Synthesis and Characterization of Nonionic Waterborne Polyurethane and Application to Wool Fabric Finishing

A nonionic waterborne polyurethane(WPU) was synthesized by the self-emulsification method using polyether diol(N220),isophorone diisocyanate(IPDI),trimethylolpropane poly(ethylene glycol monomethyl ether)(N120),1,4-butanediol(BDO) and trimethylolpropane(TMP) as the main materials.The effects of the NCO/OH ratio on the emulsion and film properties of NWPU were explored.The experimental results show that the NWPU prepared at an NCO/OH ratio of 1.1 has good emulsion stability and easy film formation,and the resultant film was elastic,soft,and transparent.The sample was used for wool finishing and the application performance was evaluated.When the NWPU dosage reached 40 g·L^(-1),the fabric area felt shrinkage rate reduced from 8.97% to 4.75%,the pilling rating raised from grade 2-3 to grade 4,and the whiteness value only decreased by 3.87%.

Modification of Nano-α-Al2O3 and Its Influence on the Surface Properties of Waterborne Polyurethane Resin Composite Passivation Films

Silane coupling agent KH560 was used to modify the surface of nano-α-Al2O3 in ethanol-aqueous solution with different proportions. The particle size of nano-α-Al2O3 was determined by nano-particle size analyzer, and the effects of nano-α-Al2O3 content, ethanol-aqueous solution ratio and KH560 dosage on the dispersion and particle size of nano-α-Al2O3 were investigated. The material structure before and after modification was determined by Fourier transform infrared spectroscopy (FTIR). Aqueous polyurethane resin and inorganic components are combined with modified nano-α-Al2O3 dispersion to form chromium-free passivation solution. The solution is coated on the galvanized sheet, the adhesion and surface hardness are tested, the bonding strength of the coating and the surface hardness of the substrate are discussed. The corrosion resistance and surface morphology of the matrix were investigated by electrochemical test, neutral salt spray test and scanning electron microscope test. The chromium-free passivation film formed after the modification of nano-α-Al2O3 increases the surface hardness of galvanized sheet by about 85%. The corrosion resistance of the film is better than that of a single polyurethane film. The results show that the surface hardness and corrosion resistance of polyurethane resin composite passivation film are significantly improved by the introduction of nano-α-Al2O3.

Preparation and Characterization of Two-component Waterborne Polyurethane Comprised of Water-soluble Acrylic Resin and HDI Biuret

A two-component waterborne polyurethane(2K-WPU) was prepared by mixing water-soluble acrylic resin and hexamethylene diisocyanate biuret, and then diluted for phase inversion with water. Compared with water-soluble acrylic resin, the phase inversion of 2K-WPU occurs at lower water content. It is indicated by TEM that 2K-WPU parti-cles show a core-shell structure, in which HDI biuret is encapsulated by hydrophilic acrylic resin. 2K-WPU emulsion with HDI biuret has larger particle size and narrower distribution index, while for 2K-WPU emulsion with HDI iso-cyanurate, the latex not only has large particle size, but also has two-peak distribution. FTIR shows that the reaction be-tween HDI biuret and acrylic resin can complete in 12h. In addition, studies on effect of composition of acrylic resin on performance of 2K-WPU show that narrowing the polar difference between water-soluble acrylic resin and HDI biuret and improving the miscibility of two components are the key to prepare the transparent and high gloss films with high crosslinking density.

Preparation and Properties of Two-Component and Double-Crosslinking Waterborne Polyurethane-Acrylic Dispersions

In this paper, isophorone diisocyanate (IPDI), polyethylene glycol (PEG), dimethylolpropionic acid (DMPA) and internal crosslinking agent trimethylolpropane (TMP) were used to prepare waterborne polyurethane. And then double-crosslinked polyurethane-acrylic composite aqueous dispersion was prepared in which polyacrylate was adopted to modify waterborne polyurethane and some special external crosslinking agents were added including silicone and trifunctional aziridine. The influence of the amounts of internal and external crosslinking agents, emulsifier, initiator on the particle size, particle size distribution, viscosity, molecular weight, as well as water adsorption ratio were studied.

Preparation and Characterization of Cellulose Nanofibril-Waterborne Polyurethane Composite Films

To improve the performance of polyurethane films,small amounts of cellulose nanofibrils(CNF)were physically blended with a waterborne polyurethane(WPU)emulsion,and then CNF/WPU composite films were prepared by cast-coating and drying.The particle size of the emulsions and the chemical structure,micromorphology,thermal stability,mechanical properties,and water resistance of the composite films were characterized using a Malvern laser particle size analyzer,Fourier transform infrared spectroscopy(FT-IR),scanning electron microscopy(SEM),thermogravimetric analysis(TGA),an electronic strength machine,water contact angle analysis(WCA),and water absorption tests,respectively.The results showed that at a low CNF content of 0.3 wt%,the particle size of the WPU emulsion and chemical structure of the film did not change significantly.In addition,the tensile strength of the composite film increased by up to 108%compared to the neat WPU film,and the thermal stability and water resistance were slightly improved.The addition of CNF greatly enhanced the tensile strength while maintaining the other original properties of the WPU film,which may greatly improve the service life and tear resistance of commercial coatings in the future.

Preparation of waterborne polyurethane/β-cyclodextrin composite nanosponge by ion condensation method and its application in removing of dyes from wastewater

Currently,polymer nanosponges have received extensive attention.However,developing new synthetic techniques for novel nanosponges remains a challenge.Furthermore,to date,composite nanosponge adsorbents based on waterborne polyurethane(WPU)andβ-cyclodextrin(β-CD)have not been reported.Herein,a novel green method,ion condensation method,was developed in this study for the preparation of polymer nanosponge adsorbents for efficient removal of dyes from wastewater.Based on the principle of charge repulsion between nanoparticles to maintain emulsion stability,waterborne polyurethane/β-cyclodextrin composite nanosponges(WPU-x,y)were prepared by coagulating the emulsions synthesized from 2,2-dimethylolpropionic acid,polypropylene glycol and hexamethylene diisocyanate as raw materials in a mixture of hydrochloric acid and anhydrous ethanol.The structure and appearance of WPU-x,y were characterized by attenuated total reflectance Fourier transform infrared spectroscopy,thermal gravimetric analyzer,scanning electron microscope and mercury intrusion porosimetry.The adsorption capacity of WPU-x,y was tested by parameters such as cross-linking degree,β-CD dosage,contact time,initial dye concentration and p H value.The study found that WPU-4,4.62 had the best adsorption effect on methylene blue(MB),the maximum removal rate was 93.42%,and the maximum adsorption capacity was 136.03 mg·g^(-1).Moreover,the Sips isotherm and pseudo-second-order-model were suitable for MB adsorption.Therefore,this study provides some perspectives for the fabrication of nanosponge adsorbents.

High Water Resistance and Enhanced Mechanical Properties of Bio-Based Waterborne Polyurethane Enabled by in-situ Construction of Interpenetrating Polymer Network

In this study,acrylic acid was used as a neutralizer to prepare bio-based WPU with an interpenetrating polymer network structure by thermally induced free radical emulsion polymerization.The effects of the content of acrylic acid on the properties of the resulting waterborne polyurethane-poly(acrylic acid)(WPU-PAA)dispersion and the films were systematically investigated.The results showed that the cross-linking density of the interpenetrating network polymers was increased and the interlocking structure of the soft and hard phase dislocations in the molecular segments of the double networks was tailored with increasing the content of acrylic acid,leading to enhancement of the mechanical properties and water resistance of WPU-PAA films.Notably,with the increase in content of acrylic acid,the tensile strength,Young’s modulus,and toughness of the WPU-PAA-110 film increased by 3 times,and 8 times,and 2.4 times compared with WPU-PAA-80,respectively.The WPU-PAA-100 film showed the best water resistance,and the water absorption rate at 96 h was only 3.27%.This work provided a new design scheme for constructing bio-based WPU materials with excellent properties.

Preparation and Surface Properties of Silicon-Containing Waterborne Polyurethane Functionalized with Fluorine-Containing Acrylate and Micro-Nano Silica

In order to prepare hydrophobic waterborne polyurethane coatings with better performances, the silicon-containing waterborne polyurethane（SiWPU） with functional chain extender hydroxyethyl acrylate（HEA） was prepared first, and then a series of silicon＆fluorine-containing polyurethane/acrylate（FSiPUA） emulsions were obtained with flourine containing acrylic monomer by seed emulsion polymerization, introducing micro-nano SiO2 into FSiPUA emulsion to make the final hybrid emulsion. The properties of Si WPU, FSiPUA and SiO2/FSiPUA were investigated by fourier transform infrared spectra（FTIR）, transmission electron microscope（TEM）, Scanning Electron Microscope（SEM） and some other analytical methods. The results revealed that FSiPUA emulsion particles possessed composite core-shell structure and FSiPUA films with suitable ratio performed better than Si WPU films in hardness, water resistance and solvent resistance. The SiO2/FSiPUA films with micro-nano dual roughness structure showed a water contact angle of 136° with good resistance to acid and alkali.

Synthesis and characterization of mixing soft-segmented waterborne polyurethane polymer electrolyte with room temperature ionic liquid

Composite polymer electrolytes based on mixing soft-segment waterborne polyurethane （WPU） and 1-butyl-3-methylimidazolium bis[（trifluoromethyl）sulfonyl]imide （BMImTFSI） have been prepared and characterized. The addition of BMImTFSI results in an increase of the ionic conductivity. At high BMImTFSI concentration （BMImTFSI/WPU = 3 in weight ratio）, the ionic conductivity reaches 4.27 × 10^-3 S/cm at 30 ℃. These composite polymer electrolytes exhibit good thermal and electrochemical stability, which are high enough to be applied in lithium batteries.

Preparation and Characterization of Waterborne Polyurethane/Cellulose Nanocrystal Composite Membrane from Recycling Waste Paper

Cellulose plays a key role in abundant organic natural materials meeting the increasing demand for green and biocompatible products.The highly crystalline nanoscale component of cellulose nanocrystals has recently attracted great attention due to the versatile performance as filler or matrix in producing functional materials.In this work,we prepared the waterborne polyurethane via a prepolymer process,and obtained cellulose and cellulose nanocrystals from waste paper via a facile acid hydrolysis process.After that,the cellulose nanocrystals were assembled into film and mixed with polyurethane to prepare flexible polyurethane/cellulose nanocrystals composite membrane with different soaking time.The correlation between the bulk structure and applied properties including thermal resistance and mechanical property was investigated by using Fourier transform infrared spectroscopy(FTIR),X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),scanning electron microscopy(SEM),thermogravimetric analysis(TGA),differential scanning calorimetry(DSC)and folding test.The structure analysis indicates that cellulose nanocrystals prepared from used paper have a quality similar to that of commercial cellulose.Meanwhile,the cellulose nanocrystals have been mixed with polyurethane uniformly.Polyurethane can significantly benefit to the thermal resistance and mechanical property of the cellulose nanocrystals film.The polyurethane/cellulose nanocrystals composite membrane present good flexibility and may hold a significantly potential application as visual and flexible material.

Synthesis of Castor Oil-based Cationic Waterborne Polyurethane Emulsion and Its Application

Castor oil-based cationic waterborne polyurethane(CWPU)was synthesized by pre-polymer process using castor oil(CO),poly(adipic acid-1,4-succinate diol)(PBA),isophorone diisocyanate(IPDI),and N-methyldiethanolamine(MDEA).The influences of the content of CO and MDEA on comprehensive performance and finished fabric properties of cationic waterborne polyurethane was investigated,especially the antibacterial properties of finished fabric.The CWPU latex particle size and its distribution decrease as the content of CO increased from 0wt%to 16.8wt%,and increases afterwards.The CWPU films show much higher thermal stability than cationic waterborne polyurethane without CO.The surface of fabrics was characterized by scanning electron microscope(SEM).The finished fabric surface is much smoother.In addition,the finished fabric with CWPU emulsion has better antibacterial property against E.coli and S.aureus.When MDEA content is 8%,the antibacterial rates of the two kinds of bacteria are 77.3%and 82.2%,respectively.

Preparation and characterization of a mixing soft-segment waterborne polyurethane polymer electrolyte

混合软片断的 WPU (水运的聚氨酯) 聚合物电解质被使用 PEO 综合(poly (乙烯氧化物)) 并且 PDMS (polydimethylsiloxane ) 作为软片断。这些聚合物电解质展出好热、电气化学的稳定性。胶化聚合物电解质的传导性是 2.52 ×；在 25 ° 的 10 −3 S/cm；有 LiTFSI/( 直接数字控制 + EC ) 的 C 130% 的内容。

Synthesis and Characterizations of 1,4-butanediol( BDO )-Regulated Poly( ε-caprolactone)(PCL) Waterborne Polyurethane with Controlled Biodegradability for Medical Applications

Waterborne polyurethane(WBPU)with controlled biodegradability and biocompatibility was synthesized by using poly(ε-caprolactone)(PCL)as the polyglycol,isophorone diisocyanate(IPDI)as the isocyanate,2,2-bishydroxymethylbutyric acid(DMPA)as the chain extender and 1,4-butanediol(BDO)as the hard-segment regulating agent.We found that BDO content significantlyinfluencedmechanicalproperties,degradable performances and cyto-biocompatibility of PCL-WBPUs.Increasing the BDO content in PCL-WBPU enhanced its tensile strength and decreases strain.Enzymolysis and hydrolysis properties were also regulated by BDO content,but with different mechanisms.Cytobiocompatibility was evaluated with ATDC5 cells.The results show that the biodegradability of PCL-WBPU is significantly determined by BDO content,which exerts a serious influence on its polymer structure,leading to resultant degradable properties.

Plant Oil-Based Waterborne Polyurethanes: A Brief Review

The increasing pressure from consumers and policy makers to reduce the use of synthetic polymers,whose production contributes to the depletion of non-renewable resources and are usually non-biodegradable,has prompted the efforts to find suitable bio-based sources for the production of polymers.Vegetable oils have been a frequently spotted in this search because they are versatile,highly available and a low cost liquid biosource,which can be used in the synthesis of a wide plethora of different polymers and reactive monomers.Following the same idea of reducing the environmental stress,the traditional polyurethanes that are soluble in organic solvents have been targeted for replacement,particularly in applications such as adhesives and coatings,in which the solvent is released to the atmosphere increasing the air pollution.Instead,waterborne polyurethanes(WBPU),which are polyurethane dispersions(PUD)prepared in aqueous media,release benign water to the atmosphere during use as supported or self-standing films for different applications.In this brief review,the contributions to the development of WBPUs based on vegetable oils are discussed,focusing mainly on the contributions of the last decade.The synthesis of ionic and nonionic PUDs,their characterization and the properties of the resulting dried materials,as well as derived composite materials are considered.

Preparation of Photochromic Waterborne Polyurethane Films:Effect of Spiropyran Concentration on Photochromic Properties

Incorporation of photochromic compounds to the polymer through chemical bonding will result in an enhancement of photoactivity and stabilization of optical properties.Here,spiropyran(SP)was introduced into polyurethane(PU)through semi-continuous emulsion copolymerization to get waterborne polyurethane dispersion(SPU).Studies on photochromic properties by UV-vis technique demonstrated the absorption intensity increased with the increasing of SP concentration and the colorless film turned to purple under UV irradiation.The kinetics for ring-opening and ring-closing reaction against SP were both first order,but the rate constants decreased with the increasing of SP concentration.The prepared SPU films showed reasonable photostability and photoreversibility according to the convenient test methods under UV-vis irradiation.Temperature dependence studies demonstrated that the photobleaching rate increased at higher temperatures with the same SP concentration.The chemical combination between SP and isocyanate(NCO)end group of polyurethane was confirmed through swelling experiments.Morphology studies were conducted by scanning electron microscope(SEM)micrographs and showed good compatibility between SP and PU.

Synthesis of Waterborne Polyurethane Modified by Nano-SiO_2 Silicone and Properties of the WPU Coated RDX

A series of nano silica/silicone modified waterborne polyurethane(WPU) have been synthesized from polytetramethylene glycol and isophorone diisocyanate, dihydroxymethyl propionic acid and triethylamine, ethylenediamine, trimethylolpropane, nano-SiO2 and the silane coupling agent KH550. The effect of the dosage of nano-SiO2 on the WPU-Si membrane and the coated RDX(cyclotrimethylenetrinitramine) particles have been studied in terms of their surface properties, mechanical properties, and thermal stability. The results showed that with the increase of Si content, the stability of the emulsion reduced gradually. The material with more Si content displayed an increased thermodynamic stability, an increased high temperature resistance, an increased tensile strength and a decreased elongation at break. With the increase of Si content, the surface tension of the material decreased, the bibulous rate reduced, and the contact angle increased gradually, so that the surface tension of the polyurethane and RDX are close to each other which could improve the performance of coating.

Preparation and Application of Anionic and Cationic Waterborne Polyurethanes and Graphene-Cellulose Nanocrystal as an Antistatic Agent for Cashmere

The main purpose of this research work is to improve anti-static properties of Cashmere fabric by introducing application comprising anti-static agent by foaming which was made with cationic waterborne polyurethane and graphene-CNC. Cashmere fabric was cut into 10 pieces of sample cloth of 5 cm * 5 cm size, washed with acetone solution, and then dried in an oven at 60℃. Three forms of waterborne polyurethanes such as two forms of Cationic waterborne polyurethane (CWPU) and a form of Anionic waterborne polyurethane (AWPU) were synthesized. Cellulose nanocrystalline (CNC)/graphite powder solution with the ratio of 0.5/1, 1/1, 2/1 was prepared by ultrasonic probe stripping method, and the concentration of graphite powder was ensured to be 1 mg/ml. The fabric was treated with anionic and cationic WPUs foaming solution until the weight gain reached 2.5 - 3.5 wt%. After drying, the elastic cloth was foamed with graphene solution until the graphite content of the cloth was close to 10%, 20%, 40%, 60% respectively, and then dried for reserving. Characterization properties of pure graphite powder, pure CNC and graphene solution with different proportions of three components were tested by Fourier transform infrared spectrometer (FTIR), X-ray diffraction (XRD), Thermalgravitimetric analysis (TGA) and scanning electron microscopy (SEM). Take the original cloth, only WPU treated cloth and four clothes with different graphite content for the fabric performance test.

Waterborne Polyurethane from Polycaprolactone and Tetramethylxylene Diisocyanate: Synthesis by Varying NCO/OH Ratio and Its Characterization as Wood Coatings

Environmentally friendly, polyacrylic-based polyurethane dispersion (PUD) was synthesised using various molar ratios of polycaprolactone, dimethylolpropionic acid and tetramethyl xylene diisocyanate. Synthesis was carried out in flowing nitrogen atmosphere. The PUD’s preparations are free of NMP (n-methyl pyrrolidone), a toxic processing solvent generally used during the preparation of PUD’s. The performance of the synthesised polyurethane dispersions with varying NCO/OH molar ratio was tested on wood surface. The physical, chemical, thermal and mechanical properties such as viscosity, particle size, chemical resistance, thermal stability and taber abrasion of applied polyurethane dispersion were carried out as a function of NCO/OH molar ratio. The PUD’s preparation with NCO/OH ratio of 1.4 or 1.6 showed better performance as a wood finish and the results are described in the present study.

Robust Waterborne Polyurethane/Wool Keratin/Silk Sericin Freeze-Drying Composite Membrane for Heavy Metal Ions Adsorption

Wool keratin(WK)and silk sericin(SS)have the ability to interact with metal ions.In order to take advantage of this potential,a novel environmentally friendly waterborne polyurethane(WPU)/WK/SS membrane named as WPU&WK&SS membrane with crosslinked structure was constructed by freeze-drying via self-assembly style.Surface morphology and chemical structure characterization were investigated by scanning electron microscopy(SEM)and Fourier transform infrared spectroscopy(FT-IR).In addition,the adsorption experiments of Cu2+and Cr6+were performed to evaluate the adsorption of WPU&WK&SS membrane,including adsorption kinetics,adsorption isotherm models and various factors affecting adsorption.Further investigation indicates that the maximum adsorption capacity of Cu2+and Cr6+can reach 54.21 mg·g-1and 85.21 mg·g-1,respectively,which are higher than most of the reported adsorbents.Through adsorption kinetics and thermodynamic analysis,it is find that the pseudo-second-order kinetic equation and the Langmuir adsorption isotherm model are more suitable for the static adsorption of Cu2+and Cr6+by WPU&WK&SS membrane.

Synthesizing Self-Crosslinking Waterborne Polyurethane-Silanol Dispersion for Waterproofing Application

Polyurethane dispersions (PUD) have diversified into a myriad of applications over the years. This has led to extensive research on both industrial and laboratory fronts as polyurethane dispersions provide liberty to interplay at the molecular level to diversify the properties of the product which has also led to the development of eco-friendly waterborne dispersions. Yet, waterborne PUDs are limited in their mechanical and physical properties as compared to solvent-based products. The incorporation of crosslinkers in the PUD further bolsters these properties thus improving water and solvent resistance. The incorporation of silanols increases solvent resistance and adhesion of the resultant PUD. In this work, a post crosslinking system based on the ketone-hydrazine mechanism was incorporated into the PUD thus providing the required structural reinforcement for construction application. The targeted application for this work is the use of PUDs for waterproofing.