Properties of waterborne polyurethane (WBPU) coatings: Effect of alkyl chain length of tertiary amines of carboxylic acid salt groups

Waterborne polyurethane (WBPU) dispersions were prepared via a pre-polymer process using 4,4-dicyclohexylmethane diisocyanate (H₁₂MDI), poly(tetramethyleneoxideglycol) (PTMG), 2,2-dimethylol propionic acid (DMPA), ethylene diamine (EDA), and tertiary amines (TAs) with varying amounts of DMPA and TAs. Three TAs with different alkyl chain lengths were used to neutralize the DMPA carboxylic group: N,N-dimethylbutylamine (DMBA, C4), N,N-dimethylhexylamine (DMHA, C6), and N,N-dimethyloctylamine (DMOA, C8). The structures of the synthesized WBPUs were determined via FT-IR and ¹H NMR spectroscopic techniques. The effects of DMPA and TA content and the TA alkyl chain length on stability of dispersions and properties such as water swelling (%), glass transition temperature (T _g ), tensile strength, binding energy and adhesive strength were investigated. The initial adhesive strength of the intact coatings increased with increasing DMPA and TA content and increasing alkyl chain length of TA. However, after immersion of the coatings in water, the adhesive strength decreased. The maximum adhesive strength under water was observed at a DMPA content of 20.20 mol% with 5.30 wt% DMOA, which has the longest alkyl chain.     

Preparation and properties of waterborne polyurethanes based on triblock glycol (CL)4.5-PTMG-(CL)4.5 for water vapor permeable coatings: Effect of soft segment content

A series of waterborne polyurethanes (WBPU) were prepared from 4,4-dicyclohexylmethane diisocyanate (H₁₂MDI), 2,2-bis(hydroxylmethyl) propionic acid (DMPA), ethylenediamine (EDA), triethylamine (TEA), and triblock glycol [TBG, (ε-caprolactone)_4.5-poly(tetramethylene ether) glycol (MW=2000)-(ε-caprolactone)_4.5: (CL)_4.5-PTMG-(CL)_4.5, MW=3000] as a soft segment. Two melting peaks of TBG at about 14°C and 38°C were observed indicating the presence of two different crystalline domains composed of CL and PTMG dominant component. The effect of soft segment content (60–75 wt%) on the colloidal properties of dispersion, and thermal and mechanical properties of WBPU films, the water vapor permeability (WVP) and water resistance (WR) of WBPU-coated Nylon fabrics, and the adhesive strength of WBPU-coated layer and Nylon fabrics was investigated. As soft segment contents increased, the water vapor permeability of WBPU-coated Nylon fabrics increased from 3615 to 4502 g/m²day, however, the water resistances decreased from 1300 to 500 mmH₂O.     

利用大豆分离蛋白制备胶粘剂

为了改善大豆胶黏剂的耐水胶合强度,采用表面活性剂θ改性大豆分离蛋白(SPI)制备胶粘剂,研究了配方及热压温度对大豆胶的胶合性能的影响,利用示差扫描量热仪(DSC)和傅里叶红外光谱(FTIR)技术分别分析了大豆胶的热学性能和结构变化.结果表明:当SPI/水(质量比)为1/10、0的添加量为SPI的0.5wt%、热压温度为160℃时,胶粘剂表现出最佳的胶合强度;大豆胶胶合过程中主要的热反应在160℃以下完成;经表面活性剂θ处理后,胶粘剂结构中的O-H和N-H键减少,大豆基胶黏剂的耐水胶合强度得到明显改善.     

甲醇联合改性大豆蛋白胶黏剂的研究

以甲醇、十二烷基磺酸钠、尿素为原料,研究了它们对大豆分离蛋白改性后胶黏性的改观作用。结果表明:随着甲醇含量的增加胶合强度先增后减,当甲醇含量占总体质量分数15%时胶合强度最好。取该条件下的大豆蛋白胶黏剂进行有关反应次序的对比试验。研究表明其部分干态胶合强度略有下降,湿态胶合强度有提升,且反应次序为SDS、甲醇、尿素所得的胶黏剂胶合强度达到最优。DSC、SEM图像和IR图像分析结果说明经此方法改性后的蛋白质展现出更多的二级结构从而大幅度的提升了其胶粘性,与此同时改性后的大豆蛋白玻璃化转化温度降低,从而降低了热压温度,说明经甲醇联合改性后的大豆蛋白胶黏剂不但能更加适应规模化的工业生产还可以节约资源。     

Effect of Urea/NaOH aqueous system on morphology and properties of cotton fabric

This paper was focused on comparing the effect of urea/NaOH aqueous system with that of single urea or NaOH treating system on cotton fabric morphology and properties. Optical microscopy (OM), scanning electron micrograph (SEM), Fourier transform infrared spectroscopy (FT-IR), and wide X-ray diffraction (WAXD) were used to study cotton fabric morphology and properties before and after treatment by urea/NaOH, single urea, and single NaOH treating systems. Results showed that the cotton fabric treated by urea/NaOH aqueous system had better dyeability than the samples untreated and treated by single urea or single NaOH treating systems. Obvious differences were observed in appearance and morphology of cotton fabrics before and after treatment by urea/NaOH aqueous system. The composition and the structure of urea/NaOH treated cotton fiber had no distinct changes, only except the reduced hydrogen bonding between cellulosic macromolecules. Tensile strength and elongation at break of cotton fabric showed a slight decrease after treatment by urea/NaOH system. In addition, shrinkage of area and weight reduction of urea/NaOH treated samples were higher than those of the samples untreated and treated by single urea or single NaOH treating system.     

环氧树脂改性大豆基木材胶粘剂的制备与表征

以表面活性剂AD改性大豆分离蛋白(SPI),然后与马来酸酐(MA)接枝后,再与环氧树脂(EPR)共混制备胶粘剂,采用L9(34)正交试验设计,探讨SPI、AD、MA及EPR用量对胶粘剂胶合性能的影响,并采用红外光谱及示差扫描量热仪探讨了SPI胶粘剂的胶粘机理。结果表明:最优工艺条件为每150 g溶剂水中,SPI用量15 g、AD用量为SPI的2.5wt%、MA1.5 g、EPR15 g;红外光谱和热性能分析表明SPI和EPR之间发生了化学反应。     

Eco-Friendly Extraction,Structure, and Gel Properties of ι-Carrageenan Extracted Using Ca(OH)2

An eco-friendly method for ι-carrageenan extraction from seaweed Eucheuma denticulatum through boiling and using a low concentration of Ca(OH)₂ is reported. Compared to the traditional method of ι-carrageenan extraction using NaOH, the reported method using Ca(OH)₂ had the advantages of using 93.3% less alkali and 86.8% less water, having a 25.0% shorter total extraction time, a 17.6% higher yield, and a 43.3% higher gel strength of the product. In addition, we evaluated the gel properties and structures of ι-carrageenan products extracted by Ca(OH)₂ (Ca-IC) and NaOH (Na-IC). The Fourier transform infrared spectroscopy results showed that the structures of Ca-IC and Na-IC did not change remarkably. The results of the thermogravimetric analysis and differential scanning calorimetry showed that Ca-IC had the same thermal stability as Na-IC. The results of the textural analysis showed that Ca-IC had a higher hardness and better chewiness compared to Na-IC. Rheological results indicated that Ca-IC and Na-IC exhibited shear-thinning and non-Newtonian fluid properties, whereas the viscosity of Ca-IC was less than that of Na-IC. In conclusion, this new method of ι-carrageenan extraction using Ca-IC is markedly better and yields higher quality carrageenan than the conventional method of using Na-IC.     

盐胁迫下钾吸收途径的抑制对小麦叶片K~+、Na~+含量的影响

为研究盐胁迫下小麦维持钾、钠平衡的生理机制,以耐盐小麦沧麦6005和盐敏感小麦矮抗58为材料,利用TEA、NEM、Ba(NO_3)_2三种药物分别抑制钾离子通道、钾载体及非选择性阳离子通道,测定正常及盐胁迫下小麦叶片K~+、Na~+含量,比较耐盐性不同的小麦品种在K~+、Na~+吸收中的差异。结果显示,盐胁迫下,沧麦6005和矮抗58叶片K~+含量下降,Na~+含量增加;沧麦6005叶片Na~+含量低于矮抗58,K~+/Na~+比值高于矮抗58。正常条件下,NEM、TEA处理均可降低沧麦6005和矮抗58叶片K~+含量,NEM处理较TEA处理效果更为明显;TEA处理显著降低了盐胁迫下矮抗58叶片K~+含量,而NEM处理则明显降低了盐胁迫下沧麦6005的叶片K~+含量;TEA、NEM、Ba(NO_3)_2处理降低了盐胁迫下矮抗58叶片Na~+含量,仅NEM处理降低了沧麦6005叶片Na~+含量。综上所述,正常条件下,钾载体是小麦K~+吸收的主要方式;盐胁迫下,耐盐品种和盐敏感品种K~+吸收途径不同,耐盐品种的NSCCs和钾离子通道具有更强的"拒钠"能力。     

Wet grinding and microfluidization of wheat bran preparations: Improvement of dispersion stability by structural disintegration

The enrichment of liquid food matrix with wheat bran has not yet been explored. This study investigated the impact of disintegrating wheat bran preparations on their stability at high moisture content. Three wheat bran preparations – standard bran, peeled bran and aleurone rich fraction – were modified by dry grinding, enzymatic degradation, wet grinding and microfluidization. The sedimentation of processed preparations was evaluated in water solution and related to their physical structure, solubilized compounds and suspension viscosity. In dry ground preparations mixed in water (5% w/w), most of the particles sedimented already in 5 min. Wet grinding disintegrated the physical structure of bran preparations (d₅₀ = 10–16 μm), causing improvement of particle stability due to reduction of gravitational sedimentation. Enzymatic treatment with xylanase efficiently increased the total solubility of the bran preparations (from 18–24% to 40–50%), but the higher solubility was not related to the better stability of particles. Microfluidization of peeled bran and aleurone increased the viscosity and stability of dispersions. The higher viscosity of the microfluidized dispersions was likely correlated with the better homogenisation of the particles, and also with the modified microstructure of treated bran preparations. Disintegrated wheat bran preparations showed high potential for beverage applications.     

A study of physical modification on grey cotton by laser irradiation

The surface morphology of the CO₂ laser treated grey cotton fabrics was studied which showed a characteristics sponge-like structure on cotton fibres after treating with CO₂ laser irradiation. The laser treatment parameters ranging from 100 to 150 pixel time and 40 to 70 dot per inch (dpi) were irradiated on the grey cotton fabrics directly and the degree of physical modifications, such as surface morphology, wettability and fabric strength, were changed accordingly with various laser treatment parameters. The surface morphology, wettability and tensile strength of cotton fibre treating with laser were evaluated using different instruments, such as Scanning Electron Microscope (SEM), contact angle meter and tensile strength machine. In spite of creating a sponge-like structure on fibre surface after treating with laser, the wettability of the samples was highly improved but the tensile strength was decreased.     

Comparision of the properties of UV-cured polyurethane acrylates containing different diisocyanates and low molecular weight diols

UV-curable polyurethane acrylate prepolymers were prepared from diisocyanates [isophorone diisocyanate (IPDI), 2,4-toluene diisocyanate (TDI), or 4,4′-dicyclohexylmethane diisocyanate (H₁₂MDI)], diols [ethylene glycol (EG), 1,4-butane diol (BD), or 1,6-hexane diol (HD)], polypropylene glycol as a polyol. UV-curable mixtures were formulated from the prepolymer (90 wt%), reactive diluent monomer trimethylol propane triacrylate (10 wt%), and photoinitiator 1-hydroxycyclohexyl ketone (3 wt% based on prepolymer/diluent). The effects of different diisocyanates/low molecular weigh diol on the dynamic mechanical thermal properties and elastic recovery of UV-cured polyurethane acrylate films were examined. The tensile storage modulus increased a little in the order of EG>BD>HD at the same diisocyanate. Two loss modulus peaks for all samples are observed owing to the glass transition of soft segments (T _gs ) and the glass transition temperature of hard segments (T _gh ). For the same diisocyanate,T _gs decreased, however,T _gh increased, in the order of HD>BD>EG. The elastic recovery also increased in the order of HD>BD>EG at the same diisocyanate. In case of same diols,T _gh increased in the order of H₁₂MDI>TDI>IPDI significantly. The ultimate elongation and elastic recovery increased in the order of TDI>IPDI>H₁₂MDI at the same diol.     

Polyester modification through synthesis of copper nanoparticles in presence of triethanolamine optimized with response surface methodology

In this paper, polyester fabric was modified through synthesis and fabrication of Cu/Cu₂O nanoparticles using a facile and cost-effective method at boil by chemical reduction through exhaustion route. Triethanolamine (TEA) was used for aminolysis of polyester fabric and pH adjusting, copper sulfate (CuSO₄) as metal salt, sodium hypophosphite (SHP) as reducing agent and polyvinylpyrrolidone (PVP) as stabilizer. A response surface methodology was also employed to optimize the reaction conditions and study the effects of SHP, PVP and TEA concentrations in the processing. The images of field-emission scanning electron microscopy (FESEM), the patterns of energy-dispersive spectroscopy (EDX) and X-ray diffraction (XRD) patterns confirmed successfully synthesis of Cu and Cu₂O nanoparticles on the polyester fabric. Further, the thermal behavior of the untreated and treated fabrics was studied by using thermogravimetric analysis (TGA) and differential scanning colorimetry (DSC). The treated fabrics indicated good properties regarding wettability and flame-retardant along with high tensile strength.     

Condensed tannins extraction from grape pomace: Characterization and utilization as wood adhesives for wood particleboard

The extraction of condensed tannins from grape pomace was examined using water medium in the presence of NaOH, Na₂CO₃, NaHCO₃ eventually in the presence of Na₂SO₃. The tannin fractions reactivity towards formaldehyde was studied by gel time analysis and thermomechanical analysis in bending and it was demonstrated that despite of their lower phenolic contents, some of these extracts displayed promising properties for adhesive applications. A resin formulation in which the total content of tannin is 75% of the total resin solids content gave good results and was employed for the elaboration of the first grape pomace based-wood particleboard which passed relevant international standard specifications for interior-grade panels.     

Fractional isolation and partial characterization of non-starch polysaccharides and lignin from sago pith

Sago pith non-starch polysaccharides were fractionated into cold water solubles (2.6%), hot water solubles (0.8%), dimethylsulfoxide solubles (0.8%), 5% NaOH soluble hemicelluloses (1.2%), 24% KOH–2% H₃BO₃ soluble hemicelluloses (0.6%), and cellulose (5.3%). Lignin was measured by 5% NaOH extraction (0.6%) and sodium chlorite oxidation (4.2%). Glucose and rhamnose were the major sugars in cold and hot water soluble non-starch polysaccharides. The neutral sugars in dimethylsulfoxide (DMSO) soluble non-starch polysaccharides were found to be enriched in rhamnose, xylose, glucose, and arabinose. Extraction of sago pith with aqueous 5% NaOH produced hemicelluloses, which were enriched in xylose and, to a lesser extent, glucose, arabinose, galactose, and rhamnose-containing polysaccharides, together with 7.4% uronic acids and 3.9% lignin. Further extraction of the delignified pith residue with aqueous 24% KOH and 2% H₃BO₃ removed the residual hemicellulosic fraction, which was enriched in glucose and xylose-containing polysaccharides, together with 5.8% uronic acids and 1.1% associated residual lignin. Six phenolic acids and aldehydes were detected in the mixtures of alkaline nitrobenzene oxidation of 5% NaOH soluble lignin and associated lignin in hemicelluloses and cellulose fractions. The lignin fraction contained a high proportion of non-condensed syringyl units and small amounts of non-condensed guaiacyl units as well as fewer non-condensed p-hydroxyphenyl units.     

The structure of wool fibers grafted with chitosan coated Ag-loading nano-SiO2 antibacterial composites

Wool fiber was grafted with chitosan coated Ag-loading nano-SiO₂ (CCTS-SLS) antibacterial composites under ultraviolet irradiation. The morphologies and structures of CCTS-SLS-wool were characterized by using scanning electronic microscopy, transmission electron microscopy, and Fourier transformation infrared spectrometry. The results show that a uniform and smooth antibacterial layer of 200 nm in thickness was formed on the surface of wool fiber by covalent bonding. The mechanical properties of the antibacterial wool fiber were improved. The antibacterial performance was found to be excellent, with antibacterial effect up to 90 % even after repeated washing. CCTS-SLS-wool possessed soft hand-feeling and good color.     

酒石酸酰化改性制备低固体含量大豆蛋白胶黏剂的研究

以L-酒石酸和乙酰氯在极少量磷酸做催化剂的条件下制备二乙酰基酒石酸,之后将二乙酰基酒石酸溶于乙醇中制备改性剂,加入到制备好的p H10.50~10.90低浓度大豆分离蛋白预处理液中,制备胶黏剂。测试胶黏剂的固体物含量、DSC、胶合强度以及胶黏剂横切面。结果表明:p H10.7~10.8时,200 m L大豆分离蛋白预处理液中加入0.4 g二乙酰基酒石酸和10 m L无水乙醇制备的改性剂,最终得到的胶黏剂有良好的耐水性,胶合强度2 MPa,远超过国家对Ⅱ类胶合板胶合强度的要求(≥0.7 MPa)。     

乙酸甲酯对大豆蛋白胶胶膜快干性的影响

提出了大豆蛋白胶胶膜概念,通过单因素试验研究了乙酸甲酯对大豆蛋白胶胶膜快干性及胶膜胶合强度的影响.结果表明:乙酸甲酯可以显著提高胶膜的快干性,且随着添加量的增加而增快,综合考虑乙酸甲酯大豆蛋白胶膜的干燥速率及胶合强度的影响,100 g大豆蛋白胶添加15 mL乙酸甲酯为最适添加量.     

Preparation and properties of Nano-TiO2 photo-catalytic silk respirator paper

In order to obtain paper respirator with dust resistance performance and antibacterial property, silk photo-catalytic respirator paper was made by loading nano-TiO₂ photo-catalyst on silk based respirator paper. The pore structure, surface topography and TiO₂ distribution, and the filtration performance of silk respirator paper were studied by using a pore size meter (PSM), a field emission scanning electron microscope (FESEM), and a filter tester, respectively. In addition, the antibacterial property of silk respirator paper was also investigated. The results showed that the pore structure and filtration performance of silk respirator paper could be controlled by changing the degree of beating of silk pulp and the basis weight of silk paper. Silk respirator paper of 45 g/m² made from silk pulp having beating degree of 85 ^oSR had high filtration efficiency and appropriate filtration resistance. Nano-TiO₂ particles were mainly attached to the surface of silk paper, and the loading of nano-TiO₂ photo-catalyst resulted in a slight decrease in filtration resistance and filtration efficiency of silk respirator paper. It, however, improved the antibacterial property of silk respirator paper effectively.     

The effect of alkali pre-treatment on formation and adsorption of silver nanoparticles on cotton surface

This study is an attempt to investigate the feasibility of alkali pre-treatment to activate surface hydroxyl groups of cellulose fibers in order to enhance the deposition efficiency of silver nanoparticles (AgNPs) onto cotton fabrics. Cotton samples were pre-treated with various alkali solutions containing different earth metal hydroxides (LiOH, NaOH, and KOH). The as-prepared samples were then treated with aqueous silver nitrate followed by reduction treatment with aqueous ascorbic acid, which caused in situ formation of AgNPs on fiber surfaces. The surface structure of the fabrics was characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) analysis, and colorimetric data. The amount of silver was measured by using inductively coupled plasma-optical emission spectrometer (ICP-OES). Antimicrobial activity was measured against Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli bacteria. It was established that alkali pre-treatment had a substantial effect on the formation and adsorption of AgNPs on the fibers. Alkali pre-treated samples were homogeneously coated by AgNPs with high surface coverage. Alkali type had significant effect not only on the amount of AgNPs on the surface but also on its size. High antibacterial activity against both Gram-positive and Gram-negative strains was also demonstrated, even after 10 cycles washing.     

国内大豆胶粘剂的改性研究进展

大豆胶粘剂是一种绿色环保胶粘剂,在人造板领域具有很大的应用潜力.为改善大豆胶黏剂的耐水胶合性能及防腐性能,人们进行了大量的改性研究,其中耐水胶合性能的改性研究较多,包括物理改性、尿素改性、酸碱盐改性、接枝共聚、共混改性、有机试剂改性、晶须、纳米改性等.该文对目前国内有关大豆胶粘剂的改性研究进展进行了综述.