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 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.展开更多
1,2-Dioxetane is a well-known chemiluminescent mechanophore allowing real-time monitoring of polymer chain scission,but usually suffers from fluorescence quenching in polar environments.Herein,a series of mechanochemi...1,2-Dioxetane is a well-known chemiluminescent mechanophore allowing real-time monitoring of polymer chain scission,but usually suffers from fluorescence quenching in polar environments.Herein,a series of mechanochemiluminescent waterborne polyurethanes/carbon dots composites(WPU-CDs)have been synthesized by incorporating fluorescent CDs to promote the energy transfer process in different environments.The resulting bulk WPUs,and in particular,their swollen films filled with a large amount of polar solvents(water and ionic liquid)emit intense mechanochemiluminescence.Thus force-induced covalent bond scission and stress distribution within these different WPU-CDs films can be sensitively visualized.Furthermore,the ionic liquid containing films exhibited both electrical and luminescent signal changes under stretching,which offer a new kind of force sensor responsive at a broad detecting strain range and for multi-mode strain analysis.This study is expected to stimulate new research endeavors in mechanistic insight on waterborne polyurethanes and the corresponding stretchable sensing devices.展开更多
To obtain an aqueous polymer system with good antibacterial properties, a series of gemini waterborne polyurethanes （GWPU） were designed and synthesized using isophorone diisocyanate, polyoxytetramethylene glycol, p...To obtain an aqueous polymer system with good antibacterial properties, a series of gemini waterborne polyurethanes （GWPU） were designed and synthesized using isophorone diisocyanate, polyoxytetramethylene glycol, poly（ethylene glycol）, L-lysine and a novel L-lysine-derivatized diamine containing gemini quaternary ammonium salt （EG12） without any other organic agent involved in the whole synthetic process. EG12 was first synthesized and characterized with proton nuclear mag- netic resonance spectra and mass spectra. The antibacterial activities of EG12 and GWPU were evaluated by quanti- fying the minimal inhibitory concentration. The results indicated that the gemini quaternary ammonium chain extender EG12 and GWPU showed excellent antibacterial activity against a broad spectrum of gram-positive and gram-negative bacteria. This work provides a new and facile approach to prepare novel antibacterial materials, which could be applied as coatings in various fields to prevent microbial contamination.展开更多
To better investigate the degradation and biocompatibility of waterborne biodegradable polyurethanes for tissue engineering, a series of new waterborne biodegradable polyurethanes （PEGPUs） with low degree of crossli...To better investigate the degradation and biocompatibility of waterborne biodegradable polyurethanes for tissue engineering, a series of new waterborne biodegradable polyurethanes （PEGPUs） with low degree of crosslinking was synthesized using IPDI, BDO and L-lysine as hard segments, PCL and PEG as soft segment. The bulk structures and properties of the prepared polyurethanes were characterized by Fourier transform infrared spectroscopy （FTIR）, differential scanning calorimetry （DSC）, tensile mechanical tests and water contact angle （WCA） measurements. The degree of microphase separation was slightly improved because of the lowered crosslinking degree of these PEGPUs in comparison with the high cross-linking degree samples, leading to good mechanical properties, as indicated by DSC and stress-strain data. Moreover, biodegradability of the polyurethanes was evaluated in phosphate buffer solutions （PBS） under different pH values and enzymatic solution at pH 7.4 through weight loss monitoring. The results suggested that the degradation of these PEGPUs was closely related to their bulk and surface properties. And the degradation products didn＇t show apparent inhibition effect against fibroblasts in vitro. These studies demonstrated that the waterborne biodegradable polyurethanes could find potential use in soft tissue engineering and tissue regeneration.展开更多
An environmentally friendly waterborne polyurethane(CWPU)emulsion was developed via a dual modification strategy by combining both the silane coupling agent KH-602 with renewable castor oil(CO)as a sustainable substit...An environmentally friendly waterborne polyurethane(CWPU)emulsion was developed via a dual modification strategy by combining both the silane coupling agent KH-602 with renewable castor oil(CO)as a sustainable substitute for petroleum-based polyols.The resulting materials were thoroughly characterized using Fourier-transform infrared spectroscopy(FTIR),thermogravimetric analysis(TGA),and differential scanning calorimetry(DSC).Furthermore,the influence of KH-602 content on the material properties was systematically investigated.The experimental results reveal that the incorporation of KH-602 significantly improves the thermal stability of the composite coating.As the KH-602 content increases,the tensile strength exhibits a gradual enhancement,while the elongation at break displays an initial increase followed by a subsequent decline.At an optimal KH-602 content of 3%,the coating demonstrates a balanced performance,achieving a tensile strength of 14.19 MPa and an elongation at break of 731.12%.These results suggest that the dual modification approach enhances mechanical and thermal properties while maintaining water resistance,making it suitable for sustainable coating applications.展开更多
As a coupling agent,(3-aminopropyl)triethoxysilane(APTES)was used to synthesize a series of silanized waterborne polyurethanes(Si-WPUs)through the acetone process.The Fourier transform infrared spectroscopy(FTIR)toget...As a coupling agent,(3-aminopropyl)triethoxysilane(APTES)was used to synthesize a series of silanized waterborne polyurethanes(Si-WPUs)through the acetone process.The Fourier transform infrared spectroscopy(FTIR)together with the X-ray photoelectron spectroscopy(XPS)was utilized to measure both elements and structures of these samples.The scanning electron microscope(SEM)results explained that APTES would be agglomerate on the surface of WPU films when the mass fraction of the agent concentration was more than 8%.Besides,the contact angle of water(CAW)can be improved from 56.5°to 90.0°by adjusting APTES concentration in Si-WPU.The decomposition temperature of films was also improved with the increase of APTES,and a significant increase could be seen in the glass temperature from 51.00℃to 85.74℃.展开更多
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 ac...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.展开更多
Suspended and waterborne polyurethane immobilized nitrifying bacteria have been adopted for evaluating the effects of environmental changes, such as temperature, dissolved oxygen （DO） concentration and pH, on nitrif...Suspended and waterborne polyurethane immobilized nitrifying bacteria have been adopted for evaluating the effects of environmental changes, such as temperature, dissolved oxygen （DO） concentration and pH, on nitrification characteristics under conditions of low ammonia concentrations. The results showed that nitrification was prone to complete with increasing pH, DO and temperature. Sensitivity analysis demonstrated the effects of temperature and pH on nitrification feature of suspended bacteria were slightly greater than those of immobilized nitrifying bacteria. Immobilized cells could achieve complete nitrification at low ammonia concentrations when DO was sufficient. Continuous experiments were carried out to discuss the removal of ammonia nitrogen from synthetic micropollute source water with the ammonia concentration of about 1mg/L using immobilized nitrifying bacteria pellets in an up-flow inner circulation reactor under different hydraulic retention times （HRT）. The continuous removal rate remains above 80% even under HRT 30 min. The results verified that the waterborne polyurethane immobilized nitrifying bacteria pellets had great potential applications for micro-pollution source water treatment.展开更多
The mixing soft-segment WPU （waterborne polyurethane） polymer electrolytes were synthesized by using PEO （poly（ethylene oxide）） and PDMS （polydimethylsiloxane） as the soft segments. These polymer electrolytes ...The mixing soft-segment WPU （waterborne polyurethane） polymer electrolytes were synthesized by using PEO （poly（ethylene oxide）） and PDMS （polydimethylsiloxane） as the soft segments. These polymer electrolytes exhibit good thermal and electrochemical stabilit）＇. The conductivity of the gel polymer electrolyte is 2.52 × 10^-3 S/cm at 25 ℃ with the LiTFSI/（DMC ＋ EC） content of 130%.展开更多
In this study, to improve hemocompatibility of biomedical materials, a waterborne polyurethane （WPU）haepafin release coating system （WPU/heparin） is fabricated via simply blending biodegradable WPU emulsions with ...In this study, to improve hemocompatibility of biomedical materials, a waterborne polyurethane （WPU）haepafin release coating system （WPU/heparin） is fabricated via simply blending biodegradable WPU emulsions with heparin aqueous solutions. The surface compositions and hydrophilicity of these WPU/heparin blend coatings are characterized by attenuated total reflectance infrared spectroscopy （ATR-FTIR） and water contact angle measurements. These WPU/heparin blend coatings show effectively controlled release of heparin, as determined by the toluidine blue method. Furthermore, the biocompatibility and anticoagulant activity of these blend coatings are evaluated based on the protein adsorption, platelet adhesion, activated partial thromboplastin time （APTT）, thrombin time （TT）, hemolysis, and cytotoxicity. The results indicate that better hemocompatibility and cytocompatilibity are obtained due to blending heparin into this waterborne polyurethane. Thus, the WPU/heparin blend coating system is expected to be valuable for various biomedical applications.展开更多
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 firs...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.展开更多
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 ...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.展开更多
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 att...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.展开更多
A novel waterborne stilbene-based polyurethane fluorescent brightener dispersion WPU-VBL was synthesized by incorporating chemically disodium 4,4＇-bis[（4-anilino-6-hydroxyethylamino-1,3,5-triazin-2-yl）amino]stilben...A novel waterborne stilbene-based polyurethane fluorescent brightener dispersion WPU-VBL was synthesized by incorporating chemically disodium 4,4＇-bis[（4-anilino-6-hydroxyethylamino-1,3,5-triazin-2-yl）amino]stilbene-2,2＇-disulphonate（VBL） into the polyurethane chain using isophorone diisocyanate,poly（propylene glycol） and 2,2-dimethylol propionic acid.The structure of WPU-VBL was confirmed by means of Fourier transform infrared spectroscopy.The UV-vis absorption analysis showed a hypsochromic shift of 16 nm when VBL was blocked into polyurethane chain.Number average molecular weight of 2.1×10~4, molecular weight distribution of 2.1 and average latex particle size of about 70 nm for WPU-VBL were determined based on the analysis of gel permeation chromatography and laser particle size analyzer.It was found that the fluorescence intensity of WPU-VBL was prominently enhanced because of the micro-circumstance of VBL and the fluorescence of WPU-VBL was very stable.展开更多
The rheological properties of two specific waterborne polyurethane （PU） paints were studied by both macrorheological and microrheological methods. During the macrorheological measurement on a rotary rheometer, evapo...The rheological properties of two specific waterborne polyurethane （PU） paints were studied by both macrorheological and microrheological methods. During the macrorheological measurement on a rotary rheometer, evaporation of solvent cannot be totally excluded, which has an influence on the reliability of rheological results. So, the linear oscillatory frequency sweep results （storage and loss modulus versus frequency） and steady shear results （viscosity versus shear rate） got from the rotary rheometer measurement are only used for qualitative analysis. As the evaporation of solvent can be neglected during microrheological measurements on a diffusing wave spectroscope （DWS）, the results of storage modulus （G3 and loss modulus （G＇~） versus frequency are more credible than the results obtained from the rotary rheometer measurement. Thus, the results of G＇ and G＂ versus frequency from DWS measurements are used for quantitative analysis in this work. The G＇ for both of the waterborne PU paints are larger than G＂ at low frequency and that is opposite at high frequency in the experimental angular frequency range. The values of modulus at same frequency and viscosity at low shear rate for the two PU paints have apparent difference, which determines the difference of their application.展开更多
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(MDE...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.展开更多
A series of nano silica/silicone modified waterborne polyurethane(WPU) have been synthesized from polytetramethylene glycol and isophorone diisocyanate, dihydroxymethyl propionic acid and triethylamine, ethylenediamin...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.展开更多
To impart polymers with high electrical conductivity and satisfactory electromagnetic interference shielding efficiency,it is crucial to efficiently construct interconnecting networks of conductive nanofillers in poly...To impart polymers with high electrical conductivity and satisfactory electromagnetic interference shielding efficiency,it is crucial to efficiently construct interconnecting networks of conductive nanofillers in polymer matrices.Herein,on the basis of the three-dimensional(3D)skeleton and volume-exclusion effect of silane-modified tetra-needle ZnO(ST-ZnO)whiskers and the high conductivity of two-dimensional MXene nanosheets,multifunctional MXene/ST-ZnO/waterborne polyurethane(MTW)nanocomposite films are fabricated by coating of MXene on ST-ZnO followed by compounding with waterborne polyurethane.The 3D four-needles of the whiskers facilitate the formation of an interconnecting network in the waterborne polyurethane matrix,while the coating of MXene efficiently makes the interconnecting network of the whiskers conductive at a low amount of the MXene.The resultant MTW ternary nanocomposite film exhibits not only a high electrical conductivity of 4.8×10^(4)S/m,but also an excellent electromagnetic interference shielding effectiveness of over 70 dB in the X-band at a low thickness of 100µm.In addition,the ternary film also exhibits outstanding Joule heating performances with an equilibrium temperature of 113℃at a low driving voltage of 3 V.The multifunctional nanocomposite films are promising for applications in portable and wearable electronics and flexible electromagnetic interference shielding devices.展开更多
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 waterb...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.展开更多
A technology to achieve stable and high ammonia nitrogen removal rates for corn distillery wastewater （ethanol fuel production） treatment has been designed.The characteristics of nitrifying bacteria entrapped in a w...A technology to achieve stable and high ammonia nitrogen removal rates for corn distillery wastewater （ethanol fuel production） treatment has been designed.The characteristics of nitrifying bacteria entrapped in a waterborne polyurethane （WPU） gel carrier were evaluated after acclimation.In the acclimation period,nitrification rates of WPU-immobilized nitrobacteria were monitored and polymerase chain reaction （PCR） was also carried out to investigate the change in ammonium-oxidizing bacteria.The results showed that the pellet nitrification rates increased from 21 to 228 mg-N/（L-pellet·hr） and the quantity of the ammonia oxidation bacteria increased substantially during the acclimation.A continuous ammonia removal experiment with the anaerobic pond effluent of a distillery wastewater system was conducted with immobilized nitrifying bacteria for 30 days using an 80 L airlift reactor with pellets at a fill ratio of 15% （V/V）.Under the conditions of 75 mg/L influent ammonia,hydraulic retention time （HRT） of 3.7-5.6 hr,and dissolved oxygen （DO） of 4 mg/L,the effluent ammonia concentration was lower than 10 mg/L and the ammonia removal efficiency was 90%.While the highest ammonia removal rate,162 mg-N/（L-pellet·hr）,was observed when the HRT was 1.3 hr.展开更多
基金the Consejo Nacional de Investigaciones Científicas y Técnicas(CONICET,Argentina)(PIP 20170100677)the Fondo para la Investigación Científica y Tecnológica(FONCYT)(PICT-2017-1318)the Universidad Nacional de Mar del Plata(UNMdP,15/G557,ING561/19)and to the Comisión de Investigaciones Científicas de la Provincia de Buenos Aires(CIC)and the Universidad Tecnológica Nacional(UTN)for their financial support.
文摘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.
基金financially supported by the National Natural Science Foundation of China(Nos.21905200,21975178 and 21734006)China Postdoctoral Science Foundation(No.2019M661006)。
文摘1,2-Dioxetane is a well-known chemiluminescent mechanophore allowing real-time monitoring of polymer chain scission,but usually suffers from fluorescence quenching in polar environments.Herein,a series of mechanochemiluminescent waterborne polyurethanes/carbon dots composites(WPU-CDs)have been synthesized by incorporating fluorescent CDs to promote the energy transfer process in different environments.The resulting bulk WPUs,and in particular,their swollen films filled with a large amount of polar solvents(water and ionic liquid)emit intense mechanochemiluminescence.Thus force-induced covalent bond scission and stress distribution within these different WPU-CDs films can be sensitively visualized.Furthermore,the ionic liquid containing films exhibited both electrical and luminescent signal changes under stretching,which offer a new kind of force sensor responsive at a broad detecting strain range and for multi-mode strain analysis.This study is expected to stimulate new research endeavors in mechanistic insight on waterborne polyurethanes and the corresponding stretchable sensing devices.
基金This work was supported by the National Natural Science Foundation of China （51173118, 51273124, 51273126 and 51121001） and the National Science Fund for Distinguished Young Scholars of China （51425305）. We thank Prof. Zhang HR （Southwest University for Nationalities, Sichuan） for help with an- tibacterial test.
文摘To obtain an aqueous polymer system with good antibacterial properties, a series of gemini waterborne polyurethanes （GWPU） were designed and synthesized using isophorone diisocyanate, polyoxytetramethylene glycol, poly（ethylene glycol）, L-lysine and a novel L-lysine-derivatized diamine containing gemini quaternary ammonium salt （EG12） without any other organic agent involved in the whole synthetic process. EG12 was first synthesized and characterized with proton nuclear mag- netic resonance spectra and mass spectra. The antibacterial activities of EG12 and GWPU were evaluated by quanti- fying the minimal inhibitory concentration. The results indicated that the gemini quaternary ammonium chain extender EG12 and GWPU showed excellent antibacterial activity against a broad spectrum of gram-positive and gram-negative bacteria. This work provides a new and facile approach to prepare novel antibacterial materials, which could be applied as coatings in various fields to prevent microbial contamination.
基金supported by the National Natural Science Foundation of China(Nos.51073104 and 51173118)the Changjiang Scholars and Innovative Research Teams in Universities(No.IRT1163)the Sichuan Provincial Science Fund for Distinguished Young Scholars(No.09ZQ026-024)
文摘To better investigate the degradation and biocompatibility of waterborne biodegradable polyurethanes for tissue engineering, a series of new waterborne biodegradable polyurethanes （PEGPUs） with low degree of crosslinking was synthesized using IPDI, BDO and L-lysine as hard segments, PCL and PEG as soft segment. The bulk structures and properties of the prepared polyurethanes were characterized by Fourier transform infrared spectroscopy （FTIR）, differential scanning calorimetry （DSC）, tensile mechanical tests and water contact angle （WCA） measurements. The degree of microphase separation was slightly improved because of the lowered crosslinking degree of these PEGPUs in comparison with the high cross-linking degree samples, leading to good mechanical properties, as indicated by DSC and stress-strain data. Moreover, biodegradability of the polyurethanes was evaluated in phosphate buffer solutions （PBS） under different pH values and enzymatic solution at pH 7.4 through weight loss monitoring. The results suggested that the degradation of these PEGPUs was closely related to their bulk and surface properties. And the degradation products didn＇t show apparent inhibition effect against fibroblasts in vitro. These studies demonstrated that the waterborne biodegradable polyurethanes could find potential use in soft tissue engineering and tissue regeneration.
基金Funded by the Basic Scientific Research of Liaoning Provincial Department of Education(No.LJ212410153030)。
文摘An environmentally friendly waterborne polyurethane(CWPU)emulsion was developed via a dual modification strategy by combining both the silane coupling agent KH-602 with renewable castor oil(CO)as a sustainable substitute for petroleum-based polyols.The resulting materials were thoroughly characterized using Fourier-transform infrared spectroscopy(FTIR),thermogravimetric analysis(TGA),and differential scanning calorimetry(DSC).Furthermore,the influence of KH-602 content on the material properties was systematically investigated.The experimental results reveal that the incorporation of KH-602 significantly improves the thermal stability of the composite coating.As the KH-602 content increases,the tensile strength exhibits a gradual enhancement,while the elongation at break displays an initial increase followed by a subsequent decline.At an optimal KH-602 content of 3%,the coating demonstrates a balanced performance,achieving a tensile strength of 14.19 MPa and an elongation at break of 731.12%.These results suggest that the dual modification approach enhances mechanical and thermal properties while maintaining water resistance,making it suitable for sustainable coating applications.
基金Shanghai Undergraduate Training Program on Innovation and Entrepreneurship Grant,China(No.cs1904006)。
文摘As a coupling agent,(3-aminopropyl)triethoxysilane(APTES)was used to synthesize a series of silanized waterborne polyurethanes(Si-WPUs)through the acetone process.The Fourier transform infrared spectroscopy(FTIR)together with the X-ray photoelectron spectroscopy(XPS)was utilized to measure both elements and structures of these samples.The scanning electron microscope(SEM)results explained that APTES would be agglomerate on the surface of WPU films when the mass fraction of the agent concentration was more than 8%.Besides,the contact angle of water(CAW)can be improved from 56.5°to 90.0°by adjusting APTES concentration in Si-WPU.The decomposition temperature of films was also improved with the increase of APTES,and a significant increase could be seen in the glass temperature from 51.00℃to 85.74℃.
文摘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.
文摘Suspended and waterborne polyurethane immobilized nitrifying bacteria have been adopted for evaluating the effects of environmental changes, such as temperature, dissolved oxygen （DO） concentration and pH, on nitrification characteristics under conditions of low ammonia concentrations. The results showed that nitrification was prone to complete with increasing pH, DO and temperature. Sensitivity analysis demonstrated the effects of temperature and pH on nitrification feature of suspended bacteria were slightly greater than those of immobilized nitrifying bacteria. Immobilized cells could achieve complete nitrification at low ammonia concentrations when DO was sufficient. Continuous experiments were carried out to discuss the removal of ammonia nitrogen from synthetic micropollute source water with the ammonia concentration of about 1mg/L using immobilized nitrifying bacteria pellets in an up-flow inner circulation reactor under different hydraulic retention times （HRT）. The continuous removal rate remains above 80% even under HRT 30 min. The results verified that the waterborne polyurethane immobilized nitrifying bacteria pellets had great potential applications for micro-pollution source water treatment.
基金supported by the National Key Program for Basic Research of China(No.2002CB211800 and 2009CB220100)the National 863 Program(No.2007AA03Z226).
文摘The mixing soft-segment WPU （waterborne polyurethane） polymer electrolytes were synthesized by using PEO （poly（ethylene oxide）） and PDMS （polydimethylsiloxane） as the soft segments. These polymer electrolytes exhibit good thermal and electrochemical stabilit）＇. The conductivity of the gel polymer electrolyte is 2.52 × 10^-3 S/cm at 25 ℃ with the LiTFSI/（DMC ＋ EC） content of 130%.
基金financially supported by the National Natural Science Foundation of China(Nos.51173118,51273124 and51273126)the National Science Fund for Distinguished Young Scholars of China(No.51425305)+1 种基金the Youth Science and Technology Innovation Team of Sichuan Province(No.2015TD0001)State Key Laboratory of Polymer Materials Engineering(No.sklpme2014-2-03)
文摘In this study, to improve hemocompatibility of biomedical materials, a waterborne polyurethane （WPU）haepafin release coating system （WPU/heparin） is fabricated via simply blending biodegradable WPU emulsions with heparin aqueous solutions. The surface compositions and hydrophilicity of these WPU/heparin blend coatings are characterized by attenuated total reflectance infrared spectroscopy （ATR-FTIR） and water contact angle measurements. These WPU/heparin blend coatings show effectively controlled release of heparin, as determined by the toluidine blue method. Furthermore, the biocompatibility and anticoagulant activity of these blend coatings are evaluated based on the protein adsorption, platelet adhesion, activated partial thromboplastin time （APTT）, thrombin time （TT）, hemolysis, and cytotoxicity. The results indicate that better hemocompatibility and cytocompatilibity are obtained due to blending heparin into this waterborne polyurethane. Thus, the WPU/heparin blend coating system is expected to be valuable for various biomedical applications.
基金Funded by the National High Technology Research and Development Program("863"Program)(No.2003AA305071)
文摘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.
基金financially supported by the National 863 Program(No.2007AA03Z226)the National Key Program for Basic Research of China(No.2002CB211800 and 2009CB220100).
文摘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.
基金support provided by the National Natural Science Foundation of China[Grant No.51802259]China Postdoctoral Science Foundation Funded Project[Grant No.2019M663785]+4 种基金the Natural Science Foundation of Shaanxi[Grant No.2019JQ-510]the Natural Science Basic Research Plan in Shaanxi Province of China[Grant No.2018JM5053],Xi’an and Xi’an Beilin District Programs for Science and Technology Plan[Grant No.201805037YD15CG21(18)and GX1913]the Promotion Program for Youth of Shaanxi University science and technology association[Grant No.20190415]Fund of Key laboratory of Processing and Quality Evaluation Technology of Green Plastics of China National Light Industry council[Grant No.PQETGP2019003]the Ph.D.Start-up fund project[Grant No.108-451118001]of Xi’an University of Technology.
文摘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.
基金Financial supports from the National Natural Science Foundation of China(No.51073144)Anhui Provincial Education Department(Nos.KJ2008B165 and KJ2010B039)
文摘A novel waterborne stilbene-based polyurethane fluorescent brightener dispersion WPU-VBL was synthesized by incorporating chemically disodium 4,4＇-bis[（4-anilino-6-hydroxyethylamino-1,3,5-triazin-2-yl）amino]stilbene-2,2＇-disulphonate（VBL） into the polyurethane chain using isophorone diisocyanate,poly（propylene glycol） and 2,2-dimethylol propionic acid.The structure of WPU-VBL was confirmed by means of Fourier transform infrared spectroscopy.The UV-vis absorption analysis showed a hypsochromic shift of 16 nm when VBL was blocked into polyurethane chain.Number average molecular weight of 2.1×10~4, molecular weight distribution of 2.1 and average latex particle size of about 70 nm for WPU-VBL were determined based on the analysis of gel permeation chromatography and laser particle size analyzer.It was found that the fluorescence intensity of WPU-VBL was prominently enhanced because of the micro-circumstance of VBL and the fluorescence of WPU-VBL was very stable.
基金financially supported by the National Natural Science Foundation of China(Nos.2127415251473168 an21234007)
文摘The rheological properties of two specific waterborne polyurethane （PU） paints were studied by both macrorheological and microrheological methods. During the macrorheological measurement on a rotary rheometer, evaporation of solvent cannot be totally excluded, which has an influence on the reliability of rheological results. So, the linear oscillatory frequency sweep results （storage and loss modulus versus frequency） and steady shear results （viscosity versus shear rate） got from the rotary rheometer measurement are only used for qualitative analysis. As the evaporation of solvent can be neglected during microrheological measurements on a diffusing wave spectroscope （DWS）, the results of storage modulus （G3 and loss modulus （G＇~） versus frequency are more credible than the results obtained from the rotary rheometer measurement. Thus, the results of G＇ and G＂ versus frequency from DWS measurements are used for quantitative analysis in this work. The G＇ for both of the waterborne PU paints are larger than G＂ at low frequency and that is opposite at high frequency in the experimental angular frequency range. The values of modulus at same frequency and viscosity at low shear rate for the two PU paints have apparent difference, which determines the difference of their application.
文摘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.
基金the financial support by the National Natural Science Foundation of China(No.20973022 and No.11472048)
文摘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.
基金the National Natural Science Foundation of China(Nos.51922020 and 52090034)the Fundamental Research Funds for the Central Universities(Nos.BHYC1707B and XK1802-2).
文摘To impart polymers with high electrical conductivity and satisfactory electromagnetic interference shielding efficiency,it is crucial to efficiently construct interconnecting networks of conductive nanofillers in polymer matrices.Herein,on the basis of the three-dimensional(3D)skeleton and volume-exclusion effect of silane-modified tetra-needle ZnO(ST-ZnO)whiskers and the high conductivity of two-dimensional MXene nanosheets,multifunctional MXene/ST-ZnO/waterborne polyurethane(MTW)nanocomposite films are fabricated by coating of MXene on ST-ZnO followed by compounding with waterborne polyurethane.The 3D four-needles of the whiskers facilitate the formation of an interconnecting network in the waterborne polyurethane matrix,while the coating of MXene efficiently makes the interconnecting network of the whiskers conductive at a low amount of the MXene.The resultant MTW ternary nanocomposite film exhibits not only a high electrical conductivity of 4.8×10^(4)S/m,but also an excellent electromagnetic interference shielding effectiveness of over 70 dB in the X-band at a low thickness of 100µm.In addition,the ternary film also exhibits outstanding Joule heating performances with an equilibrium temperature of 113℃at a low driving voltage of 3 V.The multifunctional nanocomposite films are promising for applications in portable and wearable electronics and flexible electromagnetic interference shielding devices.
基金supported by the National Natural Science Foundation of China(21704047,21801145)the Natural Science Foundation of Shandong Province(ZR2017BB078,ZR2021QE137)+1 种基金the Foundation(ZZ20190407)of State Key Laboratory of Biobased Material and Green Papermakingthe Major Scientific and Technological Innovation Projects of Shandong Province(2019JZZY020230)。
文摘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.
基金supported by the National Water Pollution Control and Management Technology Major Projects(No. 2008ZX07101-010-03)the National Natural Science Foundation of China (No. 50708058)+2 种基金the National High Technology Research and Development Program (863)of China (No. 2012AA062703)the Shanghai Municipal Science and Technology Commission Major Project (No.04DZ12030-2)the Shanghai Committee of Science and Technology (No.10231201800)
文摘A technology to achieve stable and high ammonia nitrogen removal rates for corn distillery wastewater （ethanol fuel production） treatment has been designed.The characteristics of nitrifying bacteria entrapped in a waterborne polyurethane （WPU） gel carrier were evaluated after acclimation.In the acclimation period,nitrification rates of WPU-immobilized nitrobacteria were monitored and polymerase chain reaction （PCR） was also carried out to investigate the change in ammonium-oxidizing bacteria.The results showed that the pellet nitrification rates increased from 21 to 228 mg-N/（L-pellet·hr） and the quantity of the ammonia oxidation bacteria increased substantially during the acclimation.A continuous ammonia removal experiment with the anaerobic pond effluent of a distillery wastewater system was conducted with immobilized nitrifying bacteria for 30 days using an 80 L airlift reactor with pellets at a fill ratio of 15% （V/V）.Under the conditions of 75 mg/L influent ammonia,hydraulic retention time （HRT） of 3.7-5.6 hr,and dissolved oxygen （DO） of 4 mg/L,the effluent ammonia concentration was lower than 10 mg/L and the ammonia removal efficiency was 90%.While the highest ammonia removal rate,162 mg-N/（L-pellet·hr）,was observed when the HRT was 1.3 hr.
