Phosphate selective alkylenebisurea receptors: structure-binding relationship

New host molecules for anions, adamantane, and alkyl urea derivatives substituted by naphthalene chromophores, were synthesized. Their binding with F⁻, Cl⁻, Br⁻, OAc⁻, HSO₄⁻, NO₃⁻, and H₂PO₄⁻ was investigated by UV-vis, fluorescence and NMR spectroscopy. The anion binding ability of adamantyl bisurea derivatives was compared with the analogous host molecules, wherein the urea moieties are separated by flexible alkyl linkers of the same length, and adamantane monourea derivative. The host molecules show the highest selectivity toward F⁻ and H₂PO₄⁻. The binding stoichiometry and the values of the association constants depend on the basicity of anions, availability of H-bonding sites, preorganization, and rigidity of the hosts, as well as solvent polarity and H-bonding availability. Rigid adamantane receptors, compared to flexible analogues show increased selectivity for H₂PO₄⁻, whereas binding of OAc⁻ is better with flexible receptors. The binding of OAc⁻ and H₂PO₄⁻ was investigated by microcalorimetry. The stoichiometries and the stability constants of the corresponding complexes obtained by this method were in good agreement compared to those determined by UV-vis titrations. In both cases the enthalpic contribution to the overall complex stability was predominant.     

Preparation and characterization of a novel fluorinated acrylate resin

The novel fluorinated acrylate resin was successfully prepared by solution polymerization of 2-(perfluoro-(1,1-bis-isopropyl)-2-propenyl)oxyethyl methacrylate (POMA) with butyl acrylate (BA), methyl methacrylate (MMA) and methacrylic acid (MAA) initiated by AIBN in the co-solvents of ethyl acetate, butyl alcohol and toluene. POMA was synthesized from the intermediate perfluoro nonene and 2-hydroxyethyl methacrylate as the staring reactants. Films of the novel fluorinated acrylate resin were prepared by coating the resin directly on the clean glass sheet and allowed to dry at room temperature. The characteristics of the film such as hydrophobicity, glass transition temperature and thermal stability were characterized with the contact angle, differential scanning calorimetry and thermo-gravimetric analysis respectively. The structure of the novel fluorinated acrylate resin was investigated by Fourier transform infrared (FTIR) spectrometry. The influences of the fluorine content on the performance of the acrylate resin were studied. Results show that the hydrophobicity, chemical resistance, glass transition temperature and thermal stability of the acrylate resin are improved when the fluorinated monomer is introduced to copolymerize with other monomers. However, the hydrophobicity of the fluorinated acrylate resin is improved slightly via annealing.     

PAR螯合树脂相光度法测定钯

树脂相光度法是一种灵敏、快速、简单的分离富集与测定同时进行的新型方法[1 ,2 ] 。该方法以离子交换树脂作载体 ,直接对显色树脂进行光度测定 ,避免了洗脱、分离等复杂过程 ,使灵敏度得到了很大提高 ,迄今为众多研究者关注[3] 。铂族金属钯的光度分析法报道较多[4] ,但迄今少见用树脂相光度法测定钯的报道。星野仁等[5 ,6] 指出在ＥＤＴＡ ＮａＯＨ 硼砂介质中 ,ＰＡＲ Ｐｄ(Ⅱ )配合物与十四烷基二甲基苄基氯化铵形成离子缔合物 ,该缔合物能被ＣＨＣｌ3定量萃取 ,其摩尔吸光系数为 3.2 9× 1 0 4 ,方国桢等[7] 确定了在ＥＤ ＴＡ ＮａＯ…     

A STUDY ON THE ADSORPTION OF LOW CONCENTRATION FREE ALKALI BY SUBACID RESIN

The absorption of free alkali at low concentration by subacid resin was traced with electric conductance method,the effect of temperature on the adsorption,the activation energy of adsorption (Ea) and interaction energy(U) was studied.The result showed that,the process of low concentration alkali adsorption by subacid resin was in accordance with mechanism of monomolecular layer absorption,in addition,with the increasing of temperature,the interaction energy between adsorbate and sorbent increase,so did the surface adsorption rate(k),and linear correlation existed between interaction energy(U) and temperature(T).     

STUDY ON THE DETERMINATION OF TRACE Fe(Ⅲ) BY THIN LAYER RESIN PHASE SPECTROPHOTOMETRY

A method to determine Fe(Ⅲ) by thin layer resin phase spectrophotometry has been developed in this paper. The colored complex formed by Fe(Ⅲ) and 1,2-benzendiol is concentrated on the 717# resin, then Fe(Ⅲ) can be determined directly by making thin layer. The method is sensitive with a apparent molar absorption of 4.8×104L/mol. cm, which is 16 times higher than that of liquid phase spectrophotometry, most coexisting ions do not influence the determination. The detection limit for Fe(Ⅲ) is 1.47μg/L with the precision of 3.3% [n=6, 7μg/50mL Fe(Ⅲ)]. The calibration curve is linear in the range of 0～25μg/50mL. The preposed method was applied to the determination of Fe(Ⅲ) in water sample with satisfactory results.     

Modification of sulfonated poly(ether ether ketone) with phenolic resin

Soluble phenol formaldehyde resin containing hydroxymethyl groups has been used to modify sulfonated poly(ether ether ketone) (SPEEK). Modification has been carried out with films containing both the polymers and using dimethyl formamide (DMF) as casting solvent at various temperatures under reduced pressure. Associated solvent and the hydrogen‐bonded by‐product dimethyl amine (DMA) were removed through mild alkali–acid–water treatment. Cured and treated films show good and consistent mechanical properties, water uptake (22–25%), ion‐exchange capacity (1.1–1.5 meq/g) and proton conductivity (125–150 mS/cm) at 30°C and hold promise for application in fuel cells, as indicated by a polarization study in a fuel cell test station. Copyright © 2007 John Wiley & Sons, Ltd.     

Hybrid resins from polyisocyanate/vinyl ester/water glass systems: Structure and properties

Polysilicate modified polyurea/vinyl ester hybrid resins were produced by dispersing water glass (WG) in a mixture of vinyl ester (VE) and polyisocyanate in presence of a liquid phosphate as emulsifier. As styrene-crosslinkable VE resins bisphenol A (BA) and novolac types (N), whereas as polyisocyanate a polymeric methylene diphenyl isocyanate (PMDI) were used. The structure and selected properties of the hybrid resins were determined and compared to those of the neat VEs and polysilicate filled polyurea (denoted as 3P resin). Using VE for resin hybridization, which worked as an additional emulsifier for the WG/PMDI/phosphate system, resulted in a fine particle dispersion of the polysilicate. It was found that the type of VE affected not only the dispersion of WG (and thus of the polysilicate) but also the network formation of the polyurea/VE hybrids and their properties. Information about the structure of the polysilicate filled hybrid resins was gained from dynamic-mechanical thermal analysis (DMTA), scanning electron and atomic force microscopic measurements. It was argued that the resin hybridization yielded a conetwork instead of an interpenetrating one. The properties of the hybrid systems were determined by DMTA, fracture mechanical tests, thermogravimetric analysis and flammability measurements. It was established that the stiffness and resistance to thermal degradation of the initial 3P resin was strongly improved by hybridization with VEs. The fracture toughness (K_c) proved to be less sensitive to the formulation of the hybrid resins. On the other hand, the fracture energy (G_c) and limiting oxygen index experienced a positive deviation from the additivity as a function of the 3P/VE composition, at least in a given range.     

Studies on curing kinetics of a novel combined liquid crystalline epoxy containing tetramethylbiphenyl and aromatic ester‐type mesogenic group with diaminodiphenylsulfone

The curing kinetics of a novel liquid crystalline epoxy resin with combining biphenyl and aromatic ester‐type mesogenic unit, diglycidyl ether of 4,4′‐bis(4‐hydroxybenzoyloxy)‐3,3′,5,5′‐tetramethyl biphenyl (DGE‐BHBTMBP), and the curing agent diaminodiphenylsulfone (DDS) was studied using the advanced isoconvensional method (AICM). DGE‐BHBTMBP/DDS curing system was investigated the curing behavior by means of differential scanning calorimetry (DSC) during isothermal and nonisothermal processes. Only one exothermal peak appeared in isothermal DSC curves. A variation of the effective activation energy with the extent of conversion was obtained by AICM. Three different curing stages were confirmed. In the initial curing stage, the value of E_a is dramatically decreased from ～90 to ～20 kJ/mol in the conversion region 0–0.2 for the formation of LC phase. In the middle stage, the value of E_a keeps about ～80 kJ/mol for cooperative effect of reaction mechanism and diffusion control. In the final stage, a significant increase of E_a from 84 to 136 kJ/mol could be caused by the mobility of longer polymer chains. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3922–3928, 2007     

环丁烯砜的精制及其UV-Vis和FTIR光谱分析

利用吸附法,考察了活性炭、离子交换树脂精制环丁烯砜的方案,利用UV-Vis,FTIR,XRD对其进行分析检测,重点对环丁烯砜、环丁砜的FTIR谱图进行了解析.活性炭、离子交换树脂串联去除工业级环丁烯砜杂质的效果最佳.利用精制的环丁烯砜催化加氢,合成出了高纯度的环丁砜,转化率大于99.8%,为工业装置技术改造提供了实验依据.     

Improvement in fracture behaviors of epoxy resins toughened with sulfonated poly(ether sulfone)

The sulfonated poly(ether sulfone) (SPES) was successfully prepared using chlorosulfonic acid as a sulfonating agent. Diglycidylether of bisphenol-A (DGEBA) epoxy resins were modified with different contents of SPES, and the thermal and mechanical interfacial properties of DGEBA/SPES blends were investigated. As a result, the surface free energy of the blends was increased by the addition of SPES. DSC measurements revealed that the curing reaction was delayed with the increase of SPES content. Whereas, the thermal stabilities of the blends were slightly decreased as the SPES content increased. Meanwhile, the glass transition temperature and fracture toughness of the blends were increased with increasing SPES content, due to the improved intermolecular interactions, such as hydrogen bonding, between the hydroxyl group of DGEBA and the sulfonic group of SPES in the blends. The agreement could be observed by SEM which revealed phase separated morphology of DGEBA/SPES blends.