Self-stratifying antimicrobial polyurethane coatings

In this work antimicrobial polyurethane coatings were prepared aiming at self-stratification. A hydroxyl end-capped liquid oligoester consisting of three equimolar diacids and an excess of 1,4-butanediol has been synthesized by a condensation reaction. A set of quaternary ammonium compounds (QACs) which are well known contact killers, was synthesized via a straightforward quaternization reaction. These synthesized precursors were later covalently bonded to the polymer network by addition of a polyisocyanate crosslinker resulting in antimicrobial polyurethane coatings. Self-stratification was confirmed by dynamic contact angle analysis and X-ray photoelectron spectroscopy. The final films showed strong antimicrobial activity against both Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli type bacteria.     

Preparation and antimicrobial activity of terpene-based polyurethane coatings with carbamate group-containing quaternary ammonium salts

A series of novel carbamate group-containing quaternary ammonium salts (QASs) have been synthesized, which were subsequently used as antimicrobial agent and incorporated into polyurethane coatings through crosslinking with terpene-based polyol and polyisocyanate. The chemical structures of QASs were characterized by FT-IR, ¹H NMR, and ¹³C NMR. The effects of QASs on the properties of coatings were investigated. The results showed that the resulting coatings exhibited significant antimicrobial activity against both Staphylococcus aureus and Escherichia coli by introducing QASs into the polyurethane networks. Furthermore, with the increasing of QAS content, the antimicrobial activity and adhesion of the coatings were enhanced, while the pencil hardness, water resistance and thermal stability of the coatings were decreased.     

Synthesis and characterisation of star branched polyesters with dendritic cores and the effect of structural variations on zero shear rate viscosity

A series of branched polyesters consisting of poly(ε-caprolactone) (PCL) (degree of polymerisation: 5-200) initiated from hydroxy-functional cores and end-capped with methylmethacrylate have been prepared. The cores were third-generation hyperbranched polyester, Boltorn, with approximately 32 hydroxyl groups, a third-generation dendrimer with 24 hydroxyl groups and a third-generation dendron with eight hydroxyl groups. Finally, a linear PCL was synthesised as a reference material. All initiators were based on 2,2-bis(methylol) propionic acid (bis-MPA). ¹³C NMR spectra of the polymers showed that those with shorter arms contained unreacted hydroxyl groups on the core. Rheological measurements of zero shear rate viscosity, η₀, showed that the branched polyesters had a considerably lower η₀ than linear polyester with similar molecular weight. The low melt viscosity and the crystallity produced a rheological behaviour suitable for the film formation process for powder coatings. Measurements of mechanical properties of cured films showed that those with low arm molecular weight, M_a, were amorphous while those of high M_a were crystalline.     

Pervaporation separation of benzene/cyclohexane through AAOM-ionic liquids/polyurethane membranes

Supported ionic liquids/polyurethane (PU) membranes were prepared by immobilizing ionic liquids on a porous anodic aluminum oxide membrane (AAOM) support that was coated on one side with polyurethane (PU). The microstructure of all membranes was characterized using scanning electron microscopy (SEM). The pervaporation separation performance of the supported ionic liquids/polyurethane membranes was investigated for benzene/cyclohexane (Bz/Cy) mixtures. The SEM results demonstrated that the porous surface of the AAOM support was sealed by the dense polyurethane membrane and the pores of the AAOM support were impregnate with ionic liquids. The ionic liquids filling in the AAOM support enhanced the separation selectivity of Bz/Cy. The separation factor of Bz to Cy increased from 5 to 34.4 and the largest PSI of AAOM-[C₄mim]PF₆/PU membrane reached 452.54 g m⁻² h⁻¹ at 55 °C for a 50 wt.% Bz/Cy mixture. Because the polyurethane prevented the leakage of ionic liquids filled in the AAOM support, the supported ionic liquids/polyurethane membranes exhibited excellent stability.     

Silver- and Zinc-Decorated Polyurethane Ionomers with Tunable Hard/Soft Phase Segregation

Segmented polyurethane ionomers find prominent applications in the biomedical field since they can combine the good mechanical and biostability properties of polyurethanes (PUs) with the strong hydrophilicity features of ionomers. In this work, PU ionomers were prepared from a carboxylated diol, poly(tetrahydrofuran) (soft phase) and a small library of diisocyanates (hard phase), either aliphatic or aromatic. The synthesized PUs were characterized to investigate the effect of ionic groups and the nature of diisocyanate upon the structure–property relationship. Results showed how the polymer hard/soft phase segregation was affected by both the concentration of ionic groups and the type of diisocyanate. Specifically, PUs obtained with aliphatic diisocyanates possessed a hard/soft phase segregation stronger than PUs with aromatic diisocyanates, as well as greater bulk and surface hydrophilicity. In contrast, a higher content of ionic groups per polymer repeat unit promoted phase mixing. The neutralization of polymer ionic groups with silver or zinc further increased the hard/soft phase segregation and provided polymers with antimicrobial properties. In particular, the Zinc/PU hybrid systems possessed activity only against the Gram-positive Staphylococcus epidermidis while Silver/PU systems were active also against the Gram-negative Pseudomonas aeruginosa. The herein-obtained polyurethanes could find promising applications as antimicrobial coatings for different kinds of surfaces including medical devices, fabric for wound dressings and other textiles.     

UV-curable nano-silver containing polyurethane based organic–inorganic hybrid coatings

The preparation of nano-silver containing polyurethane based UV-curable organic–inorganic hybrid coatings that have antibacterial activity is presented in this paper. Trimethoxysilane end-capped bis[(4-β-hydroxyethoxy)phenyl] methyl phosphine oxide urethane was synthesized as a coupling agent and used to improve the compatibility between the organic and inorganic phases of the hybrid coating. Due to its strong antibacterial activity, silver nanoparticles were prepared and added to the nanocomposite formulations. The relationships between the amount of coupling agent and the final coating properties were investigated. The hybrid coatings presented good thermal stability. Tests for abrasion, hardness, gloss, and adhesion of the coatings were also performed. The morphological investigation was performed by SEM to determine the size of the silver nanoparticles. The nano-silver containing coatings exhibited good antibacterial activity against E. coli and S. aureus.     

Fixation of ionic liquids into polyether-based polyurethane films to maintain long-term antistatic properties

Ionic liquids (ILs) were fixed into polyether-based polyurethane (PU) films for sustainable antistatic properties. Preliminarily, ILs were screened in terms of efficiency of antistatic effect. Surface resistivity (ρ_s) for IL-doped PU films changed depending the anion species, and the smallest ρ_s was found for the PU films containing bis(trifluoromethanesulfonyl)imide ([Tf₂N])-type ILs. Then, [Tf₂N]-type ILs composed of ammonium cations having hydroxyl groups were fixed into the PUs through urethane bonds. The fixation of 1000 ppm of the ILs reduced the ρ_s of the PU films from 2.1 × 10¹² to 2.1 × 10⁹ Ω sq⁻¹. These IL-fixed PU films were revealed to possess high washing durability confirmed by negligible change of ρ_s before and after ultra-sonication treatment in methanol.     

Synthesis and characterization of triazole rich polyether polyols using click chemistry for highly branched polyurethanes

The present work describes development of moisture cured polyurethane–urea coatings based on 1,2,3-triazole rich polyether polyols. In this paper, two polyether polyols were synthesized by using 1,3-dipolar azide–alkyne cycloaddition reaction and they were named as PL-1 and PL-2 where PL-1 is 9 terminal hydroxyl groups and PL-2 is 6 terminal hydroxyl groups. These polyols were reacted with 4, 4′-diisocyanatodicyclohexylmethane (H₁₂MDI) at OH:NCO ratio of 1:1.2 in order to obtain isocyanate terminated polyurethane prepolymers. The resulted prepolymers were casted on tin foil and cured under atmospheric moisture in order to get completely cured polyurethane–urea free films. The free films were characterized by using Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and dynamic mechanical thermal analysis (DMTA) techniques. The TGA and DMTA results showed that these films have good thermal and mechanical stability. Anti-microbial studies proved that these polyurethane films show good resistance towards different bacterial and fungal attacks. These polymers were also coated on mild steel panels in order to evaluate corrosion resistance properties by using salt spray and electro chemical polarization studies.     

Preparation and characterization of waterborne polyurethane/silica hybrid dispersions from castor oil polyols obtained by glycolysis poly(ethylene terephthalate) waste

Castor oil polyols (COLs) have been synthesized from glycolyzed oligoester polyol in order to produce waterborne polyurethane (WPU)/silica hybrid dispersions. Soft drinks poly(ethylene terephthalate) (PET) bottles were depolymerized by glycolysis with different molar ratio of poly(ethylene glycol) ( PEG 400), in the presence of zinc acetate as catalyst. The obtained glycolyzed products were reacted with castor oil (CO) to attain castor oil polyols by the process of transesterification. Five castor oil polyols were used with hydroxyl values of 255, 275, 326, 366 and 426 mg KOH g⁻¹. Several castor oil-based, polyurethane/silica hybrid dispersions having soft segment content of 39.6% to 28.2% and two concentrations of SiO₂ nanoparticles (0.5 and 1.0) have been prepared.The incorporation effect of SiO₂ nanoparticles into the PU matrix and the hydroxyl functionality of the COLs on the thermal and mechanical properties of resulting polyurethane films has been examined by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermal gravimetric analysis (TG) and measurement of the mechanical properties. The degree of phase separation (DPS) between oxide nanoparticles and hard segment, and particle size in the polyurethane, depends to some extent on nanosilica content and the hydroxyl functionality of the polyols employed in the polyurethane preparation process.Thermal stability of obtained hybrid materials depends on the hydroxyl functionality of the COLs and nanosilica content. The T_10% and T_50% (the temperature where 10 and 50% weight loss occurred) of WPU films decreased with the rise of OH functionality of castor oil polyols, caused by the increase of hard segment content. Glass transition temperature increased with increasing OH functionality and SiO₂ content. The hardness, adhesion and gloss quality of the polyurethane films were also determined with a view to assessing the effect of mole ratios of PET to glycol in glycolyzed products, the hydroxyl functionality and the SiO₂ content.     

Facile synthesis of waterborne UV-curable polyurethane/silica nanocomposites and morphology,physical properties of its nanostructured films

Waterborne UV-curable polyurethane (WUPU)/silica nanocomposites were prepared by in situ method using aqueous silica sol. SEM examinations of hybrid films indicated that the nanosilica were well dispersed in the matrix. Atomic force microscopy revealed that the microphase separation between polyurethane and silica was significantly affected by the amount of silica incorporated. DMA analysis showed that the nanocomposite films with silica nanoparticles showed a single tan δ peak, which implies that soft and hard segments of polyurethane are well phase mixed. The nanostructure films displayed enhanced storage modulus, tensile strength without sacrificing high elongation at break. The resulting transparent hybrid films are promising for a number of applications, e.g. for high performance water-based UV-curable coatings.     

Investigation of the effect of ZnO nanoparticles on the thermomechanical and microbial properties of hyperbranched polyurethane‐urea hybrid composites

Hybrid coatings of hyperbranched polyurethane‐urea (HBPUU) containing ZnO nanoparticles were prepared by mixing the hyperbranched polyurethane with the nanoparticles. The films were stored at room temperature and laboratory humidity conditions for one week to yield completely cured hybrid films. The ZnO nanoparticles were found to be well dispersed in the polymer up to 3 wt%. The structure–property relationship of various HBPUU–ZnO hybrid coatings was analysed using a Fourier transform infrared peak deconvolution technique with a Gaussian curve‐fitting procedure, while their viscoelastic, thermomechanical and surface morphology were studied using X‐ray diffraction, dynamic mechanical thermal analysis, thermogravimetric analysis, a universal testing machine, scanning electron microscopy, atomic force microscopy and contact angle instruments. The thermal stability and mechanical properties of the hybrid composite films improved with increasing ZnO content, which was believed to be due to thermal insulation in the presence of nanoparticles. Water contact angle data suggested that the hydrophobic character of the hybrid composites increased with increasing nanoparticle concentration. The antimicrobial property of the HBPUU–ZnO hybrid coatings was studied using the disc diffusion method. HBPUU–ZnO hybrid coatings showed good antimicrobial properties compared to HBPUU. Copyright © 2012 Society of Chemical Industry     

Preparation and evaluation of nonionic amphiphilic phenolic biocides in urethane hydrogels

Phenols are rarely used in the preparation of polyurethanes because of the inherent competitive reaction of the phenolic moiety with isocyanates. This work represents a successful application of the combination of phenols with isocyanates toward the development of phenolic‐based antimicrobial urethane coatings for niche applications. In this effort, a series of nonionic amphiphilic phenolic molecules were prepared by condensation of 4‐hexylresorcinol with the corresponding hydroxyl‐terminated monomethyl poly(ethylene glycol) in the presence of a catalytic amount of acid in refluxing toluene. These new molecules were evaluated against a variety of Gram‐positive and Gram‐negative bacteria for their antimicrobial activity in minimum inhibitory concentration solution testing. The same amphiphilic molecules were also incorporated into a hydrophilic polyurethane hydrogel and dispensed as films for evaluation of surface activity with a newly developed protocol. All samples possessed some degree of surface antimicrobial activity, which was expressed as a log kill reduction in colony‐forming units starting from an initial bacterial concentration of 10⁷ CFU, and structural features of the phenolic compound were found to contribute significantly to the observed antimicrobial activity. The highest activity was observed in samples containing the phenolic compound with the shortest ethylene oxide polar structural feature and therefore highest mobility in the highly polar urethane resin. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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.     

Anionic waterborne polyurethane dispersions based on hydroxyl‐terminated polybutadiene and poly(propylene glycol): Synthesis and characterization

Nonpolluting systems based on anionic polyurethane aqueous dispersions were obtained. The prepolymer based on hydroxyl‐terminated polybutadiene (HTPB), isophorone diisocyanate (IPDI), poly(propylene glycol) (PPG), and dimethylolpropionic acid (DMPA) were synthesized in bulk. After neutralization with triethylamine (TEA), the anionomer prepolymer was dispersed in water, followed by a chain‐extension reaction with ethylenediamine (EDA). The prepolymers were characterized by Fourier transform infrared spectrometry (FTIR) and the average particle size of the aqueous dispersions was determined by laser light scattering (LLS). The mechanical behavior of polyurethane‐cast films and the adhesive properties of the aqueous dispersions as coatings for wood were evaluated. It was observed that an increase in the HTPB content provoked an increase in the viscosity and in the particle size of the dispersions. The tensile strength and the modulus values of the films and the adhesiveness of the coatings in wood were also increased by increasing the HTPB content. On the other hand, the elongation of the polyurethane‐cast films and the tackness of the surface coatings decreased as the HTPB was increased. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 566–572, 2001     

Electrochemical behavior of C60 films and C60/lipid films in ionic liquids

Cyclic voltammograms (CVs) of C₆₀ films and C₆₀ embedded in cast films of triple-tailed cationic surfactant solutions and salt-free zero-charged cationic/anionic (catanionic) surfactant vesicles on glassy carbon electrode in a typical room-temperature ionic liquid (RT-IL), 1-n-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]), were examined. CVs show typically electrochemical oxidation and reduction. The salt-free zero-charged catanionic surfactant bilayer vesicles were determined by freeze-fracture transmission electron microscopy (FF-TEM) images and small-angle X-ray scattering (SAXS) measurements. The cast films of the salt-free zero-charged catanionic surfactant vesicles incorporated C₆₀ molecules were employed to study the electrochemical properties in RT-ILs, which would open new fields for the bulk electronic properties of fullerenes or their derivatives in ionic liquids.     

Antimicrobial properties and thermal stability of polycarbonate modified with 1‐alkyl‐3‐methylimidazolium tetrafluoroborate ionic liquids

Four water immiscible ionic liquids (ILs): 1‐hexyl‐3‐methylimidazolium tetrafluoroborate, 1‐heptyl‐3‐methylimidazolium tetrafluoroborate, 1‐octyl‐3‐methylimidazolium tetrafluoroborate and 1‐dodecyl‐3‐methylimidazolium tetrafluoroborate have been synthesized. Polycarbonate (PC) films containing ILs were prepared by solvent casting from methylene chloride solutions. Scanning electron microscopy measurements showed the high homogeneity of PC/IL films with the IL content up to 4 wt %. The tendency to IL aggregation was observed for polymeric films with higher IL content (5%). PC/IL composites were found to have the reduced thermal decomposition temperature under both an air and a nitrogen atmosphere in comparison with the neat PC. The effect of IL content on the antimicrobial activity of PC films against Escherichia coli bacteria was studied. Pronounced antimicrobial efficacy was revealed for PC/IL films for all studied ILs starting from 3 wt % of IL. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40050.     

Structure and thermo-mechanical properties study of polyurethane-urea/glycidoxypropyltrimethoxysilane hybrid coatings

A series of organic–inorganic hybrid coatings were prepared using polyurethane (PU)-urea and glycidoxypropyltrimethoxysilane (GPTMS) To prepare this first acid terminated saturated polyester, having 230 hydroxyl value and acid value 25 mg/KOH, were reacted with coupling agent GPTMS at different concentrations in the presence of base catalyst and each of them were further reacted with isophorone diisocyanate (IPDI) at NCO/OH ratio of 1.6:1 for 4–5 h at 70–80 °C These prepolymers were casted on tin foil and cured at ambient conditions for 6 h and prepared the hybrid coating free films by amalgamation. These free films were stored in the room temperature for 40 days and used for further characterization. The coating without and with different concentrations of GPTMS were named as base polymer and hybrid coatings, respectively. FTIR spectroscopy was used for the structural analysis of the coatings. Thermogravimetric analysis (TGA) showed that thermal stability of the hybrids was significantly higher than the base polymer. The onset degradation temperature of the base polymer starts at 268.9 °C, while it ranges from 279.1 °C to 290.8 °C for the hybrids based on the concentration of GPTMS used. The glass transition temperature (T_g) and storage modulus as determined from DMTA were higher for hybrid coatings as compared to base polymer. T_g of base polymer was 42.3 °C while it varies between 65.8 °C to 83.5 °C for hybrids.     

Development of moisture cure polyurethane–urea coatings using 1,2,3-triazole core hyperbranched polyesters

This article reports the development of moisture cure polyurethane–urea coatings. The coating has been developed using different generations of novel 1,2,3-triazole core containing hyperbranched polyester polyols (THBP). For the synthesis of THBP, the core molecule, tetra hydroxyl-terminated di-triazole (THTD), has been synthesized by click reaction involving ethylene diazide and 2-butyne-1,4-diol. The polycondensation reaction between the core THTD and 2,2-bis (hydroxymethyl) propionic acid (Bis-MPA) at different mole ratios has been used to get first (THBPG-1), second (THBPG-2), and third (THBPG-3) generations of triazole core hyperbranched polyesters. The structural investigations of these THBPs have been carried out by ¹H NMR, ¹³C NMR, and FTIR spectroscopy. The different generations of THBPs were further reacted with 1-isocyanato-4-[(4-isocyanatocyclohexyl) methyl] cyclohexane (H₁₂-MDI) at OH:NCO ratio of 1:1.2 to get –NCO terminated triazole core hyperbranched polyurethanes. They were cured under atmospheric moisture to get hyperbranched polyurethane–urea coatings and were named as THBPUG-1, THBPUG-2, and THBPUG-3. FTIR has been used to confirm the formation of polyurethane coatings. The TGA and DMTA have been used to determine the thermal stability and dynamic mechanical properties of the coatings, respectively. The corrosion resistance properties of the coatings have been studied by salt spray and electrochemical test. The coatings were also evaluated for microbial resistance. The results indicate that the thermal stability, glass transition temperature, and corrosion resistance properties increase with an increase in generation number of THBPs used for coating development. All three generations of coating films show excellent antimicrobial activity. Based on overall combined structure–property relationship study, these types of coatings will be useful as multifunctional applications in marine and moist environments.     

Effect of isocyanate to hydroxyl index on the properties of clear polyurethane films

Clear polyurethane films were made from aqueous polyurethane pre-polymer dispersions and water-dispersible aliphatic isocyanate pre-polymer, varying the amount of isocyanate used to cure the films. Film series were made from one of two polyol dispersions; the control XP-7110 having a higher molecular weight and containing 10 wt.% n-methylpyrrolidone (nmp) was compared to a zero-volatile organic compound (VOC) lower molecular weight alternate polyol XP-2591. Increasing the relative number of isocyanate groups to hydroxyl groups in these films provided an increase in glass transition temperature (T_g), tensile strength, elastic modulus and improved barrier properties to dimethyl methylphosphonate (DMMP) for both polyols in this study. At all indices in this study XP-7110 films achieved slightly higher T_g and slightly better resistance to permeation by DMMP than the XP-2591 films. Water resistance of the films was not improved at higher indices nor was there any difference between the polyols. Yet, the experimental results suggest that it is possible to produce polyurethane binders with acceptable film properties while reducing the VOC content of the formulation by using t-butyl acetate as the isocyanate reducing solvent. The zero-VOC polyol achieved better tensile properties with higher indexing than the current polyol containing 10 wt.% VOC. While the zero-VOC polyol did not perform as well as the baseline polyol in some tests, the differences in performance were small and thus there may be an opportunity to use the zero-VOC polyol as a partial or even a complete replacement of the current material.     

Development of polyetheramide based corrosion protective polyurethane coating from mahua oil

Mahua (Madhuca indica) is a widely grown tree in tropical regions of India. The estimated annual production of it is higher as compared to karanja oil and neem oil. In the present work mahua oil was reacted with diethanol amine resulting in the formation of mahua oil fatty amide (MFA) which was further reacted with bisphenol-A forming mahua polyetheramide resin (MPEA). The structures of the synthesized intermediate and polyetheramide resin were confirmed by spectroscopic methods and estimated physico-chemical properties like acid value, iodine value, saponification value, hydroxyl and acid value. The prepared MPEA resin was converted to polyurethane coatings by reacting with methylene diphenyl diisocyanate (MDI) and toluene diisocyanate (TDI) with 1.1:1 NCO/OH ratio. Thermal stability and coating properties of polyurethane coatings on steel panels and particle board panels were investigated. The coating performance of the resin was tested by measurement of gloss, mar resistance, flexibility, scratch, pencil hardness, adhesion and chemical resistance using standard methods. The results presented better physico-mechanical as well as corrosion resistance performance of the polyurethane coating obtained from mahua oil based polyetheramide resin.