The effect of first-stage polymer Tg on the morphology and thermomechanical properties of structured polymer latex particles

A series of heterogeneous latexes having stage ratios of 40:60 between the first and second stage polymers were prepared by emulsion polymerization. The first-stage polymers were non-polar S-BuA with T_gs ranging from + 100 °C to + 20 °C and the second stage polymer was polar MMA–BuA–MAA having a T_g of 20 °C. The latex particle morphologies were studied using TEM and the thermomechanical properties of the resulting latex films were studied with DSC and DMA. Calculated diffusion rates for propagating species during the reactions were correlated to the observed morphologies and to the amount of interphase in the latex particles. To cite this article: O.J. Karlsson et al., C. R. Chimie 6 (2003).     

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     

Poly(N-ethylmethacrylamide) thermally-sensitive microgel latexes: effect of the nature of the crosslinker on the polymerization kinetics and physicochemical properties

Thermally-sensitive crosslinked submicronic particles were prepared by an emulsion/precipitation process of N-ethylmethacrylamide (NEMAM), using potassium persulphate as initiator and four different crosslinkers; ethylene glycol dimethacrylate (EGDMA), 1,3-butanediol dimethacrylate (1,3-BDDMA), 1,4-butanediol dimethacrylate (1,4-BDDMA) and tetraethylene glycol dimethacrylate (TEGDMA). At first, polymerization kinetics was studied by NMR, revealing the negligible effect of the crosslinker nature. On the contrary, the water-soluble polymer amounts, the final hydrodynamic particle size, the swelling ability, the electrokinetic properties were found to be dependent upon the nature of crosslinker. The final latexes were found to be narrowly size distributed irrespective of the crosslinker agent’s chemical nature. In this study, the water solubility of the cross-linker was reported to be an important criterion, but other factors, such as diffusion and reactivity, have to be taken into consideration. To cite this article: P. Hazot et al., C. R. Chimie 6 (2003).     

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.     

Uniform nonspherical latex particles as model interpenetrating polymer networks

Polystyrene/polystyrene latex interpenetrating polymer networks (IPNs) were prepared by seeded emulsion polymerization of styrene–divinylbenzene mixtures in crosslinked monodisperse polystyrene particles. The resulting latexes comprised uniform nonspherical particles, e.g., ellipsodal and egg-like singlets, symmetry and asymmetric doublets, and ice cream cone-like and popcorn-like multiplets. The nonspherical particles, which were formed by separation of the second-stage monomer from the crosslinked seed network during swelling and polymerization, are excellent models for studying phase separation in IPN's. The degree of phase separation increased with increasing degree of crosslinking of the seed particles, monomer/polymer swelling ratio, polymerization temperature, and seed particle size, and with decreasing divinylbenzene concentration in the swelling monomer. The results were consistent with a thermodynamic analysis based on the elastic-retractile force of the polymer network, the monomer/polymer mixing force, and interfacial tension force.     

Polystyrene (1)/poly(butyl acrylate/amide type functional monomer) (2) two-stage emulsion polymers. Synthesis and thermomechanical properties of latex films

Polystyrene (PS) (1)/Poly (n-butyl acrylate (BA)/amide type functional monomer) (2) structured latex particles were prepared through emulsion polymerization varying the hydrophilicity of the functional monomer employed. The second-stage polymerization kinetics, the size and morphology of latex particles, and the location of the functional groups in the final latexes were studied, in order to relate them to the thermomechanical properties of films cast from these latexes. It has been shown that, as expected, increasing the hydrophobicity leads to a better homogeneity in the copolymer formed during the second-stage polymerization, while the more hydrophilic functional monomer partly homopolymerizes in a separate phase. However, the functionalization by all the monomers used in this work, prevents the PS seed particles to form a continuous skeleton (percolated network). Further heat treatments at 140°C do not lead to the formation of a continuous PS phase as for pure BA/pure PS two-stage particles. In addition, some thermally induced crosslinking effects are discussed in relation with the functional monomer location within the particles. © 1995 John Wiley & Sons, Inc.     

Viscoelastic behaviour of butyl acrylate/styrene/2-hydroxyethyl methacrylate/acrylic acid latices thickened with associative thickeners

The rheological behaviour of butyl acrylate/styrene/acrylic acid latices thickened with a hydrophobically modified ethoxylated polyurethane (HEUR) or hydrophobically modified alkali-soluble polyacrylate emulsion (HASE) was investigated. While the pseudoplastic character of frequency dependence of complex viscosity was similar for both thickeners, viscoelastic behaviour, expressed as the ratio of loss and storage moduli, significantly differed, indicating that the HEUR molecules, unlike swollen HASE particles, create a viscoelastic space structure. The increase in hydrophilicity of the particle surface, achieved by incorporation of 2-hydroxyethyl methacrylate (HEMA) monomer into the latex copolymer reduced the viscoelasticity of latices thickened with HEUR, but not of those thickened with HASE. This confirms that adsorption of hydrophobic end-groups on particle surface is important for thickening of latices with HEUR and that a physical network of latex particles interconnected by the thickener macromolecules is formed. To cite this article: O. Quadrat et al., C. R. Chimie 6 (2003).     

Study of poly(St/BA/MAA) copolymer latexes with trimodal particle size distribution

A new strategy was developed for producing a polymer latex with trimodal particle size distribution by adding a second seed of polymer particles and some additional surfactants during polymerization. The polymerization was investigated by following the variation of the particle size, the size distribution, the number of particles, the surface tension and surfactant surface coverage at different stages of the polymerization process. The results showed that both the size and the size distribution can be easily controlled by varying the amount of additional surfactants and the second seed of polymer particles. The secondary nucleation was achieved when the surface coverage of particles was over 70%, and the amount of small particles formed increased with increasing amount of additional surfactants. The introduction of the additional surfactants had no significant effect on the size and number of middle particles, but reduced the size of large particles and caused the number of large particles to remain more stable because of the suppression of limited flocculation. Copyright © 1998 John Wiley & Sons, Ltd.     

New ethyl cellulose/acrylic hybrid latexes and coatings via miniemulsion polymerization

Ethyl cellulose (EC) was incorporated into copolymer latexes via miniemulsion polymerization. The effects of EC viscosity and EC content on droplet size, particle size, and polymerization kinetics were investigated. The higher the EC content and viscosity, the larger the droplet size and the less stable the latex suspension. Small droplets that could be efficiently nucleated were formed for the lower‐viscosity EC but the latex still showed limited colloidal stability. This was attributed to some phase‐incompatibility between EC and the acrylic polymer. These stability issues were overcome by using an oil‐soluble initiator and a crosslinker. The later enabled to physically entrap EC inside the polymer particles, whereas the former allowed in situ grafting of the growing acrylic radicals to the EC backbone decreasing thereby the extent of phase separation. Thermal‐mechanical analyses evidenced that the films obtained from the hybrid latexes displayed better properties than the EC‐free latex films or the physical blends. This supports the hypothesis of formation of hybrid latexes that synergistically combine the properties of the acrylic matrix and the EC polymer. Interestingly, a significant increase of the elastic modulus was observed between 50 and 90 °C. This mechanical reinforcement was tentatively attributed to the formation of a percolating EC‐based hybrid phase. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2329–2339, 2010     

Emulsion polymerization of vinyl acetate using a polymerizable surfactant. II. Polymerization mechanism

The mechanism of growth of latex particles in the emulsion polymerization of vinyl acetate using a polymerizable surfactant, sodium dodecyl allyl sulfosuccinate (TREM LF-40; Henkel) was investigated. Both the aqueous phase and the particle/water interface were found to be loci for the copolymerization of TREM LF-40 with vinyl acetate. Competitive growth experiments using TREM LF-40 and its nonpolymerizable derivative were conducted to separate the effects of aqueous phase and particle surface. Particle size analysis of the seeded and unseeded polymerizations coupled with kinetic results suggested that the reactions at the particle/water interface are more important and that the particle size of the latexes is a key parameter controlling the polymerization rate through copolymerization and chain transfer to the polymerizable surfactant at the particle surface. A decrease in particle size lead to an increase in the amount of TREM LF-40 polymerized at the particle surface and to a decrease in polymerization rate. © 1992 John Wiley & Sons, Inc.     

氯丁胶乳-聚甲基丙烯酸甲酯复合乳胶粒结构形态

以氯丁胶乳（Pa）为种子乳液,甲基丙烯酸甲酯（Pb）为第二单体,采用种子乳液聚合法,制备了氯丁胶乳-聚甲基丙烯酸甲酯复合乳胶粒。 热力学分析表明,当Pb的体积分数Φb＜0.69时,可同时形成Pa-Pb型正核-壳和（Pa＋Pb）分离型乳胶粒,当Φb＞0.69时,形成Pb-Pa型翻转型核壳结构乳胶粒,并伴有Pa-Pb型正核-壳结构乳胶粒的形成。 动力学分析表明,引发剂类型、第二单体的加入方式、种子乳胶粒的交联、单体/聚合物质量比是影响乳胶粒形态的主要因素。 采用水溶性引发剂过二硫酸钾（KPS）,以饥饿态方式加入单体,氯丁胶乳 聚甲基丙烯酸甲酯(PCR-PMMA)复合乳胶粒呈现正核-壳结构,以充溢态方式加入单体则不能形成明显的核-壳结构;而以油溶性偶氮二异丁腈（AIBN）为引发剂时,单体无论以充溢态方式加入还是饥饿态加入均倾向于形成翻转核-壳型粒子。 在种子乳胶粒中加入一定量交联剂二缩三乙二醇二甲基丙烯酸酯,有利于形成明显的正核壳结构。 以饥饿态进料,KPS为引发剂时,随着单体用量增加,壳层变厚,仍呈正核-壳结构,与热力学分析结果相吻合;以AIBN为引发剂时,随着单体用量增加,PCR-PMMA复合乳胶粒逐渐由翻转核壳型结构变为互穿结构。     

Polymer mediated peptide immobilization onto amino-containing N-isopropylacrylamide-styrene core-shell particles

Monodisperse cationic core-shell latex particles have been prepared using a shot polymerization process, with N-(3-aminopropyl)-methacrylamide-hydrochloride (APMH) as the functional monomer. The final latexes were characterized with respect to final polymerization conversion, water soluble polymer formation, particle size and size distribution, surface charge density and electrokinetic properties. Then the covalent grafting of maleic anhydride-alt-methyl vinyl ether (MAMVE) copolymer onto aminated latex particles was investigated. The most efficient conditions to obtain derivatised particles with no alteration of the colloidal stability were to control both polymer amount/latex particles concentration ratio and the mixing method of the two species. The charge inversion of the hydrolysed MAMVE functionalized particles was demonstrated by measuring the electrophoretic mobility as a function of pH. Finally, the covalent binding approach was implemented with peptide-MAMVE conjugates, confirming the great potential of this promising methodology for the preparation of reactive latex particles bearing peptides.     

Surface heterogeneity of polystyrene latex particles determined by dynamic force microscopy

Atomic force microscopy (AFM) was employed to characterize the surface chemistry distribution on individual polystyrene latex particles. The particles were obtained by surfactant-free emulsion polymerization and contained hydrophilic quaternary ammonium chloride, sodium sulfonate, or hydroxyethyl groups. The phase shift in dynamic force mode AFM is sensitive to charge/chemical interactions between an oscillating atomic force microscope tip and a sample surface. In this work, the phase imaging technique distinguished phase domains of 50-100 nm on the surfaces of dried latex particles in ambient air. The domains are attributed to the separation of ion-rich and ion-poor components of the polymer on the particle surface.     

Study of bulk morphology of polymer latex films using laser confocal fluorescence microscopy

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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.     

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.     

Phase separation in polystyrene latex interpenetrating polymer networks

Polystyrene/polystyrene latex interpenetrating polymer networks (IPNs) were prepared by seeded emulsion polymerzation of styrene–divinylbenzene mixtures in crosslinked monodisperse polystyrene seed latexes. The resulting latexes comprised uniform nonspherical particles, which were formed by separation of the second-stage monomer from the crosslinked seed network during swelling and polymerization. The kinetics of phase separation were investigated by examining the changes in particle morphology using optical microscopy, which revealed that the phase separation was induced by the relaxation of the polymer chains before polymerization began and was enhanced by increased conversion. The thermodynamics of phase separation were investigated by analysis of the free-energy changes during swelling and polymerization, and the phase separation was described by a nucleation-and-growth mechanism. The results of this study have been applied to the design and synthesis of a series of uniform nonspherical particles of different morphology.     

Biodegradable materials by reactive extrusion: from catalyzed polymerization to functionalization and blend compatibilization

This contribution aims at reviewing how reactive extrusion (REx) technique can participate in the design and development of biodegradable polymeric materials more particularly based on aliphatic polyesters issued from both renewable (agrochemical) and fossil (petrochemical) resources. On one side, REx will be approached for producing in a continuous way biodegradable aliphatic polyesters by ring-opening polymerization of lactones. Tin and aluminum-based catalysts will be considered for quantitatively converting the cyclic monomer in high molecular weight polyester chains within residence time of a few minutes only. On the other hand, such polyesters will undergo various chemical modifications again performed by REx. Self-branching reactions will be investigated in order to compensate the characteristic molecular weight reduction of the polyester chains as triggered by hydrolysis and/or transesterification side-reactions. Controlled functionalization reactions by maleic anhydride treatment will be studied as well. Finally biodegradable composite materials will be produced by REx and will rely upon the interface compatibilization between the polyester matrix and natural fillers such as starch granules or talc microparticles. To cite this article: J.-M. Raquez, et al., C. R. Chimie 9 (2006).     

A Computational Study of the Polymerization‐Induced Phase Separation Phenomenon in Polymer Solutions under a Temperature Gradient

This paper studied the polymerization‐induced phase separation phenomenon (spinodal decomposition) in a model binary polymer solution under a linear spatial temperature gradient for the purpose of fabricating anisotropic polymeric materials by using mathematical modeling and computer simulation. Reaction kinetics were incorporated with the non‐linear Cahn‐Hilliard theory and the Flory‐Huggins free energy expression in the model. Moreover, the slow mode theory and Rouse law were used to account for polymer diffusion. It was found that an anisotropic morphology was obtained when a temperature gradient was imposed along the polymer solution sample. The direction of the structural anisotropy, however, depended significantly on the overall phase separation time. The presence of a temperature gradient along the polymer solution sample generated a spatial variation in polymerization rate, which resulted in a spatial variation of quench depth. Consequently, at a given instant, the phase separation at different locations of the polymer solution was at different stages of spinodal decomposition. The droplet size formed along the polymer solution was therefore dependent on the polymerization rate, the quench depth and the stage of spinodal decomposition. Furthermore, the spatial temperature gradient produced a spatial variation in the process induction time, which contains the polymerization induction time and phase separation induction time. It was also found that the polymerization induction time played a significant role on the spatial variation in the overall process induction time.

     

Recent progress in nitroxide-mediated polymerizations in miniemulsion

Recent developments in nitroxide-mediated polymerizations conducted in emulsion and miniemulsion have advanced the field across a range of both experimental and theoretical fronts. This article reviews progress in bicomponent initiating systems (including use of camphorsulfonic acid to enhance rate), unimolecular initiating systems, miniemulsions not requiring the use of volatile costabilizers, polymerization of acrylates, mathematical modeling and simulation, and theoretical understanding with regards to issues such as compartmentalization, preservation of polymer chain livingness, the role of aqueous phase kinetics and phase partitioning. These topics are discussed and analyzed to present an integrated portrait of the current status of nitroxide-mediated polymerizations in emulsion/miniemulsion and to identify the most pressing concerns, issues, and opportunities. To cite this article: M.F. Cunningham, C. R. Chimie 6 (2003).