Conductive coating films based on low density In2O3 powders and polymer latexes

Several kinds of conductive coating films were prepared from a low-density indium(III) oxide powder (which was employed because it provides a much higher volume for the same weight) and polymer latexes. The low-density In₂O₃, which is an electrically conductive pigment, was prepared by pyrolysis followed by the combustion of water-swellable polymer microspheres imbibed with In(NO₃)₃, the precursor of In₂O₃. Either acrylamide/N,N'-methylenebisacrylamide or poly(vinylalcohol)/glutaricdialdehyde was used to generate spherical hydrogel particles. The polymer latexes with which the In₂O₃ was mixed had a soft core and a hard shell structure to ensure that the coating film has suitable mechanical properties in addition to conductivity. Acrylonitrile/butadiene/styrene copolymer ABS or acrylonitrile/butylacrylate/styrene copolymer ABAS latexes were used as binders for the conductive pigment. The powder coating followed by hot pressing, the water-borne coating consisting of low-density In₂O₃ and polymer latexes followed by curing, or the colloidal dispersion coating was used to deposit flexible conductive coating films on polyester sheets. The conductive pigment density and the polymer latexes' size and flowability are the factors that affect the characteristics of the film. We found that the colloidal suspension coating procedure based on ABAS latexes achieves better electrical and mechanical properties for the coating films. © 1996 John Wiley & Sons, Inc.     

Semiinterpenetrating polymer network latexes via concentrated emulsion polymerization

Latexes of semiinterpenetrating polymer networks (SIPN) of polyurethane (PU) and poly(methyl methacrylate) (PMMA) were prepared via the concentrated emulsion polymerization. In this procedure, a partially cross-linked PU was first prepared in a low polarity solvent from the appropriate precursors. Subsequently, MMA and an initiator were introduced into the solution, and the solution was used as the dispersed phase of a concentrated emulsion in water. Finally, SIPN latexes were obtained via the polymerization of the concentrated emulsion. For comparison purposes, SIPN materials have been also prepared via bulk polymerization. The studies with differential scanning calorimetry and transmission electronic microscopy showed that partial interpenetration was achieved in the SIPN latexes. The tensile behavior and particle morphology of the SIPN materials were investigated by changing the proportion of PU, the molar ratio of NCO/OH, the theoretical cross-link density, and the concentration of the initiator. The SIPN latexes prepared possess a high toughness. © 1995 John Wiley & Sons, Inc.     

Electrolyte stability of carboxylated latexes prepared by several polymerization processes

Carboxylated isoprene/styrene copolymer or polystyrene latexes have been prepared by several polymerization processes. The density of carboxyl groups chemically bound to the surface of particles (surface carboxyl groups), and the electrolyte stability of these carboxylated latexes was determined to elucidate the relationship between them. The critical coagulation concentration (CCC), which represents the electrolyte stability of latex, decreases considerably with increasing valency of the cation, as expected from theory. The CCC increases remarkably with increase in the density of surface carboxyl groups or increase in the degree of neutralization of surface carboxyl groups. The electrolyte stability of these carboxylated latexes seems to be governed substantially by the density of carboxylate ions on the surface of particles irrespective of the polymerization process or the composition of polymers in the interior of particles.     

Polystyrene latex particles bearing primary amine groups via soap‐free emulsion polymerization

Polystyrene latexes were prepared in the presence of an amino‐containing functional comonomer, N‐(3‐aminopropyl)methacrylamide hydrochloride (APMH), via soap‐free batch emulsion polymerization initiated by the cationic initiator 2,2′‐azobis(2‐amidinopropane) dihydrochloride. These latexes were characterized by studying the influence of the ionic comonomers on the polymerization kinetics, particle size, surface charge density and colloidal properties. The synthesized latexes were monodisperse with a final size between 100 and 600 nm depending on the APMH concentration. The initial polymerization rate and the particle number increased in accordance with the Smith–Ewart theory for soap‐free styrene emulsion polymerization with a hydrophilic functional comonomer. The final functionalization rate of the particles has been particularly studied with the intention of fitting the prepared latexes to be used in the immobilization of biological molecules for biological sample preparation and diagnostic applications. © 2020 Society of Chemical Industry     

Characterization of polystyrene latexes

Polystyrene latexes were prepared by emulsion polymerization. Styrene was used as monomer, potassium persulfate was the reaction initiator and sodium hydrogen carbonate was used as buffer. Surfactant may or may not be used. Three types of surfactant, ie sodium dodecylbenzene sulfonate (anionic), Triton X‐100 and Vulcastab LW (nonionic), and hexadecyltrimethyl ammonium bromide (cationic), were used. The prepared latexes were characterized according to concentration, density, pH, ionic strength, particle size, particle size distribution and surface charge. For prepared latexes with anionic surfactant, the effects of temperature, initiator concentration, surfactant concentration and amount of monomer on the latex size were investigated. Scanning electron microscopy was used as a tool for latex characterization. The results show that by increasing temperature, initiator and emulsifier concentration, the latex diameter decreases. However, size increases by increasing the amount of monomer. A potentiometric titration technique was employed for determination of surface charge. It was found that for all latexes, surface charge densities are in the same range. © 2000 Society of Chemical Industry     

Effects of surface functional groups on film formation and tensile strength development in reactive latex systems

The effect of surface functional groups on chain interdiffusion at the interfacial zone of reactive latexes was investigated. A series of latexes with different surface functionalities was prepared by batch or shot-growth emulsion polymerizations. The particle surface properties were varied by changing the number density of functional groups. The rate of tensile strength development decreases with the increasing number density of surface functional groups, which indicated that inter-particle crosslinking restricted the interdiffusion of polymer chains during film formation and annealing. The average diffusion coefficient D of polymer chains across particle interfaces was obtained from dynamic mechanical analysis and compared well with the results from the rate of tensile strength development. The magnitude of D of the reactive latex film was lower than that of the homopolymer film. The lower chain mobility of reactive latexes prevented mechanical strength development.     

Waterborne acrylic–casein latexes as eco-friendly binders for coatings

The use of casein as renewable resource to produce eco-friendly hybrid latexes has an increasing importance in industrial applications especially for high performance waterborne coatings. This work describes the synthesis of hybrid acrylic–casein latexes by emulsion polymerization of acrylic monomers in presence of varied casein concentration, and in absence of emulsifier which is usually a challenge for preparing stable nanocomposite latexes. The production and microstructure characterization of the casein–acrylic nanoparticles, as well as the properties of the films obtained from the hybrid latexes are here reported. The synthesized acrylic–casein latexes are able to form films with promising properties for a potential application as waterborne bio-based coatings.     

The determination of particle size distribution by hydrodynamic chromatography. An analysis of dispersion and methods for improved signal resolution

Various methods are described and compared for the determination of particle size distributions (PSD) in the submicron range by a technique known as hydrodynamic chromatography (HDC). Data are presented for a series of monodisperse latexes to establish the validity of the Mie theory of light scattering in describing the detector optical density signal. Analyses for the PSD involve corrections to the experimental HDC chromatograms for the effects of dispersion and are broadly classified as integral and numerical methods. Comparisons of calculations are made to chromatograms for polydisperse latexes as well as synthetic, discontinuous distributions and show the critical role of the optical density–particle size relationship in determining resolution and calculation stability. An integral method involving a non-Gaussian form for the dispersion function and a polynomial expansion for the chromatogram and an iterative numerical method involving modifications of a previously published technique are shown to give the best results for the PSD. The discussion includes an analysis of the possibility of improved signal resolution using turbidity in the absorption wavelength region and refractive index measurements. The conclusion is reached that increased resolution with turbidity is preferable to refractive index measurement since lower particle concentrations can be used.     

Transition behavior,surface characteristics and film formation of functionalized poly(methyl methacrylate-co-butyl acrylate) particles

Carboxylic functionalized poly(methyl methacrylate-co-butyl acrylate) particles were synthesized by soap free emulsion polymerization using sodium salts of itaconic acid and acrylic acid. Transition behaviors of these latexes in terms of glass transition of matrix and cluster were found to be completely different from those synthesized by solution polymerization. This disparity was attributed to the difference between co-monomers sequence distribution along the chains. Distribution of functional groups in the latexes was determined by conductometric titration. Film formation process of the latexes was also examined and interpreted based on the density of surface functional groups, transition behaviors, and particle size. AFM images revealed that, as the amount of these ionic co-monomers increases, more ordered films are obtained, while the particle inter-diffusion is greatly retarded. A dimensionless parameter indicating relative roughness of the films further supported the aforementioned findings.     

Facile fabrication and modification of epoxy acrylate latexes by epoxy resin and silane coupling agent

For the purpose of obtaining solvent-free epoxy acrylate latexes of good stability and excellent integrated performance, the epoxy acrylate latexes were fabricated using facile semi-continuous emulsion polymerization with varying amounts of epoxy resin and were modified by a silane coupling agent γ-methacryloxypropyltrimethoxysilane (KH-570). The effects of epoxy resin and KH-570 amounts on the performance of latexes and films were investigated from the aspects of particle size, morphology, tensile measurements, resistance properties, adhesion force, and thermal behavior. The results indicated that the acrylate monomers did graft onto the molecular chain of E-51 characterized by both epoxy value and Fourier transform infrared. Additionally, an emulsion of 80–100 nm particle size with a narrow distribution was obtained. The latex films retain resistances to satisfactory water, acid, alkali, and alcohol while maintaining good thermal stability, adhesion force, and flexibility. The importing of KH-570 could reinforce the spatial structure and cross-linking density and then improve the tensile strength of the latex films properly while keeping other performances well. This work provides a facile pathway for the optimized performance for epoxy acrylate latexes, and represents a tendency for environmental protection.     

A perspective on resins for aqueous coatings

Aqueous binder resins are becoming increasingly diversified and encompass classical latexes, latex-like polyurethane dispersions, and various aqueous dispersion polymers. Unlike classical and urethane latexes, the dispersion polymers are synthesized in non-aqueous media, have low molecular weights and are dispersed into water by mechanical means. The preparation of classical latexes from unsaturated monomers is scientifically well understood. Modem classical latex technology provides precise particle size control and the means to impart core-shell morphology to the particles. Core-shell morphology is beneficial for improved film formation, rheology and crosslink acceptance. Polyurethane dispersions are made by extending the molecular weight of isocyanate-terminated prepolymers with aqueous diamines. Though more expensive, polyurethane dispersion binders complement classical latexes by yielding tougher and generally more solvent resistant films. The low molecular weight acrylic, alkyd, polyester and epoxy dispersion polymers have advantages in good atomization, high gloss and flow-out in film formation Current progress includes improved scientific understanding of urethane latexes and of dispersion polymers. This is paralleled by the development of novel crosslinking systems.     

Preparation and characterization of carboxylated isoprene/styrene copolymer latexes

Carboxylated isoprene/styrene copolymer latexes were prepared, and the concentration of surface carboxyl groups and the freeze–thaw stability of these latexes were measured. It is clarified that the introduction method of the carboxylic monomer governs the distribution of carboxyl groups in latex particles. Introduction of the carboxylic monomer prior to the initiation of polymerization localizes only 12–13% of total carboxyl groups on the surface of particles, whereas introduction of the carboxylic monomer at the last stage of polymerization localizes more than 60% of total carboxyl groups on the surface of particles, though the percentage is strongly dependent on the conversion when the monomers are shot. These latexes show a remarkable increase in the freeze–thaw stability with the increase in the degree of neutralization of surface carboxyl groups in a fairly narrow range. There exists a linear relationship between the surface area occupied by a surface carboxyl group and the degree of neutralization of surface carboxyl groups at which the remarkable increase in the freeze–thaw stability is observed. The result suggests that the freeze–thaw stability is substantially determined by the density of carboxylate ion on the surface of particles.     

Photo-initiated miniemulsion polymerization as a route to the synthesis of gold nanoparticle encapsulated latexes

We report the first use of photo-initiated miniemulsion polymerization for the synthesis of well defined poly(methyl methacrylate) (PMMA) latexes. Furthermore, the application of photo-initiation is employed to the incorporation of decanethiol-capped gold nanoparticles (AuNPs). The procedure provides a low temperature polymerization for an oil-in-water miniemulsion with temperatures not exceeding 40 °C and polymerization times of only one hour. Using these mild reaction conditions allows the use of miniemulsion polymerization for the encapsulation of temperature sensitive species within the latex. Furthermore, we demonstrate the applicability of this method for the incorporation of decanethiol-capped AuNPs. Particle size distribution and morphology was studied using dynamic light scattering (DLS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). PMMA latexes ranged between 100 and 200 nm in diameter showing good particle size distribution and tendencies to form semi-ordered domains. We show that variations in surfactant, hydrophobe and initiator concentrations behave in the same manner as miniemulsions initiated through conventional thermal methods. TEM observations revealed that the latexes with encapsulated AuNPs displayed even distributions of AuNPs throughout the PMMA latex with no aggregation witnessed.     

Swelling behavior of emulsion polymer particles: comparison between fully cross-linked and partially cross-linked poly(acrylate) latexes

Summary Measurement of swelling is used to estimate the extent of cross-linking of latex particles prepared by emulsion polymerization. In this paper we report swelling data as a function of solvent activity for two latexes: (1) a poly(butylacrylate) (PBA) latex, and (2) a poly(isodecylacrylate) latex. In the latter case comparison is made between the swelling behavior of fully cross-linked, i.e., networks without free polymer chains, and partially cross-linked latexes. It is demonstrated that the equilibrium swelling properties are only slightly affected by the presence of uncross-linked chains. Swelling gives reliable results for the cross-link density only if the latex does not contain free chains. Received: 3 March 1998/Revised version: 13 May 1998/Accepted: 10 June 1998     

Retardation effect of styrene-acrylate copolymer latexes on cement hydration

Interactions between styrene-acrylate latexes and cement are investigated with emphasis of the charge properties of the polymer particles by means of calorimetry, adsorption measurement, and confocal laser scanning microscope. Three latexes with varied surface charges of polymer particles were prepared by respectively using methacrylic acid (MAA), sodium styrene sulfonate (SSS) and methyl poly(ethylene glycol) methacrylate (MPEGMA) as water soluble monomers during synthesis. It is found that the polymer latexes retard cement hydration in two manners, namely the delaying effect represented by a delayed hydration peak and the slowing down effect characterized by a reduced main hydration peak during the acceleration period. The delaying effect is closely related to the concentration of carboxylic groups existing in the latex, while the depression effect of hydration rate is majorly caused by the adsorption of polymer particles on surface of cement grains and proportional to the total charge density of polymer particles.     

Preparation of high molecular weight monodisperse polystyrene latexes by concentrated emulsion polymerization

The preparation of high molecular weight monodisperse polystyrene (PS) latexes by the concentrated emulsion polymerization is investigated. The PS latexes thus obtained have diameters in the range of 0.1–0.3 μm. The average size and the dispersity of the latexes are dependent on the concentration of surfactant (SDS), the monomer volume fraction, and the amount of monpolymerizable additive (decane). The ionic strength does not seem to affect the size but affect the dispersity of the latexes. Under proper conditions, monodisperse particles can be prepared with a quite small standard deviation. © 1993 John Wiley & Sons, Inc.     

PS/PMMA-CdSe/ZnS Quantum Dots Hybrid Nanofibers for VOCs Sensors

Hybrid nanofibers containing CdSe/ZnS quantum dots have been produced by electrospinning of hybrid latexes to characterize the electro-optical behavior of this novel luminescent sensing material. The latexes are synthesized by seeded semi-batch emulsion polymerization yielding cross-linked core-shell PS/QDs/PMMA particles with efficiently encapsulated quantum dots guaranteeing a good optical stability. Addition of polyvinyl alcohol (PVA) or polyethylene oxide (PEO) to the latexes is necessary to produce polymeric dispersions suitable for electrospinning manufacture of the nanometric fibers. The optimized polymeric dispersions are successfully electrospun obtaining fluorescent nanofibers in both cases. The hybrid nanofibers are sensitive to selected solvents (acetone, methanol and THF) and present positive response making them good candidates for the production of VOC sensors.     

Method for the determination of surface basic groups in cationic polystyrene latexes

The method for the determination of basic groups chemically bound to the surface of particles (surface basic groups) in cationic polystyrene latexes has been investigated. It is clarified that surface basic groups such as amidino groups resulting from 2,2′-azobis(2-amidinopropane) hydrochloride used as initiator and amino groups resulting from dimethyl aminoethyl methacrylate copolymerized can be determined accurately by the following method. First, latexes are cleaned and surface basic groups are converted into unneutralized from by ion exchange; then, latexes are titrated conductometrically with strong acid. By this method, however, surface amidino groups and surface amino groups cannot be determined separately.     

Relative shear stability of mini- and macroemulsion latexes

The shear stability of mini- and macroemulsion latexes is compared and quantitatively evaluated with respect to their particle-size distributions. The effect of a few externally added large particles on the shear stability of these two types of latexes was also investigated. All the latexes selected were in the colloidal size range (less than 1 micron). The original particle sizes for the macroemulsion latexes ranged from 141 to 241 nm, and those for the miniemulsion latexes ranged from 96 to 209 nm. The miniemulsion latexes were found to be more shear stable than were their macroemulsion latex counterparts over the particle-size range investigated. This trend was repeated even in the presence of a few large particles. Additionally, seeding experiments suggest that mini- and macroemulsion latexes incur different levels of shear aggregation due to inherent differences in their particle-size distributions. The shear rate used along with the particle size and number were quantitatively shown to significantly influence the aggregation process. Finally, a quantitative method for evaluating relative shear stability in emulsion polymerization was demonstrated, which, although not very rigorous, could serve as a starting point for further quantitative isolation and investigation of the various parameters that affect the shear aggregation process. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1317–1324, 1997     

环氧乳液改性水泥基材水化过程的硬化机理

极端环境和复杂荷载条件对混凝土结构的材料性能提出了更高的要求,聚合物通过改性水泥基材提高混凝土性能的方法已经得到了广泛应用。本研究为揭示环氧乳液改性水泥基材水化过程的硬化机理,通过等温放热试验分析环氧乳液对水泥水化放热过程的影响,结合原位XRD技术跟踪水泥主要矿物熟料和水化产物在水化反应早期的相含量发展。研究结果表明,环氧乳液对水泥水化的阻滞作用与环氧颗粒、水泥矿物熟料和水化产物之间的相互作用有关,并随着水化时间的延长,相互作用效果越明显。在水泥胶凝体系中,环氧乳液会减缓水化放热速率,降低水化放热峰值,减少累积放热量。环氧乳液通过抑制水泥矿物(C₃S、C₃A、石膏)的溶解和水化产物(钙矾石、氢氧化钙)的析出,延缓硅酸盐反应和铝酸盐反应;环氧乳液对水泥水化的影响随着其掺量的增加而增强。