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 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 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 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.

Towards Solar-Driven Formation of Robust and Self-Healable Waterborne Polyurethane Containing Disulfide Bonds via in-situ Incorporation of 2D Titanium Carbide MXene

Waterborne polymers are vital for coating industry to reduce carbon emissions.However,formation of robust and self-healable films at ambient temperature remains a challenge owing to high energy cost of film formation process.This work reports a solar-driven film formation of waterborne polyurethanes(WPUs)containing disulfide bonds via in-situ incorporation of 2D titanium carbide(MXene)with ability to convert light to heat.Instead of directly mixed with WPUs,MXene is added to join the reaction with isocyanate-terminated pre-polymer before emulsification process.This approach not only prevents aggregation of MXene in water but stabilizes MXene against thermal degradation which is the key hurdle for mass production of MXene/WPU composites.More importantly,our results show that mechanical performance of WPU films under visible light(100 mW/cm^(2))is overwhelmingly competitive with that processed in oven.Furthermore,the existence of disulfide bonds in PU chains enables fast self-healing of micro-cracks under natural visible light which could vanish completely within 40 min.The fractured specimens were repaired under natural visible light for 2 h,and the self-healing efficiency of tensile strength and elongation at break reached over 94.00%.

Biosensors for waterborne virus detection: Challenges and strategies

Waterborne viruses that can be harmful to human health pose significant challenges globally,affecting health care systems and the economy.Identifying these waterborne pathogens is essential for preventing diseases and protecting public health.However,handling complex samples such as human and wastewater can be challenging due to their dynamic and complex composition and the ultralow concentration of target analytes.This review presents a comprehensive overview of the latest breakthroughs in waterborne virus biosensors.It begins by highlighting several promising strategies that enhance the sensing performance of optical and electrochemical biosensors in human samples.These strategies include optimizing bioreceptor selection,transduction elements,signal amplification,and integrated sensing systems.Furthermore,the insights gained from biosensing waterborne viruses in human samples are applied to improve biosensing in wastewater,with a particular focus on sampling and sample pretreatment due to the dispersion characteristics of waterborne viruses in wastewater.This review suggests that implementing a comprehensive system that integrates the entire waterborne virus detection process with high-accuracy analysis could enhance virus monitoring.These findings provide valuable insights for improving the effectiveness of waterborne virus detection,which could have significant implications for public health and environmental management.

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.

Prevention of Q235 Steel Corrosion using Waterborne Rust Inhibitor

Sorbitol,triethanolamine,sodium benzoate,boric acid,and sodium carbonate were mixed to prepare a waterborne rust inhibitor.A temperature and humidity accelerated corrosion test was applied to investigate the corrosion behaviour of waterborne rust inhibitor coated Q235 steel and original Q235 steel,which was carried out in a temperature and humidity test chamber(WSHW-1000)at a temperature of 80℃and humidity of 95%.Compared with the original Q235,waterborne rust inhibitor coated Q235 has better resistance to corrosion in hot and humid ambient conditions.Electrochemical impedance spectroscopy and potentiodynamic polarization were measured with a three-electrode cell in 3.5%NaCl aqueous solution on a CHI760E potentiostat/galvanostat.Molecular dynamics was simulated to verify the synergistic corrosion inhibitory mechanism of sodium carbonate and triethanolamine.The test shows that the prepared waterborne rust inhibitor can reduce the tendency of Q235 to corrosion and can also effectively reduce the corrosion rate.

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.

Analysis of College Students’ Test Scores Based on Two-Component Mixed Generalized Normal Distribution

In order to improve the fitting accuracy of college students’ test scores, this paper proposes two-component mixed generalized normal distribution, uses maximum likelihood estimation method and Expectation Conditional Maxinnization (ECM) algorithm to estimate parameters and conduct numerical simulation, and performs fitting analysis on the test scores of Linear Algebra and Advanced Mathematics of F University. The empirical results show that the two-component mixed generalized normal distribution is better than the commonly used two-component mixed normal distribution in fitting college students’ test data, and has good application value.

Comparison of Nanofibrillated Cellulose and Hydroxyethyl Cellulose in Improving the Storage Stability of Waterborne Coatings

Waterborne coatings often delaminate and settle during long-term storage,requiring the addition of thickeners.The effects of nanofibrillated cellulose(NFC)and the commonly used thickener,hydroxyethyl cellulose(HEC),on the storage stability of waterborne coatings were compared in this study.The morphology of NFC was characterized using infrared spectroscopy(FT-IR)and scanning electron microscopy(SEM).The rotational viscosity and rheological properties of the waterborne coatings with NFC and HEC were tested.Stationary settling experiments were also conducted at different temperatures to compare the difference of NFC and HEC on improving the storage stability of the waterborne coatings.The results showed that the waterborne coating with NFC exhibited pseudoplastic fluid characteristics;a small addition of NFC can achieve the same improvement effect on the storage stability of waterborne coatings as HEC.Further,the improvement effect of NFC was not affected by temperature.The waterborne coating with NFC still exhibited good storage stability at high temperatures,which was significantly superior to that of HEC.Therefore,NFC is a feasible agent for improving the prolonged storage stability and warming-induced delamination of waterborne coatings.

PROGRESS IN PHASE INVERSION EMULSIFICATION FOR EPOXY RESIN WATERBORNE DISPERSIONS

In this review, our recent work in phase inversion emulsification （PIE） for polymer （especially epoxy resin） waterborne dispersions is summarized. Based on experimental results about PIE process, the physical model is proposed which can guide the synthesis of the waterborne dispersions such as polymer/nanoparticle composite dispersion. In the presence of a latent curing catalyst, PIE can give a crosslinkable epoxy resin waterborne dispersion. The dispersions can form cured transparent coatings with some unique properties such as UV shielding. They are promising in functional coatings, waterborne resin matrices for composites, and sizing for high performance fibers.

INFLUENCE OF SILOXANE CO-SEGMENT LENGTH AND CONTENT OF WATERBORNE POLYSILOXANE-URETHANE COPOLYMERS ON THEIR WATER RESISTANCE,THERMAL STABILITY AND MECHANICAL PROPERTIES

A series of stable waterborne polysiloxaneurethane （WPSUR） dispersions were prepared using amino-terminated polydimethylsiloxane （NS）, dimethylolpropionic acid （DMPA）, castor oil, polypropylene glycol and toluene diisocyanate. Meanwhile, NS with different molecular weights was synthesized and used as the soft co-segment. Effects of types and contents of soft co-segments as well as chain extenders on the thermal degradation and stability for WPSUR films were examined. Results reveal that WPSUR films exhibit excellent water resistance and mechanical properties as compared with pure polyurethane （PU） films, and the NS soft co-segment possesses a remarkable effect on the second stage （stage Ⅱ）, while the content of the hard segment is propitious to the initial stage （stage Ⅰ）. Moreover, the highest temperature of stage Ⅱ （T2m） for WPSUR films using NS as soft co-segment is 413℃, approximately being 30℃ higher than that of those typical PUs using HDA and APDMS as the chain extenders, respectively.

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.

Waterborne Epoxy Resin Modified by AMPS

A stable epoxy emulsion was prepared with epoxy resin （EP） as raw material, 2-acrylamido-2- methyl-l-propanesulfonic acid （AMPS） as modifier and benzoyl peroxide as initiator. By criterion of yield of the copolymer AMPS-EP, water-solubility, change of the acid value and intrinsic viscosity [η] along with reaction time, the copolymerization course was deduced. It is found that during the process, AMPS takes part in both the grafting copolymerization with epoxy principal chain and the ring-opening polyaddition with epoxy group. It is also discovered that the yield of AMPS-EP and water dispersing varies with reaction time. When it reaches 1.5 h, AMPS-EP can obtain good water-solubility; but the water-solubility will go bad gradually if it exceeds 3.5 h.. R spectrum analysis indicates that partial epoxy group partially remains and the others create sulfonic ester.

PREPARATION OF WATERBORNE ULTRAFINE PARTICLES OF EPOXY RESIN BY PHASE INVERSION TECHNIQUE

Waterborne ultrafine particles of epoxy resin were prepared by phase inversion technique. The results of SEM revealed that the particles diameter was in the range of 50 to 100 nm and the effects on amount of water required at phase inversion point were also discussed.

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.

The PhoR/PhoP two-component system regulates fengycin production in Bacillus subtilis NCD-2 under low-phosphate conditions

Bacillus subtilis strain NCD-2 is an excellent biocontrol agent for plant soil-borne diseases, and the lipopeptide fengycin is one of the active antifungal compounds in strain NCD-2. The regulator PhoP and its sensor kinase PhoR compose a two-component system in B. subtilis. In this study, the phoR- and phoP-knockout mutants were constructed by in-frame deletion and the role of PhoR/PhoP on the production of fengycin was determined. Inactivation of phoR or phoP in B. subtilis decreased its inhibition ability against Botrytis cinerea growth in vitro compared to the strain NCD-2 wild type. The lipopeptides were extracted from strain NCD-2 wild type and its mutant strains by hydrochloric acid precipitate, and the lipopeptides from phoR-null mutant orphoP-null mutant almost lost the inhibition ability against B. cinerea growth compared to the lipopeptides from strain NCD-2 wild type. Fast protein liquid chromatography （FPLC） analysis of the lipopeptides showed that inactivation of phoR or phoP genes reduced the production of fengycin by strain NCD-2. The fengycin production abilities were compared for bacteria under low-phosphate medium （LPM） and high-phosphate medium （HPM）, respectively. Results indicated that the regulation of fengycin production by the PhoR/PhoP two-component system occurred in LPM but not in HPM. Reverse transcriptionaI-PCR confirmed that the fengycin synthetase gene fenC was positively regulated by phoP when cultured in LPM. All of these characteristics could be partially restored by complementation of intact phoR or phoP gene in the mutant. These data indicated that the PhoR/PhoP two-component system greatly regulated fengycin production and antifungal ability in B. subtilis NCD-2 mainly under low-phosphate conditions.

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.