Synthesis and performance of alkyd–acrylic hybrid binders

Preparation and properties of alkyd–acrylic hybrids have been studied. Hybrids with different alkyd–acrylic ratios and acrylic parts were prepared via free radical polymerization of acrylic monomers in a presence of an unsaturated alkyd resin using emulsion polymerization technique. The binders were characterized according to their solid content, conversion, viscosity, pH and particle size. Evidence on formation of true copolymer was obtained via NMR spectroscopy and molecular weight and glass transition temperature measurements, as well as via performance studies. The performance evaluation was focused on investigation of drying, penetration and water repellency ability, as well as on film formation and surface topography studies. The binders were compared to references of an alkyd emulsion, acrylic latex and a blend made of them. The results showed that alkyd–acrylic hybrids with synergistic and improved properties can be prepared.     

Structure–property relationship in aging acrylic latex films

We have used environmental scanning electron microscopy (ESEM) and mechanical testing to study the effect of aging parameters (temperature, T and relative humidity, RH) on the structure–property relationship of aged specimens from two acrylic latex compositions, referred to as ‘standard’ and ‘novel’. It was found that the tensile strength of the novel system increases as a function of aging time, whereas the tensile strength of the standard specimens remains almost unchanged. This was attributed to the formation of salt dendrites in the aged novel samples. It was also found that humidity does not have a significant effect on the microstructures observed. However, it was found that aging at lower temperatures results in decreased rate of dendritic formation, which is suggested to be due to decreased diffusion of the species taking part in the crystallisation process. Further examination of fractured surfaces of the studied latex systems revealed features indicative for a more ductile behaviour of the standard specimens and a more brittle behaviour for the novel latex samples.     

Synthesis and characterization of potassium humate–acrylic acid–acrylamide hydrogel

A novel potassium humate–acrylic acid–acrylamide (KHA–AA–AM) superabsorbent polymer was prepared from the reaction among leonardite potassium humate, acrylic acid and acrylamide by free radical initiating process using ammonium persulfate as the initiator and N, N′-methylene bisacrylamide as the crosslinker. Various effects of synthesis conditions on superabsorbent polymer were studied and the optimal reaction condition was obtained with crosslinker concentration 0.44–0.74 wt%, initiator concentration 1.12–2.22 wt%, n(KOH)/n(AA) 0.51–0.70, monomer concentration 10.95–12.59 wt%, graft reaction temperature 83 ± 1°C, monomer mole ratio of acrylic acid to acrylamide 1.42–2.30, and potassium humate content 17.54 wt%. Under the optimal conditions, the solution absorbency of KHA–AA–AM superabsorbent polymer to deionized water, tap water, 0.5% carbamide solution and 0.9% NaCl solution were 733–756, 161–284, 786–825, and 76–83 g/g, respectively.     

Waterborne acrylic–polyaniline nanocomposite as antistatic coating: preparation and characterization

An antistatic and electrically conductive acrylic–polyaniline nanocomposite coating was successfully synthesized by interfacial polymerization of aniline in the presence of acrylic latex. The acrylic latex was prepared through emulsion polymerization, and aniline was polymerized by in situ interfacial polymerization at the interface of acrylic latex/chloroform phase. Fourier transform infrared spectroscopy (FTIR), UV–Vis spectroscopy and CHNS elemental analysis revealed the existence of 6.24 wt% emeraldine salt of polyaniline (PAni) in the dried film of the nanocomposite. Scanning electron microscopy (SEM) confirmed the presence of colloidal polymer particles in the aqueous phase which was confirmed to have some advantages, including prevention of aggregation of particles, dispersibility improvement and enhancement of the PAni nanofibers aspect ratio in the acrylic polymer matrix. According to SEM results, PAni fibers with the length ranging from 12 to 67 µm and diameters between 0.078 and 1 µm, highly dispersed in the acrylic polymer matrix, were successfully synthesized. Thermal, electrical and mechanical properties of the acrylic copolymer were significantly affected by PAni incorporation. The onset degradation temperature in thermogravimetric analysis revealed that the thermal stability of the nanocomposite was improved compared to that of the pure acrylic copolymer. The nanocomposite film showed electrical conductivity of about 0.025 S/cm at room temperature, along with satisfactory mechanical properties, attractive as an antistatic material in coating applications.     

Study on bonding properties of PVC-based WPC bonded with acrylic adhesive☆

In this paper, the bonding properties of polyvinylchloride (PVC)-based wood–plastic composite (WPC) materials bonded with acrylic adhesive have been studied. The results showed that dry compression shear strength of bonded specimens glued with acrylic adhesive was 6.12?MPa, and reached 58.8% of the strength of the PVC-based WPCs. The results also showed that wet compression shear strength in accordance with Chinese standard GB/T17657 was 0.9 times the dry compression shear strength of 5.48?MPa. In addition, the retention rate of the compression shear strength of the bonded specimens gluing with acrylic adhesive after UV aging for 7?days and 14?days was 69.1 and 66.8%, respectively. The aging was done in accordance with UV-aging test process as given in this paper. The scanning electron microscopy (SEM) analysis of the bonded specimens of PVC-based WPCs showed that the J-39 acrylic adhesive penetrated into the adjacent porous regions of the PVC-based WPC which had resulted from foaming. This penetration enhanced the mechanical interlocking between the substrate and the acrylic adhesive.     

Microsphere pressure sensitive adhesives—acrylic polymer/montmorillonite clay nanocomposite materials

In this study, the synthesis and characterization of acrylic polymer/montmorillonite (MMT) clay nanocomposite pressure sensitive adhesives (PSA) are presented. Different types and amounts of modified and unmodified montmorillonite clays were dispersed in ethyl acrylate (EA)/2-ethylhexyl acrylate (2-EHA) monomer mixture, which was then polymerized using a suspension polymerization technique. Polymerization was monitored in-line using attenuated total reflectance-fourier transform infrared (ATR-FTIR) spectroscopy. The adhesion properties of the synthesized nanocomposite materials were determined using standard measurements of tack, peel and shear strength. Viscoelastic properties of dried adhesive films were analyzed using dynamic mechanical analysis (DMA). The results showed that the kinetics of suspension polymerization was independent of the addition of MMT clays. On the other hand, adhesive properties were strongly influenced by the type and the amount of MMT clay added. While peel strength and tack gradually decreased with higher amount of modified MMT clay, a substantial increase in shear strength was determined with a maximal value at 1 wt% of added MMT clay. Moderate influence on tack, peel and shear strength was observed when the unmodified type of MMT clay was used. DMA analysis showed an increase in storage modulus (G′) for adhesives synthesized with MMT clay addition, but no significant differences were determined between particular types of MMT clays. A decrease in tan δ value for adhesives with 1 wt% of added MMT clay was observed, which also concurs with higher shear strength and implies to the improved cohesion of adhesive.     

Synthesis and fluorescence properties of a waterborne polyurethane–acrylic hybrid polymeric dye

A waterborne polyurethane–acrylic hybrid polymeric dye was prepared depending on soap-free emulsion polymerization method. The resulting polymeric dye composed of methyl methacrylate (MMA) monomer which was polymerized into polymethyl methacrylate (PMMA) as cores and waterborne polyurethane-based dye was synthesized by anchoring dye monomers (6-amino-2-cyclohexyl-benz[de]isoquinone-1,3-dione) to polyurethane chains as shells. The average particle sizes of the hybrid polymeric dye emulsions were found to be increased with the increase in MMA contents for MMA monomers. Compared with dye monomers, the absorption intensities and fluorescence intensities of the hybrid polymeric dye were enhanced with the increase of particle sizes. This study revealed that enhanced fluorescence intensity of the hybrid polymeric dye was mainly attributed to the hindered formation of exciplexes among dye monomers and an augmented light absorption area. It was found that the fluorescence intensity of the hybrid polymeric dye was increased with increasing temperature and the trend first increased and then decreased with increase in concentration. Furthermore, the fluorescence of the hybrid polymeric dye emulsions was found to be very stable and not sensitive to the fluorescence quencher.     

Synthesis and evaluation of water-reducible acrylic–alkyd resins with high hydrolytic stability

Relatively poor hydrolytic stability is one of the major drawbacks of waterborne alkyd resins. Therefore, the shelf life of the paints containing these kinds of resins is usually short. In this research, the hydrolytic stability of water-reducible alkyd resins has been improved by employing polyacid acrylic copolymers in alkyd resins structure. In addition, the effect of other raw materials (such as neutralizing agent) and synthesis conditions on the resins properties was investigated. The results showed that the optimum synthesized water-reducible acrylic–alkyd resins had a high hydrolytic stability and their acid values increased only 23.5% after 4 months storage at ambient temperature. The synthesized resin was also used in an air-drying water-reducible lacquer formulation and its physical and mechanical properties were evaluated.     

Influence of ingredients in water-based polyurethane–acrylic hybrid latexes on latex properties

Polyurethane–acrylic (PU–AC) hybrid latexes were prepared. Main monomers for PU preparation were isophorone diisocyanate, DMPA (dimethylol propanic acid) and polypropylene oxides (PPO) of different molecular weights. Acrylic monomers included butyl acrylate, methyl methacrylate and a crosslinker, trihydroxymethyl propane triacrylates (TMPTA). Several important ingredients in PU–AC latex preparation, such as surfactants, initiator, DMPA and PU/AC ratio, etc., were varied, and their effects on latex properties studied. Compared with surfactant free latexes, a sharp increase in particle size was observed in latexes done with 0.1% of surfactant regardless of the nature of the surfactants used (anionic, nonionic and anionic with long chain of amphiphilic alkylphenyl polyethoxylate). Further increase in surfactant content, however, led to latexes with smaller particle size and narrower particle size distribution when compared between latexes prepared using a same surfactant. When amount of the oil soluble initiator, azobisisobutyronitrile, was increased, AC monomers conversion was increased. It is interesting to observe that PPO with long propylene oxides brought about larger particle size combined with broader size distribution and less charge on particle surface; whereas lower DMPA levels led to latexes also of larger size combined with broader size distribution but more charges on particle surface. AC monomer crosslinker, TMPTA, contributed to reduce particle size, narrower size distribution and lower particle surface charges. By increasing AC amount in PU–AC latex, latex particle size significantly increased accompanied by a remarkable increase in particle surface charges. Mechanisms of particle formation and of DMPA stabilization were discussed in order to understand the experimental results.     

Mechanical characterization and modeling stress relaxation behavior of acrylic–polyurethane-based graft-interpenetrating polymer networks

The stress relaxation behavior of acrylic–polyurethane (PU)-based graft-interpenetrating polymer networks (IPNs) was characterized via dynamic mechanical analysis (DMA) and modeled using finite element method (FEM) analysis. Stress relaxation of glassy IPN specimens was experimentally studied under flexural testing, while rubbery IPN specimens were tested in tension. The effects of varying the styrene content in the acrylic copolymer phase, compatibility of the two phases in IPNs, and changing the concentration of acrylic copolymer and PU were studied. A higher percentage of styrene content resulted in higher homogeneity of IPN specimens, and decrease in initial modulus for acrylic copolymer specimens. Additionally, glassy IPN specimens with 90% styrene shows resistance to relaxation as high as acrylic copolymer samples. Experimental results were used to develop a numerical model to study stress relaxation response of specimens. While polymer systems have been studied computationally, numerical modeling of IPN systems is still in its infancy. A three-dimensional FEM model was developed using the Generalized Maxwell model and four-term Prony series constants, which were extracted from the stress relaxation experiments. With four terms in the Prony series, a good match was observed between experimental observations and results from the FEM model.     

3D-Printed Poly(acrylic acid–vinylimidazole) Ionic Polymer Metal Composite Actuators

Ionic polymer–metal composites (IPMC)—constructed using an ionic polymer sandwiched between metal electrodes—have shown great potential for the fabrication of soft actuators. IPMC architectures have many advantages including low actuation voltage, fast response, basic control, and relatively light weight. Poly(acrylic acid) (PAA)-based ion exchange membranes are of particular interest for IPMC devices due to their large ion exchange capacity and ease of preparation; however, they suffer from relatively weak mechanical strength. Here, PAA-based soft actuators are synthesized with enhanced mechanical properties and proton conductivity through the incorporation of hydrogen bonding interactions with imidazolium groups via copolymerization with 1-vinylimidazole. In addition to examining the impact of composition on physiochemical (swelling, glass transition, decomposition, Young's modulus, etc.) and electrochemical (specific capacitance) properties, an additive manufacturing process, digital light projection (DLP), is utilized to fabricate complex geometries demonstrating the potential for the fabrication of IPMC devices with complex actuation modalities. Planar DLP 3D-printed IPMC actuators of varied polymer compositions are fabricated with activated carbon and copper electrodes, and their actuation performance is evaluated in air, where large bending deformation is observed (14°–37°).     

Synthesis of a starch–acrylic acid–chitosan copolymer as flocculant for dye removal

Flocculants prepared with modified natural polymers have recently attracted extensive attention in the field of water treatment. In this work, acrylic acid was successfully grafted onto the backbones of starch and chitosan by free radical polymerization. The synthesis parameters of initiator concentration, reaction temperature, and neutralization degree of acrylic acid were optimized as 0.4 wt %, 50 °C, and 70%, respectively, according to the flocculation performance. The ternary copolymer starch–acrylic acid–chitosan (SAAC) could completely remove Acid Blue 113 from 100 mg/L of simulated wastewater (color removal efficiency 99.7%) at the flocculant dosage of 100 mg/L. The SAAC also had effective flocculation capability in a wide range of flocculant dosages and pH values of wastewater. The ternary copolymer based on two natural polymers has enormous potential as flocculant with its advantages of low price, ecofriendliness, and high performance. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47437.     

Effect of functionalised core–shell microgels prepared by emulsion polymerisation on acrylic coatings properties

The influence of hydroxyl-functionalised acrylic core–shell microgels incorporated into a solvent-borne acrylic binder system on the properties of coatings is described in this paper. Our approach has been to show the usefulness of prepared functionalised microgels as coating modifiers. This subject was shown to be connected with the selection of an appropriate solvent with good affinity for microgels and the film-forming polymer. Therefore the swelling behaviour of microgels in selected solvents as a function of microgel composition is discussed as well. The structured microgels were prepared by first making an aqueous emulsion via the semi-batch emulsion copolymerisation, then dehydrating the system by air drying followed by grinding in a mill. The resulting agglomerates of spherical microgel particles were dispersed in convenient organic solvent media and after that added to the thermosetting solvent-borne acrylic binder system. It was shown that the application of core–shell microgels did not affect the surface appearance and transparency of coatings. Moreover, the presence of microgel network precursors improved corrosion resistance of coatings.     

A fluorine–silicone acrylic resin modified with UV-absorbing monomers and a free radical scavenger

A novel UV-absorbing and free-radical-catching fluorine–silicone acrylic resin with 2-(4-benzoyl-3-hydroxyphenoxy) ethyl acrylate (BHEA), 2,2,6,6-tetramethyl-4-piperidyl methacrylate (TMPM), dodecafluoroheptyl methacrylate (DFMA) and 3-methacryloxypropyltrimethoxysilane (MPS) as functional monomers was successfully synthesized by solution copolymerization. Based on various investigations, our characterization results for the resin and its coating indicated that the resin exhibits high UV-absorbing and free-radical-catching performances, and the hydrophobicity of the varnish coating was promoted by the actions of fluorine and silicone. In addition, the weatherability improved because of the enduring triple protection of the UV absorbent (BHEA), free-radical-catching agent (TMPM), fluorine (DFMA) and silicone (MPS). After a 1000-h aging test, the color difference (?E) and rate of loss of gloss (?G) of varnish coatings were 2.96% and 62%, respectively, and the impact strength and flexibility of color paint coatings were 420 N cm and 2 mm, respectively. Moreover, the chemically bonded free-radical-catching agent (TMPM) showed a more enduring performance for producing nitroxides than the simple blend.     

Study of the styrene–acrylic emulsion modified by hydroxyl-phosphate ester and its stoving varnish

A styrene–acrylic copolymer emulsion containing hydroxyl-phosphate as flash-rust functional monomer and hydroxypropyl acrylate as cross-linking monomer was synthesized. The effects of the hydroxyl phosphate dosage, the hydroxypropyl acrylate dosage as well as the ratio of soft to hard monomer on the emulsion and coating film were investigated. The results showed that the emulsion of 4% hydroxyl phosphate function monomer and 3% hydroxypropyl acrylate with soft and hard monomer ratio of 1:1.6 and modified emulsion and amino resin ratio of 6:1 resulted in a coating film with the best performance.     

How does the surface free energy influence the tack of acrylic pressure-sensitive adhesives (PSAs)?

This article describes a comparative study of the tack properties of a model acrylic pressure-sensitive adhesive (PSA) crosslinked using aluminum acetylacetonate on several substrates, including stainless steel, glass, polyethylene, polypropylene, polytetrafluoroethylene, polycarbonate, and poly(methyl methacrylate). The tack measurements were conducted using a technique commonly used to measure the tack of an adhesive tape in the PSA industries. The surface free energy (SFE) values of the materials were evaluated using the Owens–Wendt and van Oss–Chaudhury–Good methods. The experiments showed a clear relationship between the SFE of the substrate and the tack of the model acrylic PSA. In general, larger differences between the SFE values of the substrate and adhesive (Δ_SFE) were correlated with greater tack values. The tack of the model acrylic PSA was found to be optimal over the Δ_SFE range of 7.0–13.1 mJ/m². The trend in the tack as a function of the SFE difference was attributed to the quantity of energy dissipated at the jointed points during the separation stage in the loop tack test.     

Preparation and sorption studies of microsphere copolymers containing β-cyclodextrin and poly(acrylic acid)

Microsphere polymeric materials containing β-cyclodextrin (β-CD) and poly(acrylic acid) (PAA) with tunable morphologies were prepared in order to improve their sorption characteristics in aqueous solution. The microsphere polymeric materials were prepared using a (water/oil) micro-emulsion-evaporation technique to condense β-cyclodextrin (β-CD) with PAA at various comonomer ratios and mixing speeds. The β-CD microsphere copolymers were characterized using FTIR, TGA, DSC, SEM, elemental (C and H) microanalyses, and solid state ¹³C-NMR spectroscopy. The sorption properties of the polymeric materials at 295 K in aqueous solution containing p-nitrophenol (PNP) were studied using a dye-based method with UV–Vis spectrophotometry at pH 4.6 and 10.3. The sorption isotherms of copolymer/PNP systems were evaluated with various isotherm models (e.g., Langmuir, BET, Freundlich, and Sips). The Sips isotherm showed the best overall agreement with the experimental results and the sorption parameters provided estimates of the sorbent surface area (12.0–331 m²/g) and the sorption capacity (Q_m = 0.359–2.20 mmol/g at pH = 4.6; Q_m = 0.070–0.191 mmol/g at pH = 10.3) for the microsphere copolymer/PNP systems in aqueous solution. The nitrogen adsorption properties of the microporous copolymers in the solid state were obtained at 77K with BET surface areas ranging from 0.275 to 4.47 m²/g. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and properties of hybrid alkyd–acrylic dispersions and their use in VOC-free waterborne coatings

Hybrid waterborne alkyd–acrylic dispersions with solid content of 40%, free from any surfactant and exempt of any organic solvent, were successfully synthesized by a melt co-condensation reaction between an acrylic prepolymer bearing carboxylic groups and a long-oil alkyd resin. Spontaneous emulsification of the ensuing hybrid resin was achieved by the addition of an aqueous ammonia solution that neutralized the carboxylic functions. The key role of the carboxylic groups on the stabilization process and on the storage stability of the dispersion was assessed and it was shown that the insertion of anhydride moieties within the acrylic prepolymer ensured the efficient coupling between the acrylic and the alkyd resin and prevented the phase separation. These dispersions are easy to implement and might be used to prepare high quality zero VOC coatings in terms of drying time, stability and gloss. The most stable dispersion was also used in the formulation of air-drying waterborne lacquers and their coating properties were evaluated.     

Structure of tall oil fatty acid-based alkyd resins and alkyd–acrylic copolymers studied by NMR spectroscopy

One- and two-dimensional NMR spectroscopy was used to evaluate the structure of tall oil fatty acid (TOFA)-based alkyd resins and waterborne alkyd–acrylic copolymers. An increase in the functionality of the polyol that is used in the alkyd resin synthesis was found to increase the reactivity of the polyol towards the diacid compared with the TOFA, which causes the formation of more branched and higher molar mass alkyd resin structures. During the copolymerization, polyacrylate chains were grafted to the double bonds and allylic sites of the fatty acid chains in the alkyd resin. Butyl acrylate preferentially grafted to the double bonds, while methyl methacrylate tended to graft to the allylic position. High proportions of the double bonds remaining after copolymerization were crucial to the film formation of copolymers, because the chemical drying of copolymer films occurred by an autoxidation process.     

Adhesive strength of steel–epoxy composite joints bonded with structural acrylic adhesives filled with silica nanoparticles

This paper reports a study on the effect of silica nanoparticles on the adhesion strength of steel–glass/epoxy composite joints bonded with two-part structural acrylic adhesives. The introduction of nano-silica in the two-part acrylic adhesive led to a remarkable enhancement in the shear and tensile strength of the composite joints. The shear and tensile strengths of the adhesive joints increased with addition of the filler content up to 1.5 wt%, after which decreased with addition of more filler content. Also, addition of nanoparticles caused a reduction in the peel strength of the joints. Differential scanning calorimeter analysis revealed that T_g values of the adhesives rose with increasing the nanofiller content. The equilibrium water contact angle was decreased for adhesives containing nanoparticles. Scanning electron microscope micrographs revealed that addition of nanoparticles altered the fracture morphology from smooth to rough fracture surfaces.