Triazole-forming waterborne polyurethane composites fabricated with silane coupling agent functionalized nano-silica

In the research work, "click" chemistry was used to modify waterborne polyurethane (WPU) with silane coupling agent (SiCA) functionalized nano-silica. The modified WPU (CWPU) was characterized by FTIR, scanning electron microscope (SEM), thermogravimetric analysis (TGA) and contact angle measurement. The experiment results show that the modification can improve the thermal stability, hardness, and water or weather resistance of CWPU.     

Modified Nanofibrous Filters with Durable Antibacterial Properties

The main aims of the research were to produce efficient nanofibrous filters with long-term antibacterial properties and to confirm the functionality of samples under real filtration conditions. A polyurethane solution was modified by micro- or nanoparticles of copper oxide in order to juxtapose the aggregation tendency of particles depending on their size. Modified solutions were electrospun by the Nanospider technique. The roller spinning electrode with a needle surface and static wire electrode were used for the production of functionalized nanofibers. The antibacterial properties of the modified nanofibrous layers were studied under simulated conditions of water and air filtration. Particular attention was paid to the fixation mechanism of modifiers in the structure of filters. It was determined that the rotating electrode with the needle surface is more efficient for the spinning of composite solutions due to the continuous mixing and the avoidance of particle precipitation at the bottom of the bath with modified polyurethane. Moreover, it was possible to state that microparticles of copper oxide are more appropriate antimicrobial additives due to their weaker aggregation tendency but stronger fixation in the fibrous structure than nanoparticles. From the results, it is possible to conclude that nanofibers with well-studied durable antibacterial properties may be recommended as excellent materials for water and air filtration applications.     

Preparation and characterization of polyurethane based self-cleaning and antibacterial coating containing silver ion exchanged montmorillonite/TiO<Subscript>2</Subscript> nanocomposite

In order to reach an antibacterial, photocatalytic, and hydrophilic coating, commercial grade polyurethane (CPU) resin was modified with silver ion exchanged montmorillonite/TiO₂ nanocomposite in various montmorillonite to TiO₂ nanoparticle ratios. To characterize the prepared nanocomposites and coatings, X-ray diffraction patterns, FTIR and UV–Vis spectroscopy and SEM images were used. The modified commercial grade polyurethane coatings containing nanocomposites show better properties, including hydrophilicity, degradation of organic pollutants, antibacterial activity and water resistivity, compared to unmodified commercial grade polyurethane coatings. The water droplet contact angle of unmodified CPU coating was 70°, however it decreased to lower than 10° in modified CPU coatings after 24 h LED lamp irradiation. Decolorization efficiency of malachite green dye solution by the use of modified CPU coatings achieved up to 70% after 5 h LED lamp illumination, compared to less than 5% for unmodified CPU coatings. Modified CPU coatings also showed significant water resistivity and antibacterial properties.     

采用层层自组装与光化学修饰法在聚氨酯表面固定生物多糖衍生物

采用层层自组装技术与光化学修饰方法相结合在聚氨酯材料表面固定生物多糖衍生物,首先合成具有光反应活性的叠氮壳聚糖,再在聚氨酯基材表面进行叠氮壳聚糖与香菇多糖硫酸酯的层层自组装,然后通过光化学反应对自组装多层膜修饰层进行交联,制备得到生物多糖衍生物层层自组装与光化学表面修饰的聚氨酯材料.通过红外光谱、X射线光电子能谱、水接触角测量仪、抗菌活性测试、溶血试验和血小板黏附测试等方法对被修饰聚氨酯材料的表面性能和生物性能进行了分析,测试结果表明修饰后的聚氨酯材料表面的亲水性和血液相容性得到改善,并且被修饰材料对大肠杆菌具有良好的抑制效果.     

A novel sensitive detection platform for antitumor herbal drug aloe-emodin based on the graphene modified electrode

This paper has presented a novel strategy to carry out direct and sensitive determination of antitumor herbal drug aloe-emodin in complex matrices based on the graphene-Nafion modified glassy carbon (GN/GC) electrode. This proposed modified electrode showed good electrochemical response towards aloe-emodin (AE). Compared with the multiwall carbon nanotubes (MWCNTs) modified electrode, the GN/GC electrode has the advantages of higher sensitivity and lower cost. Under the optimized conditions, the calibration curve for AE concentration was linear in the range from 5 nmol/L to 1 μmol/L with the detection limit of 2 nmol/L. In addition, the practical analytical performance of the GN/GC electrode was examined by evaluating the selective detection of AE in natural aloe extracts and human urine samples with satisfied recovery. Therefore, the GN/GC electrode may hold great promise for fast, simple and sensitive detection and biomedical analysis of AE in complex matrices.     

Effect of the Amount of Calcium Carbonate as Filler on the Rheological and Adhesion Properties of a Water-Based Polyurethane Dispersion

In this study, the properties of water-based adhesives based on a polyurethane ionomer (PUD) and a micronised CaCO₃ as filler was analysed. Different amounts of a micronised CaCO₃ (5-25 wt%) were added to water-based polyurethane (PUD) adhesive formulations in order to reduce its relatively high cost. The addition of a micronised calcium carbonate filler increased the viscosity, the storage and loss moduli of the PUD adhesives, and imparted pseudoplasticity and thixotropy, more noticeably for the adhesive with the highest calcium carbonate content. The creation of acid-base interactions seemed to be responsible for the improvement in the rheological properties of the PUD adhesives containing CaCO₃ as filler. On the other hand, the addition of CaCO₃ filler might deteriorate the adhesion properties to PUD adhesives.     

Antimicrobial properties of Ag loaded zeolite polyester polyurethane and silicone rubber and long-term properties after exposure to in-vitro ageing

In biomedical applications, tubes (e.g. catheters etc.) are commonly produced from polyurethane (PU) and silicone rubber which are known to be biocompatible materials. Several studies have shown that tubes, which are connected to the body (invasive) (especially urinary, tracheotomy and central venous catheters) are associated with infections. The present study reports the development of a new method aiming at obtaining antibacterial properties for PU and silicone rubber by mixing respective material with a natural antibacterial agent (Ag+ loaded zeolite) in different weight fractions. The influence of the zeolite content on the antimicrobial properties were analysed by exposure to bacteria (ISO 22196) and mixtures of fungi (ISO 846). The materials were also subject to artificial body fluids (Artificial Lysosomal Fluid (ALF) and Gamble’s solution) for periods up to three months and the subsequent changes in the chemical properties after in-vitro exposure were determined by Matrix Assisted Laser Deposition/Ionization Time Of Flight Mass Spectrometry (MALDI-TOF MS) and Attenuated Total Reflection Fourier Transform Infra Red spectroscopy (ATR-FTIR). It was established that the antimicrobial effect of the materials increased with the increase of the zeolite content. The wettability of the materials was found to decrease significantly during the in-vitro exposure, but this could not be correlated to the zeolite content. In the PU samples, the formation of free carbonyl and -OH groups was observed, which corresponds to oxidative degradation. In case of the silicone rubber the ratio of cyclic PDMS to linear PDMS (H, CH3 and dimethyl terminated) decreased, which indicates a change in the concentration of the compounds. The formation and increase of the O-H bond during the exposure was also confirmed by the infrared spectra of the material which corresponds to hydrolysis of the silicone rubber.     

Synthesis,Characterization and Physicomechanical Properties of Novel Water-based Biodegradable Polyurethane Dispersion

Novel water-based biodegradable polyurethane dispersions with an aim to develop environmentally friendly materials, including medicine, various industries, have been prepared in this study. Biodegradable ionic polyurethanes (IPU) were synthesized based on polyols from renewable resources, such as castor oil (CO), in the presence of a polyester polyol and polyethylene glycol (PEG) with hydrophilic property and 1,6-hexamethylene diisocyanate. 1,4-Butanediol and dibutyltin dilaurate, were used as a chain extender and catalyst, respectively. The comprehensive investigations of the structure and properties of five types of synthesized polyurethanes demonstrated biodegradability relationship of these polyurethanes with their structure and composition. In this research effects of different types and content of polyols on biodegradability and physico mechanical properties of prepared PUDs were investigated. The structure, properties and physico mechanical and application behavior of mentioned materials were characterized by ¹H NMR, FTIR spectroscopy, thermogravimetric analysis (TG/DTG) and dynamic mechanical thermal analysis (DMTA). The adhesion properties were measured by pull off test as well. Particle size was measured by dynamic light scattering (DLS) methods. The biodegradability of prepared polyurethane dispersions was confirmed by water uptake, hydrolytic and enzymatic degradation in phosphate buffer saline (PBS) with lipase enzyme in PBS. Results showed that by the incorporation of natural components into the polymer chain, adjusting of hydrophilic and hydrolytic liability properties of soft segments and especial relevant designs, useful polyurethane can be synthesized with desirable property of biodegradability and dispersion stability. Except for one sample, other samples were decomposed totally in enzymatic media.     

氟化聚氨酯的合成和表征

综述了各种不同结构的氟化聚醚《型和氟化聚酯型聚氨酯的合成并对产物的化学性能进行了描述。对各种表征方法的结果讨论表明,由于结构的特殊性,氟化聚氨酯有其不同于非氟化聚氨酯的特性。     

Synthesis of montmorillonite-based tris(2-ethylamine)-Schiff-base composites with remarkable antibacterial activity

A range of heterogeneous, inexpensive and benign Schiff bases-montmorillonite composites were synthesized and screened for their antibacterial activity against common microbial pathogens. Sodium montmorillonite (Na-MMT) clay was modified with tris(2-ethylamine) in the presence of dilute HCl to yield a quaternary salt of tris(2-ethylamine) modified clay. The Schiff bases were then fabricated from the reaction of the modified montmorillonite using different aldehydes. The structures of the obtained compounds were confirmed by Fourier transformer Infrared (FT-IR), X-ray diffraction (XRD), and thermal gravimetric analysis (TGA). All the obtained composite materials were screened for their antibacterial activities against the multi-drug resistant (MDR) strains. It was reasoned that the modified MMT-based composites has the ability to absorb the different micro-organisms onto the surface, and accordingly act as an effective antibacterial agent. All the composites showed significant antibacterial activity between 2.5 and 20 mg/mL against the MDR bacterial strains. The benzyl-based/modified MMT and the tertiary amino-based/modified MMT was found to be the most effective antibacterial agent.     

Surface-imprinted polyurethane having affinity sites for ampicillin

Affinity sites for an antibacterial drug, ampicillin, were created on the surface of polyurethane using the technique of non-covalent molecular imprinting. This was achieved by polymerizing aminophenylboronic acid in the presence of the ampicillin as a template. The extent of adsorption of the drug by the imprinted surface is nearly five times higher than the non-imprinted surface. The in vitro release studies have shown that the drug is retained for a prolonged period on the imprinted surface while it is rapidly released from the non-imprinted surface. These modified materials were subjected to interactions with two bacterial strains, E. Coli and S. aureus. These species could not adhere to the imprinted surface, further showing the ability of the surface to retain the drug for a prolonged period of time. The non-imprinted surface retained the bacterial strains, reflecting the lack of the drug on the surface. This novel approach seems to be useful for creating surfaces capable of retaining components of interest through non-covalent interactions to impart specific features, such as improved blood compatibility and antibacterial properties. [diagram in text].     

ε-己内酯改性聚氨酯丙烯酸酯的制备及电子束固化涂料性能研究

本文以甲基丙烯酸羟乙酯、ε-己内酯及异氟尔酮二异氰酸酯为原料制备了己内酯改性聚氨酯丙烯酸酯。使用傅里叶变换红外光谱(FT-IR)和核磁共振氢谱(~1HNMR)表征了产物结构。探究了ε-己内酯链段含量对改性聚氨酯丙烯酸酯树脂黏度的影响,并进一步对比研究了其电子束(EB)固化膜和紫外光(UV)固化膜的热机械性能、拉伸性能和涂层基本性能的差异。     

Biointeractive antibacterial fibres using polyelectrolyte multilayer modification

Contact-active antibacterial surfaces are a novel tool in the antibacterial battle. The preparation of such surfaces usually involves harsh reaction conditions and organic solvents. A more sustainable alternative would involve physical adsorption of water-soluble polyelectrolytes using a renewable substrate. Here, highly charged cationic polyvinylamines (PVAm), with or without hydrophobic modifications, have been adsorbed onto the naturally anionic cellulosic wood-fibres. To increase the amount of PVAm, polyelectrolyte multilayers were prepared using polyacrylic acid as the anionic polyelectrolyte. The modified fibres were characterised for PVAm content, water retention and antibacterial properties. The use of multilayers increased the total polymer content without notably reducing the water swelling. The fibres were shown to have excellent bioactive properties and reduced waterborne Escherichia coli and Bacillus subtilis by more than 99.9 %, which is a generally accepted definition of an antibacterial material. A large reduction in bacterial growth was observed upon addition of nutrients, although minor growth was detected after 24 h. The results further show that one adsorbed polymer layer was sufficient to obtain a contact-active surface, which makes the PVAm multilayer system seemingly unique. No polymer leaching from any of the samples was detected, indicating that the fibres work via a contact-active antibacterial mechanism. The results show the feasibility of constructing a sustainable antibacterial material using a renewable substrate and water-based solutions in the material construction process.     

环氧改性水性聚氨酯乳液的制备及其膜性能

以聚己内酯二元醇(CAPA)为软段,异佛尔酮二异氰酸酯(IPDI)和六亚甲基二异氰酸酯(HDI)为硬段,环氧树脂E-44为大分子交联剂,经相转化法合成了一系列环氧树脂改性负离子水性聚氨酯(EPPU)自乳化乳液,并制备了改性水性聚氨酯的固化膜.通过FTIR、TGA及接触角、力学性能测试对聚合物结构及其膜性能进行了研究.通过原子力显微镜(AFM)观察膜表面形态和表面粗糙度.乳液粒径及粒径分布通过动态激光光散射法(DLLS)测定.FTIR分析表明环氧树脂的羟基和环氧基都参与了发应.TGA表明,环氧树脂的加入可以提高聚氨酯的热稳定性.随着w(E-44)增大,改性聚氨酯膜的拉伸强度得到改善,断裂伸长率减小.随着w(E-44)增大,乳液粒径增大,薄膜的接触角增大,改性后的PU膜表面光滑度下降,拒水性增强.     

一种X-射线不透性聚氨酯显影材料的制备及性能研究

利用对碘苯胺对含有过量异氰酸根的聚氨酯分子进行封端,合成了一种新型的X-射线不透性聚氨酯显影材料.利用X-射线映射对不同封端量聚氨酯的显影效果进行评定;利用DSC和TGA对其热性能进行表征,并评估封端反应对聚氨酯热稳定性的影响;利用噻唑蓝(MTT)比色法测试了材料的细胞毒性;并对具有不同碘含量聚氨酯材料的显影效果、相对分子量及其分布、力学性能进行了对比研究.研究结果表明,当碘含量达到3.5wt%左右时聚氨酯材料即可达到同等厚度铝板相同的显影效果,而且在此条件下,聚氨酯材料依然保持较好的力学性能和热稳定性.MTT法测试表明对碘苯胺封端的聚氨酯材料不具有细胞毒性.     

羧甲基纤维素钠修饰的聚氨酯泡沫制备磁性吸油材料

采用聚氨酯泡沫为模板,依次修饰羧甲基纤维素钠(CMC)、Fe~(3+),在惰性气氛中高温热处理反应,制备多孔结构的磁性吸油材料.用光学显微镜、扫描电子显微镜、红外吸收光谱、X-射线衍射、接触角等技术对材料进行表征.详细考察了加热反应温度、CMC浓度和Fe~(3+)浓度对材料吸油性能和磁性的影响规律.实验表明,当加热反应温度选择230°C,CMC浓度为0.3 wt%,FeCl_3浓度为0.1 mol/L时,材料吸油性能最佳,对正己烷、二甲苯、环己烷、甲苯、乙酸乙酯、氯仿、机油、原油等有机溶剂和油类分子的吸附容量为10倍左右.磁性多孔材料具有明显的亲油、疏水特性,水的接触角达115.9°,同时材料密度只有0.036g/cm~3,能够漂浮于水面,实现对水面有机溶剂的快速吸附.吸附后的材料在外界磁场控制下,能够通过磁分离方式从水面快速分离.该材料具有良好的循环利用性能,可重复使用20次以上,吸油性能仍然保持良好.     

Preparation and Properties of Non-ionic Polyurethane Crosslinkers from 2-Ethoxyethanol/ϵ-caprolactam-Blocked Diisocyanate

A series of novel water-based non-ionic blocked polyurethane crosslinker (n-BPUC) dispersions have been synthesized by the reaction of toluene 2,4-diisocyanate (TDI), isophorone diisocyanate (IPDI), polyethylene glycol (PEG), 1,1,1-trimethylolpropane (TMP), 2-Ethoxyethanol (2-Et) and ?-caprolactam (CL). The physical properties of prepared n-BPUC dispersions such as viscosity, pH, and storage stability are measured and compared. The chemical structure of the prepared n-BPUC dispersions is confirmed by Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC). Deblocking temperatures of the n-BPUC dispersions are analyzed by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) techniques. The thermal analysis reveals that deblocking temperature obtained by DSC and TGA techniques is compared and found to be in the order DSC < TGA. Based on DSC and TGA data, it is shown that deblocking of n-BPUC dispersions based on 2-Et start at lower temperatures compared to that of the ones based on CL. The TDI-based n-BPUCs show higher reactivity than the ones based on IPDI. Hydroxyl-terminated polyurethane (HPU) is introduced to estimate the crosslinking effect of the prepared n-BPUCs. The better tensile properties and water resistance of n-BPUC modified HPU films compared to pure HPU film demonstrate the good crosslinking effect of the prepared n-BPUCs.     

Study on the adsorptive catalytic voltammetry of aloe-emodin at a carbon paste electrode

Recently, the studies and applications for the pola-rographic catalytic waves of organic compounds at dropping mercury electrode made considerable head-way. Tovopova et al.[1―4] reported the polarographic catalytic waves of the organic compounds containi…     

Polyurethane foams based on modified tung oil and reinforced with rice husk ash I: Synthesis and physical chemical characterization

A chemically modified tung oil was used as the main polyol component in the formulation of viscoelastic (low resilience) polyurethane foams. Rice Husk Ash (RHA), a residue from the rice process industry, was chosen to be incorporated as rigid filler in these materials because of its high silica content. Water was used as blowing agent in order to increase the green nature of the reinforced foams. Physico-chemical and thermal properties of the neat and reinforced foams were measured and analyzed. RHA addition leads to noticeable changes in several properties, mainly thermal conductivity, density and foam morphology, even at the low filler content used in this work. Although the thermal stability was almost unaffected by ash content, a stabilizing effect of the inorganic filler was identified, since the residual char was higher than predicted from theoretical calculations.     

胍盐键合型聚氨酯涂料的制备及其抗菌防霉性能

采用化学键合的方式将聚六亚甲基盐酸胍(PHMG)键合到聚氨酯(PU)分子链上,制得抗菌PU涂料PU-PHMG。利用红外光谱(FT-IR)、阿贝折射仪、原子力显微镜(AFM)等对其结构与性能进行了表征,用振荡法、抑菌圈法等对其抗菌性能进行了测试,同时探究了PHMG的质量分数对PU涂料各项性能的影响。研究表明:当PHMG的质量分数为1.0%时,PHMG的键合效率达到93.59%,对大肠杆菌和金黄色葡萄球菌的抑菌率达到99.5%以上,证明PU-PHMG具有优异持久的抗菌性能。此外,该涂料还兼具优异的防霉性能和力学性能。