Polyurethane Acrylate Dispersions Research Articles

High solid and low viscosity waterborne polyurethane acrylate with excellent anti-corrosion and anti-bacterial performances

The design and preparation of great corrosion resistance and high-solid waterborne polyurethane dispersion with low viscosity is still a challenge in the field of the polyurethane industry. Herein, we developed a simple method involving a core-shell process to prepare a core-shell structured waterborne polyurethane acrylate dispersion (WPUAD). First, isobornyl acrylate, a derivative of natural product borneol, dihydroxylated by a thiol-ene click reaction was used to prepare oil-based polyurethane acrylate as prepolymer A (core) and waterborne polyurethane acrylate as prepolymer B (shell). Then, the core-shell WPUAD was obtained by mixing and emulsifying the two prepolymer at a certain ratio. The study reveals that the core-shell structured WPUAD not only has a low viscosity (~1330 mPa.s) but also holds a high-solid content (~ 60 wt%). At the same time, the highly solid WPUAD has excellent stability with no breast breakage even after more than 1 year of storage. In addition, various electrochemical measurements, water contact angles, and water absorption tests were performed to determine the anti-corrosive properties of the WPUAD-derived coatings. The results show that the WPUA coatings exhibit significantly enhanced anticorrosion with respect to the single prepolymer B derived coatings, which is attributed to their high cross-linking density resulting from the core-shell structure and the introduction of hydrophobic isobornyl acrylate. In addition, because of the introduction of the dihydroxylated isobornyl acrylate as chain extenders, the WPUA coating has great anti-bacterial adhesion properties with an anti-bacterial efficiency of 82.3 %. We believe that our work provides a generic preparation method to obtain a commercially available high-solid WPUAD with excellent anti-corrosion properties.

Siloxane-modified waterborne UV-curable polyurethane acrylate coatings: Chemorheology and viscoelastic analyses

The effects of molecular weight of PDMS on chemorheology and viscoelastic behavior of siloxane modified waterborne UV-curable polyurethane acrylate dispersions (Si-WUPAs) were assessed via a photo rheometer as a versatile tool for in situ observation of chemical and mechanical characteristics during photopolymerization reaction. The roles of PDMS soft segment and its Mw on the rheological behavior were examined followed by exploring the flow curves of Si-WUPA system. The viscosity of Si-WUPA samples decreased with increasing shear rate, showing a pseudoplastic behavior for high-molecular-weight PDMS. However, the unmodified sample and specimens containing dual soft segments of PTMG and low Mw of PDMS revealed a Newtonian behavior. The curing process was accomplished using a photoinitiator to induce polymerization of acrylate double bonds at 40 °C and 60 °C, signifying a-three-step curing process. Enhanced drying time and gelation points were observed upon increasing Mw and content of PDMS. Correspondingly, the storage modulus diminished due to incomplete curing because of contribution of more flexible PDMS chains to reaction. Thermomechanical properties of UV-cured Si-WUPAs films were systematically studied via DMTA, revealing two different behaviors depending on the Mw of PDMS. Si-WPUAs systems showed enlarged width of tanδ peak in half of heights unconditionally, suggesting increased incompatibility and non-uniformity of the final film caused by micro-phase separation of PDMS chains. Mechanical properties were also inspected by tensile test confirming the DMTA results. Tensile isotherms of cured Si-WPUA specimens were remarkably sensitive to both Mw and the content of PDMS.

High-performance waterborne UV-curable polyurethane dispersion based on thiol–acrylate/thiol–epoxy hybrid networks

Synthesis, characterization, and film performance of waterborne thiol–acrylate/thiol–epoxy hybrid coatings are highlighted in this article. A dimer acid-modified epoxy (DME) polyol, containing both hydroxyl and epoxy functional groups, was prepared by reacting epoxy resin (EEW = 190 g/equi) with dimer fatty acid at 2:1 molar ratio. Further, a base UV-curable polyurethane acrylate dispersion (UV-PUD), with a pendant epoxy functional group, was prepared by reacting polyol (DME), isophorone diisocyanate, and dimethylol propionic acid and end-capped with hydroxyethyl methacrylate with subsequent dispersion in water. Prepared intermediates were characterized for the parameters relevant to the study by physical, spectroscopic, and chemical methods. UV-curable thiol–acrylate/thiol–epoxy hybrid coatings were prepared by blending UV-PUD with trimethylolpropane tris(3-mercaptopropionate) (TMPMP) at four different thiol ratios (0, 0.3, 0.6, and 1.0) with respect to acrylate/epoxy groups. Cured films of the hybrid coating were identified by FTIR spectroscopy. The impact of thiol ratio on film performance was evaluated in terms of mechanical, chemical, thermal, and coating properties. The gel content measurements confirm that the addition of TMPMP increased the double bond conversion along with the epoxy group. Evaluation of cured samples shows the significant improvement in storage modulus, glass transition temperature, tensile strength, and hardness with increase in thiol ratio. The cured films possessed excellent water and acid resistance (<4%) even after 28 days of immersion. Moreover, the notable improvement was alkali resistance of cured films, i.e., as thiol ratio was increased from 0 to 1, weight loss in alkaline environment deceased from 49.5 to 4.5% after 28 days. Better properties of the thiol–acrylate/thiol–epoxy hybrid films will allow it as a potential application in low-volatile high-performance coatings.

Waterborne epoxy-modified polyurethane-acrylate dispersions with nano-sized core-shell structure particles: synthesis, characterization, and their coating film properties

Abstract Waterborne epoxy-modified polyurethane-acrylate (EPUA) dispersions with nano-sized core-shell structure particles, with polyacrylate (PA) as core and epoxy-modified polyurethane (EPU) as shell, were successfully prepared via a two-step procedure. The waterborne EPU dispersions were first synthesized to serve as seeds, and then the butyl acrylate (BA) and methyl methacrylate (MMA) monomers were introduced into EPU particles to form polymeric core by radical polymerization under the assistance of ultrasonic treatment. Fourier transform infrared (FT-IR) spectroscopy revealed that the epoxy and PA components were successfully incorporated onto the chain of the PU and EPU to form EPU and EPUA, respectively. The transmission electron microscopy (TEM) photograph demonstrated that the EPUA particles have the core-shell structure. The as-prepared EPUA coating films exhibited good thermo-stability and mechanical properties, as revealed by thermogravimetric analysis (TGA) and tensile testing, respectively. The results of potentiodynamic polarization curves and immersion corrosion testing in 5 wt% NaCl aqueous solution both demonstrated that the anticorrosive properties of EPUA mainly depended on the mass content of PA, with the optimized value of 30 wt%.

UV-curable enzymatic antibacterial waterborne polyurethane coating

Novel ultraviolet (UV)-curable enzymatic antibacterial coatings were designed and fabricated. The coatings were prepared by simply mixture of castor oil-based cationic waterborne polyurethane-acrylate dispersion (WPUA) and acryloyl chloride modified lysozyme followed by UV curing. The covalent incorporation of lysozyme into the coatings was proved by enzyme leakage and IR analysis of the coatings. As the lysozyme content increased from 0 to 2.5% (w/w), the tensile strength of the coating enhanced by 37% (1.1MPa vs 0.8MPa), and the contact angle increased by 10% (73.1° vs 80.6°). Those changes are possibly due to enhancement of crosslinking degree and hydrogen bonding induced by modified lysozyme. Based on live/dead staining and colonies number assay, the coatings containing lysozyme (2.5%, w/w) were highly efficient in killing Staphylococcus aureus (91.3%) and Escherichia coil (62.9%) via degradation of cell wall within 2h, and the colonies number for both strains was significantly decreased to less than 1% after incubation for 24h. In addition, the killing efficiency of the coatings remained 68.3% after six continuous uses. Such UV-curable waterborne polyurethane coatings containing lysozyme (UWPU-L) may be useful in anti-bacterial stains on various common surfaces in hospital settings and food packaging.

Preparation and properties of waterborne poly(urethane acrylate)/silica dispersions and hybrid composites

The waterborne polyurethane acrylate (PUA) dispersion was prepared based on polyester polyol, isophorone diisocyanate, dimethylol propionic acid, butyl acrylate and trimethylolpropane triacrylate. Then, a series of PUA/SiO2 hybrid dispersions were prepared from PUA dispersion, coupling agent 3-glycidyloxypropyl trimethoxysilane and different content tetraethoxysilane hydrolysis solutions by the sol–gel process. The physical properties of PUA/SiO2 hybrid dispersions and the mechanical properties of PUA/SiO2 hybrid composites were measured. The PUA/SiO2 hybrids were characterised. The results showed that the nano-SiO2 particles of the hybrids had good dispersion and formed a good interfacial bonding layer on its surface. When the tetraethyl orthosilicate content was 0·5 wt-%, the hybrid film exhibited excellent comprehensive mechanical properties and water resistance. The tensile strength, hardness and water absorption of the film were 3·32 MPa, 90 and 6·7% respectively. The obtained PUA and hybrid composites have great potential application, such as coatings, leather finishing, adhesives, sealants, plastic coatings and wood finishes.

Steady rheological behaviors of UV-curable waterborne hyperbranched polyurethane acrylate dispersions

A rotational rheometer was used to investigate the steady rheological behaviors of UV-curable waterborne hyperbranched polyurethane acrylate dispersions (WHBPUADs). The flow curves of WHBPUADs were fitted mathematically using the Cross model. The effects of many factors including solid content, concentration of hydrophilic groups, and degree of neutralization on the rheological behaviors were studied and discussed. It was found that the viscosity of WHBPUAD decreased with increasing shear rate, indicating that WHBPUAD was pseudoplastic. On the other hand, at the same shear rate, the viscosity of WHBPUAD increased with increasing solid content and degree of neutralization but decreased with increasing concentration of hydrophilic groups. The Cross model could describe the flow curve of WHBPUAD accurately, with square of correlation coefficient (R 2) above 0.9. Moreover, most of the zero-shear viscosity values (η 0) obtained by the Cross model were located in the range of 0.2–10 Pa·s, which could fully meet the practical application requirement.

Synthesis, photopolymerization kinetics, and thermal properties of UV-curable waterborne hyperbranched polyurethane acrylate dispersions

A series of UV-curable waterborne hyperbranched polyurethane acrylate dispersions (WHBPUADs) were prepared via a three-step procedure based on isophorone diisocyanate (IPDI), hyperbranched polyester (HBP), maleic anhydride (MA), and hydroxy-ethyl acrylate (HEA). The structure of WHBPUADs was characterized by Fourier transform infrared spectroscopy (FTIR) and 1H nuclear magnetic resonance spectroscopy (1H NMR). FTIR was also applied to research the effect of double bond concentration on the kinetics of photopolymerization. The heat resistance of the cured films was characterized by thermogravimetric analysis (TGA), and their mechanical properties were also measured. The results showed that the double bond conversion (τ) and photopolymerization rate (R p) were affected by the concentration of double bond and viscosity of WHBPUADs. The UV-curable systems with higher double bond concentration and lower viscosity led to higher τ and R p. The maximum τ and R p reached 93% and 71 mmol g−1 s−1, respectively. The WHBPUADs films possessed better heat resistance and mechanical properties, and with the increase of crosslink density, the heat resistance and hardnesses were further improved.

Environmentally Friendly Polyurethane Composites: Preparation, Characterization and Mechanical Properties

The waterborne polyurethane (PU) prepolymer was prepared based on isophorone diisocyanate (IPDI), polyester polyol (N220), dimethylol propionic acid (DMPA) and hydroxyethyl methyl acrylate (HEMA). The modified waterborne polyurethane–acrylate (PUA) emulsions were obtained with different proportions of acrylate (butyl acrylate and methyl methacrylate) and initiating agent by in situ dispersion technique. The structures and thermal properties of prepared PU and PUA were analyzed and characterized with FT-IR, UV–Vis spectroscopy and DSC. The PUA hybrid samples had lower glass transition temperature of hard segment and higher decomposition temperatures than PU sample. Performances of the emulsion and film were studied by means of apparent viscidity, particle size and polydispersity, surface tension and mechanical properties. The results indicated that the particle sizes of the PUA dispersions were larger than those of the pure PU and the solvent resistance, mechanical properties of PUA films was improved compare with the unmodified polyurethane film. The film had the biggest hardness and the least water absorption when the BA/MMA mass ratio 5:5 modified PU. The obtained PUA have great potential application such as coatings, leather finishing, adhesives, sealants, plastic coatings and wood finishes.

Preparation, Characterisation and Mechanical Properties of Environmentally Friendly Waterborne Polyurethane and Polyurethane-Acrylate

The waterborne polyurethane (PU) prepolymer was prepared based on the polyester polyol (N220), isophorone diisocyanate (IPDI), and dimethylol propionic acid (DMPA). The waterborne polyurethane-acrylate (PUA) dispersions were prepared with different proportions of acrylate by in situ dispersion technique. The structures and properties of prepared PU and PUA were analysed and characterised with FT-IR spectroscopy, etc. The results indicated that compared with PU, the PUA dispersions had larger particle diameters, narrower particle-size distribution, lower surface tension, high temperature stability and freeze-thaw stability. The PUA films showed better optical transparency, higher tensile strength and lower elongation at break. The prepared PUA have potential application such as coatings, leather finishing, adhesives, sealants, plastic coatings and wood finishes.

Synthesis, rheological, and thermal properties of waterborne hyperbranched polyurethane acrylate dispersions for UV curable coatings

A series of waterborne hyperbranched polyurethane acrylate (WHUAs) ionomers used for ultraviolet curable waterborne coatings were synthesized. The average particle size of aqueous dispersion ranged between 48.2 and 75.3 nm at 0.05% concentration determined by laser light scattering. The effects of end group of WHUAs on rheological properties were investigated. WHUAs have much lower viscosity than EB2002, commercial linear waterborne polyurethane acrylate. Moreover, the glass transition temperature (Tg) evaluated by differential scanning calorimetry of samples showed that the influence of end capping by hard segment consisting of toluene diisocyanate–hydroxyethyl acrylate is significant due to the increase of crosslink density. All cured WHUA have higher glass transition temperatures than those of cured EB2002. The results of thermogravimetric analysis for cured WHUA films indicated good thermal stability with no appreciable weight loss until 200°C, and that an increase in the hard segment content provoked the increases in thermal degradation temperature. The activation energies were calculated by Flynn–Wall method to be 91.3, 114.3, and 139.7 kJ mol−1 for cured WHUA62, WHUA44, and WHUA26, with the individual ratios of 6:2, 4:4, and 2:6 for salt-like group to double bond at the terminals, compared with 81.1 kJ mol−1 of EB2002 in N2 atmosphere, respectively.

Investigation of ultraviolet curable waterborne polyurethane acrylate dispersion based on hydroxyl-terminated polybutadiene

A new kind of ultraviolet (UV) curable waterborne polyurethane acrylate dispersion was synthesized based on hydroxyl-terminated polybutadiene (HTPB), poly-(propylene glycol) (PPG), isophorene diisocyanate (IPDI), 2-hydroxy ethyl acrylate (HEA) and dimethylol propionic acid (DMPA) after neutralizing by triethylamine (TEA). 2-Hydroxy-1-[4-2-hydroxyethoxy) phenyl]-2-methyl-1-propanone (Irgacure 2959) was used as a photoinitiator and deionized water as a diluent. Fourier transform infrared (FTIR) analysis was used to identify the chain structure of the UV-curable polyurethane prepolymer based on HTPB and the curing process. Effects of relative content of HTPB and PPG on emulsion stability, resistance to water and ethanol, thermal stability, compatibility of soft and hard segment, as well as the mechanical property of the cured film were investigated.

UV curable waterborne polyurethane acrylate dispersions based on hyperbranched aliphatic polyester: effect of molecular structure on physical and thermal properties

AbstractA novel waterborne hyperbranched polyurethane acrylate for aqueous dispersions (WHPUDs) based on hydroxy‐functionalized hyperbranched aliphatic polyester Boltorn™ H20 was investigated. The effects of structural composition and crosslinking density have been studied in terms of swellability by water, thermal degradation, viscosity changes as well as transmission electron microscopy (TEM) morphology. The swell ratio showed an increasing trend with the higher concentration of ionic group, which is due to the increased total surface area of particles. The results of thermogravimetric analysis (TGA) for cured WHPUD films indicated good thermal stability with no appreciable weight loss until 200°C. The activation energies were evaluated and were found in the range 154–186 kJ mol−1. It was observed that an increase in hard segment content provoked the increases in thermal degradation temperature and activation energy of waterborne dispersions. The transmission electron photographs revealed that the average particle sizes of aqueous dispersions were in the range 30–125 nm. Owing to the enlargement of the stabilization site, the particle size decreased as the content of carboxyl group and degree of neutralization increased. The viscosity of WHPUDs increased rapidly with increasing the degree of neutralization. Moreover, water showed a favorable viscosity reduction effect. Copyright © 2004 John Wiley &amp; Sons, Ltd.

Photopolymerization of waterborne polyurethane acrylate dispersions based on hyperbranched aliphatic polyester and properties of the cured films

A series of novel waterborne hyperbranched polyurethane acrylates for aqueous dispersions (WHPUD) based on hydroxy-functionalized hyperbranched aliphatic polyester Boltorn™ H20 were investigated and used as UV curable oligomers. The aqueous dispersions were electrostatically stabilized with carboxyl groups incorporated into their structures, which were neutralized by triethylamine. The photopolymerization kinetics of these WHPUDs was studied with respect to polymerization rates and unsaturation conversions in the presence of a photoinitiator using differential scanning calorimetry. The polymerization rates of the resins under UV irradiation and the gel contents in the cured films showed an increasing trend with higher concentration of acrylate functionality, which is in favor of the theory of radical chain polymerization. The mechanical and thermal behaviors of UV cured films of aqueous dispersions were evaluated by tensile testing and dynamic mechanical thermal analysis (DMTA). The results of DMTA investigations indicated that the glass transition temperature shifted to higher temperature as the content of the hard segment consisting of IPDI-HEA increased. Moreover, the storage modulus and pendulum hardness also increased with increasing the hard segment content. As the degree of neutralization increased, the Tg and tensile strength decreased, whereas, the elongation at break increased.

Structure?property study of waterborne, polyurethane acrylate dispersions based on hyperbranched aliphatic polyester for UV-curable coatings

A series of waterborne, hyperbranched polyurethane acrylates for aqueous dispersions (WHPUDs) based on hydroxy-functionalized hyperbranched aliphatic polyester Boltorn H20 were synthesized and characterized by Fourier transform infrared spectroscopy (FTIR). The aqueous dispersions were electrostatically stabilized with carboxyl groups incorporated into their structures, which were neutralized by triethylamine (TEA). The effects of chemical structures of end groups on various properties of WHPUDs, such as particle size, interfacial tension, and rheological behavior were investigated. The average particle sizes of aqueous dispersions, 43–237 nm, were determined by laser light scattering. Owing to the enlargement of the stabilization site, the particle size decreased as the content of carboxyl group, degree of neutralization, and dielectric constant of the dispersion medium increased. Moreover, the surface tension of aqueous dispersions of WHPUDs decreased as the TEA/COOH mole ratio and degree of neutralization increased. The investigations of the rheological behavior of the WHPUDs suggested that all the dispersions belong to pseudoplastic fluids, and each of them has viscosity much lower compared with the commercial water-based resin EB 2002.

Chain‐extended polyurethane–acrylate ionomer for UV‐curable waterborne coatings

AbstractConventional and chain‐extended UV‐curable waterborne polyurethane–acrylate (PUA) ionomers were prepared from diisocyanate, polyethylene glycol (PEG), dimethylolpropionic acid, and hydroxyethyl methacrylate, and identified with FTIR spectra and 500‐MHz 1H‐NMR spectra. The number‐average molecular weight (Mn) and polydispersity of chain‐extended PUA were determined by gel permeation chromatography. For the synthesis of chain‐extended PUA, water was employed as the chain extender. The two kinds of PUA prepolymer could be easily dispersed in water in the form of self‐emulsified latex after the carboxyl group attaching to the backbone of PUA was neutralized with tertiary amine. The effects of Mn of PEG, carboxyl content, and type of diisocyanate on the interfacial tension and rheological behavior of PUA dispersions were investigated. The chain‐extended PUA prepolymer could photopolymerize to a greater extent than the conventional PUA, as indicated by differential photocalorimetry. The photopolymerization kinetics of chain‐extended PUA, based on different substrates, were also investigated. The differential scanning calorimetry analysis for the photo‐cured films from PUA dispersions suggested that lower Mn of PEG tended to favor phase mixing between soft and hard segment phases, and higher Mn of PEG would provoke phase separation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1818–1831, 2002; DOI 10.1002/app.10384

UV curing of aqueous polyurethane acrylate dispersions. A comparative study by real-time FTIR spectroscopy and pilot scale curing

Real-time FTIR spectroscopy was used to study the chemical and physical factors, e.g., photoinitiator and temperature, affecting the UV curing of dried films from aqueous polyurethane acrylate dispersions. Poor conversion of the acrylate double bonds (67%) observed at room temperature can be overcome by irradiation at elevated temperatures. At 353 K almost complete conversion is observed, even with reduced photoinitiator content. Single or multiple UV-light flash experiments were performed to simulate technical parameters, e.g., cure speed and number of required UV lamps, with the help of RTIR spectroscopy. The results obtained were confirmed by pilot-scale UV curing experiments: one or, at most, two UV lamps of high intensity are sufficient for the curing process with respect to the double-bond conversion. The coatings based on the polyurethane acrylate dispersion show low sensitivity towards oxygen from air. Moreover, in comparison to UV curing under inert nitrogen atmosphere, a small “positive” effect on the conversion in the presence of air has been observed, which might be due to the contribution of peroxyl radicals or their decomposition products to curing.

Synthesis and characterization of UV-curable waterborne polyurethane-acrylate ionomers for coatings

A new kind of ultraviolet (UV)-curable waterborne polyurethane–acrylate (PUA) ionomer, prepared from toluene diisocyanate (TDI), polyethylene glycol (PEG), dimethylolpropionic acid (DMPA), triethylamine (TEA), and 2-hydroxyethyl methacrylate (HEMA), was synthesized by the modified prepolymer mixing process in which water serves as a chain-extender and dispersant. Fourier transform infrared (FTIR) spectra demonstrated the formation of the PUA ionomers both in dispersions and in their corresponding cured films. Surface tension of the PUA dispersions decreased as the DMPA-to-PEG mole ratio increased. The investigation of rheological behavior of the PUA dispersions suggested that all the dispersions belong to pseudoplastic fluid and display the characteristic of common polymer dispersions. Differential scanning calorimetry (DSC) analysis showed that the increasing DMPA-to-PEG mole ratio may result in a higher Tg and a broader transition zone for the hard segment. The results of TGA for the PUA-cured films indicated good thermal stability with no appreciable weight loss until well above 200°C. Measurement of physical properties showed that all the PUA-cured films exhibited excellent adhesion, gloss, flexibility, and impact strength, as well as pendulum hardness, depending upon hard segment content. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2869–2876, 1999