸钙用量增加,产物中的碳酸钙含量也相应增加;TEM照片和计算结果显示,当碳酸钙用量为14.8%时,绝大部分碳酸钙颗粒被包覆,且基本上每个乳胶粒中包覆一个碳酸钙颗粒,复合粒子具有清晰的核壳结构,壳层厚度约为10 nm,而当碳酸钙用量增加到29.3%和58.7%时,壳层厚度减小,并且出现较多裸露的碳酸钙颗粒.     

Immobilization of cationic polymer particles having active ester groups onto solid surfaces

Monodispersed cationic polymer particles with sulfonium groups and active ester groups at their surfaces were prepared by emulsifier-free emulsion copolymerization of styrene (ST) with a water-soluble active ester monomer, methacryloyloxyphenyldimethylsulfonium methylsulfate (MAPDS). The cationic polymer particle monolayers were fabricated on unmodified and aminated glass plates by electrostatic interactions and chemical reactions, respectively. The polymer particles were immobilized onto unmodified glass plates at relatively regular intervals in the absence of electrolytes, and the morphology of particle monolayers on the glass plates was changed with solid content of latex, electrolyte and cationic surfactant concentration. The polymer particles were immobilized onto aminated glass plate as aggregates by controlling the pH of latex and electrolyte concentration. Remaining active ester groups of the particle monolayers were confirmed to react easily with primary amino compounds.     

Transmission electron microscopy observations of composite polymer colloid nucleated by functionalized silica

In this work, functionalized nanometric silica particles were engaged in emulsion polymerization of ethyl acrylate. The morphological characterization of this composite material was performed by transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS). We were particularly interested in the state of encapsulation of the silica particles and their distribution in the latex film. Initialy, we successively studied both components of the composite: polymer beads and silica particles differ by their size and also by their contrast. In addition, it was possible to perfrom dark field TEM to study this system of two amorphous phases because their respective amorphous halos are not too close. Hence, we investigated the colloid material in aqueous media and after film formation. Although no ideal encapsulation is observed in the colloid in aqueous media, the distribution of silica in the latex film is good. SAXS results are in good agreement with TEM observations.     

Preparation of styrene polymer/ZnO nanocomposite latex via miniemulsion polymerization and its antibacterial property

Styrene polymer/ZnO nanocomposite latex was fabricated using miniemulsion polymerization in the presence of coupling agent 3-aminopropyltriethoxysilane (APTES) and hexadecane as hydrophobe. The size distribution and morphology of the composite latex particles were characterized by dynamic light scattering and transmission electron micrograph. X-ray photoelectron spectroscopy and Fourier transform infrared spectrophotometer results demonstrate that ZnO nanoparticles were encapsulated into polymer phases. The coupling treatment of ZnO with APTES can improve the dynamic contact angles of ZnO nanoparticle with water to enhance its hydrophobicity. When 0.6% APTES to ZnO (wt/wt) is used to modify ZnO, the encapsulation efficiency of ZnO reaches to 95%. It shows that the high encapsulation efficiency improves dispersion of ZnO nanoparticles in polymer film by scanning electron microscope. The stable structural hybrid latex can adequately exert unique function of nanoparticles in coatings. It indicates that the coatings added the composite latex exhibits perfect antibacterial activity, which has a tremendous potentiality in the field of coating materials.     

Hydrophilic magnetic polymer latexes. 2. Encapsulation of adsorbed iron oxide nanoparticles

The encapsulation of seed polymer particles coated by anionic iron oxide nanoparticles has been investigated using N-isopropylacrylamide as a main monomer, N,N-methylene bisacrylamide as a crosslinking agent, itaconic acid as a functional monomer and potassium persulfate as an anionic initiator. The magnetic latexes obtained have been characterized with regard to particle size, iron oxide content and electrophoretic mobility. All these properties have been examined by varying several polymerization parameters: reaction medium, monomer(s) and crosslinking agent concentrations, nature of seed latexes and type of polymerization (batch versus shot process). The magnetic content in the polymer microspheres strongly depends on the polymerization procedure (i.e., encapsulation process) and varies between 6 and 23 wt%, and monodisperse magnetic polymer particles were obtained. Received: 28 December 1999 Accepted in revised form: 15 June 1999     

Controlled heterocoagulation of platelets and spheres

We report the controlled heterocoagulation of platelets and spheres, leading to the formation of colloidally stable, anisotropic hybrid particles. Anionically charged, nanosized polymer latex spherical particles were heterocoagulated on the surface of cationically charged hexagonal gibbsite platelets via the adsorption of a single layer of spheres onto both sides of the hexagonal platelets. The latex particles were annealed at a temperature above the Tg of the latex polymer, resulting in a thin polymer layer covering the gibbsite platelets. This heterocoagulation approach enabled the encapsulation of hydrophilic inorganic particles with polymer latexes and the formation of anisotropic hybrid particles.     

Mechanism of emulsion polymerization of styrene in soap-free systems

The formation and growth of monodisperse polystyrene latex particles in the absence of added surfactant has been studied by sampling polymerization reactions at different times and determining the surface and bulk properties of the latex. A large number of nuclei in excess of 5 × 10¹²/ml were generated during the first minute of reaction, but this fell due to coagulation until a constant number (10¹¹?10¹²/ml) was reached. The rate of polymerization per particle was then found to be proportional to the particle radius. Gel-permeation chromatography has shown that the initial particles consist mainly of material of MW 1000 with a small amount of polymer up to MW 10⁶, and the presence of this low molecular weight polymer, which in many cases can still be detected after 100% conversion, is taken as being indicative of particle formation via a micellization-type mechanism involving short-chain (MW 500) free-radical oligomers. M?_n values determined for the latex particles throughout the course of reactions show that the molecular weight increases to a maximum of about 10⁵ as the particles grow. The presence of anomalous regions within the particles has been confirmed by transmission electron microscopy, scanning electron microscopy, and gas adsorption studies. It has also been found possible to re-expose these regions within apparently homogeneous particles by stirring with styrene monomer; this is indicative of a molecular weight heterogeneity within the latex particles. The presence of sulfate, carboxyl, and hydroxyl groups upon the latex particle surfaces has been determined by conductometric titration.     

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.