Search Results (21)

Mica is a naturally layered material recognized for its superior insulation and exceptional barrier properties; however, it is prone to agglomeration, and its compatibility with resin remains to be resolved. In this work, phosphate butynediol ethoxylate (PBEO), synthesized by the reaction of a commercial corrosion inhibitor, butynediol ethoxylate, with phosphorus pentoxide, was employed to modify mica nanosheets (MNs), as evidenced by FTIR, Raman, and XPS. The obtained MN@PBEO demonstrated improved water dispersibility and enhanced compatibility with acrylic latex. EIS measurements revealed that the impedance (|Z|_0.01Hz) for the waterborne acrylic coating with 0.5 wt% MN@PBEO was approximately an order of magnitude greater than that of the pure waterborne acrylic coating after 28 days of immersion in a 3.5 wt% NaCl solution. Additionally, compared to the pure waterborne acrylic coating, the 0.5 wt% MN@PBEO/acrylic nanocomposite coating on Q235 carbon steel exhibited a water diffusion coefficient that was roughly ten times lower, demonstrating substantially enhanced corrosion protection, attributable to its superior barrier properties. Full article

Water-based (meth)acrylic (co)polymer dispersions are produced on a large scale for various applications including coatings, adhesives, paints, and construction materials. A major benefit of waterborne polymer dispersions as compared to more traditional solvent-based alternatives is the low volatile organic compound (VOC) content, which results in an improved environmental profile. Following the trend of sustainability that has driven the growth of acrylic dispersions, recent research has focused on further enhancing the properties of these products by incorporating biobased materials such as polysaccharides (e.g., cellulose, starch, chitin, and chitosan), and proteins (e.g., casein, soy protein, and collagen). Amongst a large number of benefits, the incorporation of biomaterials can serve to decrease the amount of petroleum-based polymers in the formulation and can also contribute to enhance the physical properties of the resulting bio-composites. In this review, the beneficial role of these biopolymers when combined with waterborne acrylic systems is summarized. Recent advances in the use of these biobased and biodegradable materials are covered, aiming to provide guidance for the development of more sustainable, high-performance latex-based bio-composites with minimal environmental impact. Full article

This work deals with the coating properties of synthetic latices comprising two kinds of polymers, specifically polyacrylate and polypyrrole, which were simultaneously formed by semi-continuous emulsion polymerization using a “one-pot” synthesis strategy. In this procedure, both the emulsion polymerization of acrylate monomers and the oxidative polymerization of pyrrole occurred concurrently in one reactor. Polyacrylate latices differing in polypyrrole loading were prepared by applying various dosages of pyrrole, specifically 0, 0.25, and 0.50, based on the fraction of acrylate monomers. The effect of the in situ incorporated polypyrrole component (having the nature of submicron composite polypyrrole-coated polyacrylate latex particles) on the physico-mechanical properties and chemical resistance of the resulting heterogeneous coating films was investigated. The interaction of incorporated polypyrrole and anti-corrosion pigments (see ZnS, Zn₃(PO₄)₂, ZnFe₂O₄, MoS₂, and ZnO) on the corrosion resistance of coatings was evaluated by using the electrochemical linear polarization technique. The polyacrylate latex prepared with the lowest polypyrrole loading (achieved by polymerizing 0.25 wt. % of pyrrole related to acrylic monomers) was found to be the optimum binder for waterborne anticorrosive coatings based on their properties and protective function. Their compatibility with the selected types of pigments was studied for these latex binders. In addition, their influence on the anti-corrosion efficiency of polyacrylate paint films was evaluated using the linear polarization electrochemical technique. For high corrosion resistance, the ZnS and MoS₂ pigments, showing compatibility with polyacrylate latices containing the polypyrrole component, proved to be advantageous. Full article

The escalating global emphasis on sustainability, coupled with stringent regulatory frameworks, has spurred the quest for environmentally viable alternatives to petroleum-derived materials. Within this context, the adhesives industry has been actively seeking renewable options and eco-friendly synthesis pathways. This study introduces geraniol, a monoterpenoid alcohol, in its unmodified form, as a key component in the production of waterborne pressure-sensitive adhesives (PSAs) based on acrylic latex through emulsion polymerization. Multiple formulations were developed at varying reaction times. The adhesives underwent comprehensive chemical characterization employing techniques such as Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), Nuclear Magnetic Resonance (NMR), Gel Permeation Chromatography (GPC), and dynamic light scattering (DLS). The viscosities of the formulations were measured between 4000 and 5000 cP. Adhesion tests showed peel strength values of 0.52 N/mm on cardboard and 0.32 N/mm on painted steel for the geraniol-based formulations. The results demonstrate the potential for geraniol-based PSAs to offer a sustainable alternative to petroleum-derived adhesives, with promising thermal and adhesive properties. Full article

The development of a dynamic network for commodity polymer systems via feasible methods has been explored in the context of a society-wide focus on the environment and sustainability. Herein, we demonstrate an adaptive post-curing method used to build a self-healable network of waterborne polyurethane–acrylate (WPUA) composite latex. The composite latex was synthesized via the miniemulsion polymerization of acrylates in the dispersion of waterborne polyurethane (PU), with commercial acetoacetoxyethyl methacrylate (AAEM) serving as the functional monomer. Then, a dynamic disulfide (S–S)-bearing diamine was applied as the crosslinking agent for the post-curing of the hybrid latex via keto-amine condensation, which occurred during the evaporation of water for film formation. It was revealed that the microphase separation in the hybrid films was suppressed by the post-curing network. The mechanical performance exhibited a high reliability as regards the contents of the crosslinking agents. The reversible exchange of S–S bonds meant that the film displayed associative covalent-adaptive networks in the range of medium temperature in stress relaxation tests, and ≥95% recovery in both the stress and the strain was achieved after the cut-off films were self-healed at 70 °C for 2 h. The rebuilding of the network was also illustrated by the >80% recovery in the elongation at break of the films after three crushing–hot pressing cycles. These findings offer valuable insights, not only endowing the traditional WPUA with self-healing and reprocessing properties, but broadening the field of study of dynamic networks to polymer hybrid latex. Full article

Waterborne polyurethane-acrylate (WPUA) grafted with polyurethane was prepared to improve the film-forming ability of hard-type acrylic latex. To balance the film-formation ability and hardness, the WPUA latex was designed with a hard core (polyacrylate) and soft shell (polyurethane). The grafting ratio was controlled through varying the content of 2-hydroxyethyl methacrylate (HEMA) used to cap the ends of the polyurethane prepolymer. The morphologies of the latex particles, film surface, and fracture surface of the film were characterized through transmission electron microscopy, atomic force microscopy, and scanning electron microscopy, respectively. An increase in the grafting ratio resulted in the enhanced miscibility of polyurethane and polyacrylate but reduced adhesion between particles and increased minimum film formation temperature. In addition, grafting was essential to obtain transparent WPUA films. Excessive grafting induced defects such as micropores within the film, leading to the decreased hardness and adhesive strength of the film. The optimal HEMA content for the preparation of a WPUA coating with excellent film-forming ability and high hardness in ambient conditions was noted to be 50%. The final WPUA film was prepared without coalescence agents that generate volatile organic compounds. Full article

Phthalocyanine pigments have many problems in waterborne coating applications because of their low polarity, poor dispersion in water, and easy agglomeration properties. In order to solve these problems, the phthalocyanine pigments were encapsulated with a copolymer of methyl methacrylate (MMA) and butyl acrylate (BA) by a mini-emulsion polymerization method. The pigments are effectively dispersed in water and have good compatibility with the resin. Concerning the bacterial reproduction and growth problem for the waterborne system, the resin-encapsulated phthalocyanine pigments were further grafted with antibacterial polymer poly(N-(2-hydroxyethyl) acrylamide) (PHEAA) on its surface using the photoemulsion polymerization technique. Comprehensive properties, including centrifugal stability and chromaticity change, were studied. The polymer encapsulation improved the centrifugal stability of the pigment. The thermogravimetric results showed that the residual mass of C.I. Pigment Green 7 (52.30%) was higher than that of C.I. Pigment Blue 15:3 (30.06%), and the sublimation fastness of PG7 was higher. The TEM results revealed that the shape of the PG7 after encapsulation and grafting was more regular than that of PB15:3. The L* of the pigment decreased after encapsulation but then increased after further grafting. The phthalocyanine pigment composite latex had good antibacterial properties after the grafting of PHEAA. Full article

In this work, two bio-based raw materials, rapeseed oil and technical-grade oleic acid, were modified to yield acrylated monomers. Polymeric latexes designed for coating applications were synthesized using emulsion polymerization. Methyl methacrylate and butyl acrylate were copolymerized with various ratios of the acrylated bio-based monomers (0–20 wt.% in the monomer mixture). The polymerization with high monomer conversion and low coagulum content was successfully performed up to the content of 15 wt.% of the bio-based monomers, leading to long-term stable latexes. The asymmetric flow field flow fractionation coupled with a multi-angle light scattering detector was used to describe the molar mass distribution of the synthesized copolymers. Ultra-high molar mass fractions were detected in copolymers comprising the bio-based monomers due to the presence of multi-acrylated bio-based ingredients originating from linoleic and linolenic fatty acids. This phenomenon became more pronounced for the rapeseed oil-originated monomer. The prepared latexes comprising copolymerized bio-based monomers showed comparable or even better coating performance in terms of gloss and water resistance in comparison with the reference acrylic coating, which makes the acrylated vegetable oil-based monomers attractive for the manufacturing of sustainable water-borne materials in the coating industry. Full article

Currently, waterborne coatings are widely used, but their poor anticorrosion performance compared with solvent-based coatings hinders their further application. In this study, a series of Zn₅Mo₂O₁₁·5H₂O@sulfonated graphene (SZMO@SG) composites are prepared using the template method. SZMO@SG is a type of two-dimensional material with a large diameter and low thickness compared to traditional zinc molybdate. Combining SZMO@SG with waterborne hydroxy acrylic latex and isocyanate, the polyurethane coatings with 3 wt% SZMO@SG achieve the best anticorrosion performance in the 3.5 wt% NaCl immersion test. In electrochemical impedance spectroscopy (EIS), the charge transfer resistance (R_ct) of polyurethane coatings with 3 wt% SZMO@SG reaches 283,100 Ω·cm² after soaking in a 3.5 wt% NaCl solution for 48 h. Its corrosion potential and corrosion current are only −0.453 V and 1.71 × 10⁻³ mA/cm², respectively. After metal substrate corrosion, the metal substrate of polyurethane coatings with SZMO@SG contain more Mo, Zn and low-state Fe atoms. It confirms that a passivation film was deposited on the metal substrate and prevents Fe from oxidation. The elemental content and distribution of the coatings after the NaCl solution immersion test indicate that SZMO@SG may have the Na⁺ adsorption function. Full article

This article deals with the simple preparation of environmentally friendly acrylic latex binders, which are functionalized with nanoparticles of metal oxides, namely MgO, ZnO, La₂O₃ and combinations of MgO and ZnO, serving as functional components to achieve antimicrobial properties, but also to improve physical–mechanical properties and chemical resilience. The incorporation of uncoated powder nanoparticles was performed during the synthesis, using the two-stage semi-continuous emulsion radical polymerization technique, to obtain latexes containing 0.5%–1.3% nanoparticles relative to the polymer content. Changes in latex performance due to nanoparticles were compared from the point of view of the type and concentration of metal oxide nanoparticles in latex. The results of the tests showed that all types of nanoparticles showed very promising properties, while with increasing concentration of nanoparticles there was an improvement in properties. The nanoparticles in latex provided interfacially crosslinked transparent smooth coating films with high gloss and good physical–mechanical properties. Latexes containing the highest concentration of nanoparticles provided coatings with significant antimicrobial activity against all tested bacterial and fungal strains, but also in-can preservative stability of liquid latex. Furthermore, the coatings were resistant to solvents, and in addition, latexes with MgO nanoparticles showed a significant decrease in the minimum film-forming temperature, and latex with a concentration of about 1.3% MgO did not show any flash corrosion under the coating film cast on a steel substrate. The latexes containing MgO and La₂O₃ nanoparticles provided coatings that were very resistant to water bleaching. Full article

To investigate the utility of acrylic monomers from various plant oils in adhesives manufacturing, 25–45 wt. % of high oleic soybean oil-based monomer (HOSBM) was copolymerized in a miniemulsion with commercially applied butyl acrylate (BA), methyl methacrylate (MMA), or styrene (St). The compositions of the resulting ternary latex copolymers were varied in terms of both “soft” (HOSBM, BA) and “rigid” (MMA or St) macromolecular fragments, while total monomer conversion and molecular weight of copolymers were determined after synthesis. For most latexes, results indicated the presence of lower and higher molecular weight fractions, which is beneficial for the material adhesive performance. To correlate surface properties and adhesive performance of HOSBM-based copolymer latexes, contact angle hysteresis (using water as a contact liquid) for each latex-substrate pair was first determined. The data showed that plant oil-based latexes exhibit a clear ability to spread and adhere once applied on the surface of materials differing by polarities, such as semicrystalline polyethylene terephthalate (PET), polypropylene (PP), bleached paperboard (uncoated), and tops coated with a clay mineral paperboard. The effectiveness of plant oil-based ternary latexes as adhesives was demonstrated on PET to PP and coated to uncoated paperboard substrates. As a result, the latexes with high biobased content developed in this study provide promising adhesive performance, causing substrate failure instead of cohesive/adhesive break in many experiments. Full article

Polymer-modified cement has found numerous applications due to its excellent tensile strength. When cement was modified with a single polymer, its tensile strength and performance marginally increased. However, when a small amount of the flexible polymer latex was added to cement, the mechanical performance of cement considerably improved. In this study, single-graded copolymer-modified pervious concrete was prepared by mixing styrene-butadiene rubber (SBR) with different acrylate polymers, and its mechanical performance and durability were systematically studied through mechanical tests and theoretical analyses. The main findings are as follows: (1) When a waterborne emulsion was added, the freeze resistance of cement concrete increased, and its mass loss rate decreased. Cement concrete with two latexes had higher sulphate corrosion resistance and substantially lower dry shrinkage strain than ordinary cement concrete. (2) Through scanning electron microscopy, the microstructural changes in the cement binder, ordinary polymer-modified concrete, and the copolymer-modified cement concrete used in this study were observed, and the findings were compared with those reported in the literature. (3) Single-graded copolymer-modified pervious concrete exhibited excellent shrinkage performance. This study showed that single-graded copolymer-modified pervious concrete satisfied the performance requirements for use as a paving material for special cases. Full article

In order to develop a waterborne epoxy-styrene–acrylate composite latex with a better stability and anticorrosion resistance, a novel synthetic approach has been proposed. First, modified by methyl acrylic, epoxy resin containing terminal C=C double bonds was successfully synthesized, where epoxide groups were partially retained. Then, by structural design and multi-stage seed emulsion copolymerization, a stable waterborne epoxy-styrene-acrylate composite latex composed of a modified epoxy resin acrylate polymer as the core, inert polystyrene ester as the intermediate layer, and carboxyl acrylate polymer as the shell was successfully fabricated. The structure of the obtained latex was characterized by fourier transform infrared (FTIR) and transmission electron microscopy (TEM). The stability of the composite latex was tested based on the wet gel weight, Zeta potential, and storage stability, and the corrosion resistance of the composite latex films was analyzed by electrochemical measurements and salt spray tests. The thickness of each layer of the composite latex was calculated by the temperature random multi-frequency modulation DSC (TOPEM-DSC) technique. In addition to the successful emulsion copolymerization that occurred between the modified epoxy resin and acrylate monomer, the presence of carboxyl groups in the obtained latex was evidenced, while the epoxide groups were partially retained. The anticorrosion resistance and stability of the multilayer composite latex with the intermediate layer are better than that of the conventional core-shell latex. The outstanding stability and corrosion resistance is attributed to the multilayer core-shell structure. The TOPEM-DSC approach can accurately determine the thickness of the intermediate layer in the multilayer core-shell particles and is a new strategy for characterizing the core-shell structure of polymer particles with a similar monomer composition. Full article

The performance of waterborne (meth)acrylic coatings is critically affected by the film formation process, in which the individual polymer particles must join to form a continuous film. Consequently, the waterborne polymers present lower performance than their solvent-borne counter-polymers. To decrease this effect, in this work, ionic complexation between oppositely charged polymer particles was introduced and its effect on the performance of waterborne polymer films was studied. The (meth)acrylic particles were charged by the addition of a small amount of ionic monomers, such as sodium styrene sulfonate and 2-(dimethylamino)ethyl methacrylate. Density functional theory calculations showed that the interaction between the selected main charges of the respective functional monomers (sulfonate–amine) is favored against the interactions with their counter ions (sulfonate–Na and amine–H). To induce ionic complexation, the oppositely charged latexes were blended, either based on the same number of charges or the same number of particles. The performance of the ionic complexed coatings was determined by means of tensile tests and water uptake measurements. The ionic complexed films were compared with reference films obtained at pH at which the cationic charges were in neutral form. The mechanical resistance was raised slightly by ionic bonding between particles, producing much more flexible films, whereas the water penetration within the polymeric films was considerably hindered. By exploring the process of polymer chains interdiffusion using Fluorescence Resonance Energy Transfer (FRET) analysis, it was found that the ionic complexation was established between the particles, which reduced significantly the interdiffusion process of polymer chains. The presented ionic complexes of sulfonate–amine functionalized particles open a promising approach for reinforcing waterborne coatings. Full article

CeO₂ nanoparticles were incorporated in waterborne binders containing high biobased content (up to 70%) in order to analyze the anticorrosion performance for direct to metal coatings. Biobased binders were synthesized by batch miniemulsion polymerization of 2-octyl acrylate and isobornyl methacrylate monomers using a phosphate polymerizable surfactant (Sipomer PAM200) that lead to the formation of phosphate functionalized latexes. Upon the direct application of such binders on steel, the functionalized polymer particles were able to interact with steel, creating a thin phosphatization layer between the metal and the polymer and avoiding flash rust. The in situ incorporation of the CeO₂ nanoparticles during the polymerization process led to their homogeneous distribution in the final polymer film, which produced outstanding anticorrosion performance according to the Electrochemical Impedance Spectroscopy measurements. In fact, steel substrates coated with the hybrid polymer film (30–40 µm thick) showed high barrier corrosion resistance after 41 days (~1000 h) of immersion in NaCl water solution and active inhibition capabilities thanks to the presence of the CeO₂ nanoparticles. This work opens the door to the fabrication of sustainable hybrid anticorrosion waterborne coatings. Full article