Synthesis and characterization of waterborne polyurethane/polyhedral oligomeric silsesquioxane composites with low dielectric constants

A facile method was developed to synthesize a new type of polyhedral oligomeric silsesquioxane (POSS). It contained a single amine group and seven aliphatic moieties on its corners. FT‐IR, ¹H‐NMR, ¹³C‐NMR, ¹³C‐¹H COSY, and ¹H‐¹H COSY confirmed that cages with eight corners were the main part of the product. This new POSS was used to modify the structure of hexamethylene diisocyanate trimer and then copolymerized with hexamethylene diisocyanate and poly (tetramethylene glycol) to get a serious of waterborne polyurethane (WPU)/POSS hybrid materials with low dielectric constants for microelectronics applications. The results showed that POSS particles were uniformly dispersed in the WPU dispersions. The WPU/POSS films did not show any macrophase separation, even when the POSS content was as high as 16%. As the POSS content increased from 0% to 16%, the tensile strength was increased from 2.3 to 7.3 MPa, the dielectric constant was decreased from about 2.9 to 2.0, and the thermal stability of the WPU/POSS was also improved.     

The use of zinc dimethacrylate functionalized graphene as a reinforcement in rubber composites

Zinc dimethacrylate functionalized graphene (Z‐GE), as reinforcing nanofiller for natural rubber (NR), was synthesized by liquid‐phase exfoliation and in situ method. The morphology and structure of Z‐GE were characterized to confirm the exfoliation and functionalization of GE. The NR/Z‐GE composites were prepared and investigated by mechanical analysis, crosslinked network analysis and the analysis of thermal conductivity. The results showed that the tensile strength, tear strength and modulus at 300% strain of NR/Z‐GE‐20 composites (contents 1.400 phr GE) were increased by 142%, 76% and 231% as compared with the pure NR, respectively. And the thermal conductivity of NR/Z‐GE‐30 composites is enhanced by 39% as that of the pure NR. This significant improvement is attributed to the formation of covalent crosslinked network and ionic crosslinked network and efficient interfacial interaction between GE and NR matrix. This method provides a new insight into the fabrication of multifunctional GE composites and enlarges its potential applications in high performance GE‐based rubber composites. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis of a biobased waterborne polyurethane with epichlorohydrin-modified lignin

Abstract

A series of lignin-based waterborne polyurethanes (ELWPUs) are prepared using epichlorohydrin-modified lignin (ELG) as the biobased component. The effect of ELG dosage on the performance of the dispersions was studied by particle sizing. The morphology, crystallinity, thermal behavior, water resistance and mechanical properties of the films were investigated as well. The results show that the particle size of ELWPU dispersions increased with the addition of ELG. Furthermore, the ELWPU exhibited noticeable thermal stability, desired mechanical properties and water resistance as the tensile strength of ELWPU film containing 0.25?wt% ELG increased to 40.6?MPa from 15.2?MPa and the water absorption rate decreased from 20.1 to 12.4% compared to the non-modified waterborne polyurethane. The ELG played an important role in improving the properties of the biomass-based materials.     

Synthesis and thermal properties of antimony doped tin oxide/waterborne polyurethane nanocomposite films as heat insulating materials

The waterborne polyurethane (WPU) was synthesized from the polycondensation between isophorone diisocyanate (IPDI) and polyoxypropylene glycol (N‐210) and then dispersed into water. Subsequently, the WPU emulsion was modified with antimony doped tin oxide (ATO) nanoparticle by ultrasonic dispersion. The ATO/WPU emulsion was cast onto Teflon molds. After being dried, ATO/WPU films were prepared. TEM indicated that the ATO nanoparticles were homogeneously dispersed in the polymer matrix at the nanometer scale. DSC showed that the ATO/WPU nanocomposites displayed increased glass transition temperatures compared to the control WPU. The mechanical properties of the films were characterized by dynamic‐mechanical analysis (DMA). The higher glass transition temperature and storage modulus indicates the superior mechanical properties of WPU modified by ATO nanoparticles over the conventional unmodified WPU. The thermal behaviors of the films were evaluated by thermogravimetric analysis (TGA). It could be found that the incorporation of ATO into WPU can improve the thermal stability dramatically. The results from UV–visible–near infrared spectra indicated that the ATO/WPU films could decrease the infrared transmission effectively. The heat‐insulation measurements showed that glass coated with ATO/WPU films possessed better heat‐insulating effect than empty glass. Copyright © 2010 John Wiley & Sons, Ltd.     

Structure and properties of composites compression‐molded from silk fibroin powder and waterborne polyurethane

The degummed silk filament was pulverized with a home‐made machine to obtain the silk fibroin (SF) powder with the diameter of around 3 µm. The resulting SF powder was blended with waterborne polyurethane (WPU) aqueous dispersion, and then was dried and compression‐molded to prepare novel blended materials with improved miscibility and mechanical properties. WPU acted as a plasticizer and one of the components for the blends during the compression‐molded process. The structure, morphology, and properties of the blended films were investigated. The results indicated that β‐sheet of SF existed in the blended films. The SEM images showed that the cross‐section of the blended films exhibited an overall homogeneous morphology. Furthermore, the transmission electron microscope observation exhibited that some sphere‐like SF particles were well dispersed in the WPU matrix. The hydrogen bond interaction between SF and WPU in the blended films led to an increase of the glass transition temperature for the soft segment of WPU in the blended films. The blended films showed an improved Young's modulus and tensile strength from 1.2 to 288.9 MPa and 0.3 to 16.5 MPa, respectively, with the increasing of SF up to a content of 70 wt%. The hydrogen‐bonding interactions existing in SF and WPU and compression molding method played the important role in improving the miscibility and mechanical properties of the blended films. Copyright © 2011 John Wiley & Sons, Ltd.     

Study on synthesis,characterizations, and properties of pyridinol-blocked isocyanates and waterborne polyurethane

A series of pyridinol-blocked isophorone isocyanates were synthesized through esterification reaction, Fries rearrangement, and blocking reaction and characterized by ¹H-NMR, ¹³C-NMR, and Fourier transform infrared spectra. Based on the synthesized blocked isocyanates, the blocked waterborne polyurethane (BWPU) was prepared by the self-emulsification method. The deblocking studies revealed that the deblocking temperature reduces with electron-withdrawing and steric hindrance substituents on the ortho position of pyridinol. The stability, molecular weight (M_w), particle size, viscosity, and hydrophilicity of BWPU were studied and compared. The results showed that with an increased amount of blocking agents, molecular weight, particle size, and viscosity decrease and the hydrophilicity increases.     

Development of environmental friendly castor oil‐based waterborne polyurethane dispersions with polyaniline

This study describes the fabrication and characterization of castor oil‐based waterborne polyurethane/polyaniline (COWPU/PAni) conducting polymer blend films. The COWPU synthesized from isophorone diisocyanate was reacted with castor oil to form prepolymers, which were chain extended by reacting it with N‐methyldiethanolamine. Quaternization and self‐emulsification including deionized water followed in COWPU dispersions. Also, COWPU/PAni hybrid dispersions were synthesized with 2, 4, and 6 wt% of PAni–dodecyl benzene sulfonic acid to make different conductive composites. The outcome of COWPU/PAni was characterized by Fourier transform infrared spectrometer, differential scanning calorimeter, thermogravimetric analysis, dynamic mechanical and thermal analyzer, and scanning electron microscopy analysis. According to Fourier transform infrared spectrometer analysis, hydrogen bonding appears between –NH of PAni and C?O of COWPU. Meanwhile, incorporating PAni can improve the thermal stability of COWPU. The resulting COWPU/PAni conducting blend films can be used as antistatic and anticorrosive coating materials. Copyright © 2016 John Wiley & Sons, Ltd.     

Physical and mechanical properties of graphene oxide/polyethersulfone nanocomposites

The aim of this study was to investigate physical and mechanical properties of graphene oxide (GO)/polyethersulfone (PES) nanocomposite films. The films were produced by solution casting method. The mechanical properties of composite films were evaluated by tensile test. A significant enhancement in the mechanical properties of neat PES films was obtained incorporating a small amount of GO loading (0.05–1 wt.%). The highest tensile strength was observed at 1 wt.% of GO. Comparisons were made between experimental data and the Halpin–Tsai model predictions for the tensile strength and modulus of GO/PES composites. The effect of an orientation factor on model predictions was also acquired. The hydrophilicity of the nanocomposite was evaluated by assessing contact angle and enhanced wet ability of the films was obtained with increasing the amount of GO up to 1%. The morphology of the nanocomposites was investigated using scanning electron microscopy and transmission electron microscopy and the results revealed a good dispersion of GO in the PES matrix. The thermal behavior of the composite was also studied. Thermal stability of composites was increased by adding the GO. Copyright © 2013 John Wiley & Sons, Ltd.     

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

A 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 & Sons, Ltd.     

Mechanical properties of rigid polyurethane composites reinforced with surface treated ultrahigh molecular weight polyethylene fibers

The mechanical properties of ultrahigh molecular weight polyethylene (UHMWPE) fibers reinforced rigid polyurethane (PU) composites were studied, and the effects of the fiber surface treatment and the mass fraction were discussed. Chromic acid was used to treat the UHMWPE fibers, and polyurethane composites were prepared with 0.1 to 0.6 wt% as‐received and treated UHMWPE fibers. Attenuated total reflection Fourier transform infrared demonstrated that oxygen‐containing functional groups were efficiently grafted to the fiber surface. The mechanical performance tests of the UHMWPE fibers/PU composites were conducted, and the results revealed that the treated UHMWPE fibers/PU composites had better tensile, compression, and bending properties than as‐received UHMWPE fibers/PU composites. Thermal gravimetric analyzer showed that the thermal stability of the treated fiber composites were improved. The interface bonding of PU composites were investigated by scanning electron microscopy and dynamic mechanical analysis, and the results indicated that the surface modification of UHMWPE fiber could improve the interaction between fiber and PU, which played a positive role in mechanical properties of composites.     

Preparation and characterization of corn starch/soy protein biocomposite film reinforced with graphene and graphene oxide nanoplatelets

Corn starch (CS) and soy protein isolate (SPI), as inexpensive, abundant, and biodegradable materials, can chemically interact well with each other to produce biofilms. However, to overcome some of their physical and mechanical limitations, it is preferred to use their composite form, employing reinforcing materials. In this study, initially, graphene (G) and graphene oxide (GO) were synthesized by a green method. Then, to enhance the polymer blend final properties, the effects of adding G and GO in the range of 0.5 to 2 wt% on physical and mechanical properties of starch/protein blend were investigated. The results showed that the presence of 0.5‐wt% G and 2‐wt% GO significantly increased the modulus of starch/protein film from 252 to 578 and 449 MPa, respectively. In addition, the thermal stability of CS/SPI/GO (2 wt%) composite film was 50°C to 60°C more than that of the pure starch/protein film. On the other hand, G‐reinforced composite films tended to decline water diffusion compared with the pure polymer film. In addition, the composite film with 2‐wt% GO content had the lowest oxygen permeation rate (3.48 cm³ μm/m²d kpa) among the other composite films.     

Preparation and corrosion resistance of polyaniline and waterborne polyurethane composite coating film

Polyaniline (PANI) particles were synthesized using aniline (AN), dodecyl benzene sulfonic acid (DBSA), and ammonium persulfate (APS). The particles were analyzed using scanning electron microscope (SEM), X-ray diffraction (XRD), and fourier transform infrared spectroscopy (FTIR). A PANI/waterborne polyurethane composite material (PANI-WPU) was obtained by combining it with polyethylene glycol (PEG600), diphenylmethane diisocyanate (MDI), dimethylol propionic acid (DMPA), N-methyl pyrrolidone (NMP), and dibutyltin lauric acid (DBTDL). The structure was characterized by the FTIR spectrum. The mechanical characteristics of the coating film were evaluated with respect to the PANI content, as well as its water absorption, glossiness, electrochemical corrosion resistance, and acid and alkali resistance. The PANI/waterborne polyurethane film has a maximum tensile strength of 23 $\pm 1$ MPa, an elongation of 1012%, a pencil hardness of 5H, a flexibility of 2 mm, an impact resistance of 50 cm, the water absorption of 14.66%, and the glossiness of 99.9 $\pm 0.1$ at 60°. When the PANI content is 0.7%, the mechanical characteristics, glossiness, and anti-corrosion performance of the composite film improve. The corrosion inhibition efficiency of the aqueous polyurethane coating film with PANI can reach 99.74%, as shown by the examination of electrochemical polarization curves and impedance spectra. The tinplate is coated with a 0.7% PANI-WPU composite material and edge sealing. This coating provides excellent protection against acid and alkali resistance, as demonstrated by its ability to withstand immersion in 10% H₂SO₄ and 10% NaOH solution for 90 days without any paint peeling off.     

Physical characteristics and properties of waterborne polyurethane materials reinforced with silk fibroin powder

Degummed silk filament was pulverized with a home‐made machine to obtain silk fibroin (SF) powder, and the structure, morphology, and particle size of the SF powder were investigated. The individual spherical particles and aggregates with different morphology of silk fibroin coexisted in water. A waterborne polyurethane (WPU) aqueous dispersion was blended with the SF powder to prepare novel blended materials with improved physical properties. The average particle size and zeta potential of the WPU/SF aqueous dispersions were characterized. The result showed that the WPU/SF dispersion with higher SF content exhibited a less negative zeta potential and a larger average particle size. Furthermore, the effect of SF content on the morphology, miscibility, and mechanical properties of the resulting blended films was studied by scanning electron microscopy, wide‐angle X‐ray diffraction, dynamic mechanical thermal analysis, and tensile testing. The films showed an improved Young's modulus and tensile strength from 0.3 to 33.8 MPa, and 0.6 to 5.2 MPa, respectively, with the increasing of SF up to a content of 26 wt %. The negative charges in the periphery and the small particle size made a good effort on dispersing SF powder into the WPU matrix as small aggregates, and the SF powder led to the efficient strengthening of WPU materials. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 940–950, 2010     

Synthesis and properties of room temperature curable trimethoxysilane‐terminated polyurethane and their dispersions

The purpose of this research is to study the synthesis and characterization of stable aqueous dispersions of externally chain extended polyurethane/urea compositions terminated by hydrolyzable or hydrolyzed trialkoxysilane groups incorporated through secondary amino groups. These dispersions with excellent storage stability are substantially free from organic solvents which cure to water and solvent resistant, tough, scratch resistant, preferably light stable (non‐yellowing) silylated polyurethane (SPU) films. The films were characterized by FT‐IR, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), tensile strength and water contact angle measurements, nanoindentation, gel content, water and xylene swellability tests. The properties of the films were discussed and correlated in detail by changing length of soft segment, diisocyanates, NCO/OH ratio and chain extender, ethylenediamine (EDA). From the results, it was found that the particle size and viscosity are lower whereas the gel content and thermal stability are higher for SPUs. Modulus, hardness and tensile properties of SPU films are superior compared to EDA‐PU film. Higher water contact angle and residual weight percentage of SPU films confirm silylation of PU by [3‐(phenylamino)propyl]trimethoxysilane (PAPTMS). Increase in NCO/OH ratios consumes more quantity of PAPTMS which makes PU with superior mechanical properties. Higher PAPTMS content in SPU results in effective crosslinking of the functional silanol groups formed by hydrolysis reaction of trimethoxysilane groups. Overall, SPUs synthesized at 1.4 NCO/OH ratio using Poly‐(oxytetramethylene)glycol (PTMG)‐2000 and isophorone diisocyanate (or) toluene‐2,4‐diisocyanate have excellent properties compared to SPUs prepared using PTMG‐1000 and at 1.2 and 1.6 NCO/OH ratios. SPUs prepared at 1.6 NCO/OH ratio are brittle due to higher crosslinking density. In addition, the crosslinking density of the films can be modified through silane end‐group modification to produce SPUs with a wide range of physical properties. Copyright © 2007 John Wiley & Sons, Ltd.     

Effects of graphene nanosheets decorated by cerium stannate on the enhancement of flame retardancy and mechanical performances of flexible polyurethane foam composites

As one of the most used polyurethane, flexible polyurethane foam (FPUF) still confronted highly flammable problems. However, current flame retardant employed in FPUF deteriorated the other utilization performances, such as mechanical properties. In this work, cerium stannate decorated graphene nanosheets (GNS@Ce₂Sn₂O₇, GCSO) was prepared to fabricate flame retardant FPUF composites. Compared to pure FPUF, the tensile strength and average compression strength of FPUF composites accomplished 100 and 412% increase, respectively, while the average rebound was basically maintained. In contrast to pure FPUF, total heat release and total smoke production of FPUF composites displayed a 42.2 and 75.1% reduction, respectively. Furthermore, the released toxic gases (such as, CO₂, CO and NO_x) during combustion were greatly decreased. These results were due to the catalytic and barrier effect of GCSO promoting the formation a high-quality char residue with a compact, intact and dense morphology. Therefore, it provides a facile method to fabricate FPUF composites with advanced comprehensive performance for the furniture field.     

Morphology and properties of waterborne polyurethane/clay nanocomposites

Aqueous emulsion of polyurethane ionomers, based on poly(tetramethylene glycol) or poly(butylene adipate) as soft segment, isophorone diisocyanate as diisocyanate, 1,4-butandiol as chain extender, dimethyl propionic acid as potential ionic center, triethylene tetramine as crosslinker, and triethyl amine as neutralizer, were reinforced with organoclay to give nanocomposites. The particle size of emulsion was measured and the morphology of these nanocomposites was observed by transmission electron microscope, where the effectively intercalated or exfoliated organoclay was observed. The reinforcing effects of organoclay in mechanical properties of these nanocomposites were examined by dynamic mechanical and tensile tests, and the Shore A hardness was measured. Enhanced thermal and water resistance and marginal reduction in transparency of these nanocomposites were observed compared with pristine polymer.     

High strength,high stiffness and toughness,defect-tolerant waterborne polyurethane with healing and antibacterial abilities

The nature creates many biomaterials such as spider silk which exhibits a combination of stiffness, strength and toughness. However, most of synthetic unfilled materials suffer from a trade-off between toughness and stiffness. Inspired by the structure of spider silk but beyond it, we proposed a novel molecular design to achieve transparent unfilled waterborne polyurethane (WPU) with simultaneously enhanced stiffness (280.9 MPa), tensile strength (25.1 MPa) and toughness (140.0 MJ/m³) as well as good elasticity (710%). The designed WPU comprised homogeneous continuous phase (soft segments) and diverse H-bonds (hard segments) dispersed in it. The increase of rigid molecular chain content and H-bonds contributed to the high stiffness of WPU. Furthermore, the mismatch of stiffness between hard domains and soft segments might promote crack deflection and branching, which endowed the robust WPU with fracture energy of 81.16 kJ/m². The robust WPU film could be healed to recover most of its original mechanical properties (strength for 24.4 MPa and elongation for 610%) under heating. In addition, the WPU films demonstrated good antibacterial performance against Staphylococcus aureus and Escherichia coli after chlorination.     

Optical and mechanical properties of polyurethane/surface-modified nanocrystalline cellulose composites

in order to improve the optical and mechanical performances of waterborne polyurethane （WPU）, nanocrystalline cellulose （NCC）/WPU composites were synthesized in this study. NCC （prepared by acid hydrolysis of cotton fiber） was modified by （3-aminopropyl）triethoxysilane （APTES） to enhance its compatibility with WPU, and the surface-modified NCC was characterized by grafting ratio, crystallinity and contact angle （CA）. NCC/WPU composites were examined by scanning electron microscopy （SEM）, X-ray powder diffraction （XRD） and thermogravimetric analysis （TG）. The anti-yellowing property, specular gloss, pencil hardness, and abrasion resistance of NCC/WPU composites were investigated by the methods of Chinese National Standards GB/T 23999-2009, GB/T 9754-2007, GB/T 6739-2006 and GB/T 1768-2006, respectively. The results showed that the grafting ratio of NCC modified by 6% APTES was 36.01% and the crystallinity of modified NCC was decreased with the enhancement of APTES. CA of the modified NCC was decreased by 28.8% and the nanoparticles were homogeneously dispersed in the WPU matrix. The XRD patterns of the NCC/WPU composites were relatively steady, while the thermal stability of the composites was enhanced by 6.7% with 1.0 wt% modified NCC. Modified NCC affected the specular gloss of NCC/WPU composites more obviously than the anti-yellowing property. The pencil hardness of NCC/WPU composites was increased from 2H to 4H by addition of NCC and the abrasion resistance of the composites was enhanced significantly. In general, NCC/WPU composites showed significant improvements in the optical and mechanical performances.     

Hydrogen bonding,mechanical properties,and surface morphology of clay/waterborne polyurethane nanocomposites

A novel clay/waterborne polyurethane (WPU) nanocomposite was synthesized from polyurethane and saponite organoclay. The clay was organically modified with various swelling agents, the effect of which has been investigated. Hydrogen bonding between organic and inorganic materials was characterized with Fourier transform infrared (FTIR) spectroscopy. The results implied that hydrogen bonding increased when organoclay was added. Mechanical and wear property studies revealed that introducing clay into waterborne polyurethane will enhance the Young's modulus (from 56 to 126 MPa), the maximum stress (from 3.9 to 7.6 MPa), and the elongation at break (from 27.7 to 58.7%) of the nanocomposite by a factor of two, whereas the wear loss will be only one third of the neat waterborne polyurethane. Atomic force microscopy (AFM) was used to analyze the surface morphology of the nanocomposite. An AFM microphotograph showed that the surface of the clay/waterborne polyurethane nanocomposite was smoother when clay was added in waterborne polyurethane. The average roughness (R_a) decreased from 1.00 to 0.12. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1–12, 2005     

Properties of amphoteric polyurethane waterborne dispersions. I. Dependence on pH value in salt‐free media

The characteristics of amphoteric, amphiphilic polyurethanes (APUs) that depend on the pH value of the medium were studied. The dependence of the particle size and distribution as well as absorbency of the APU waterborne dispersions on the pH value of the medium were investigated by photon correlation spectroscopy and spectrophotometry methods, respectively. The results indicated that the pH dependence of the properties of APU aqueous dispersions can be characterized by two static balance states, a dynamic equilibrium state and two turbulent states with a changing pH of the medium. This can be attributed to the conformation changes of APU macromolecules as a result of the interaction between APU macromolecules affected by the ionization degree of the acid or base groups pendent on APU macromolecular chains. A reorganization process of APU macromolecules in its aqueous dispersion took place when the pH of the system was changed from basic to acidic or from acidic to basic. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 972–979, 2002