聚合物乳液的稳定性

简要讨论了乳液稳定性的原理,综述了乳液配方、乳胶粒组成和结构对聚合物乳液电解质稳定性、机械稳定性、冻融稳定性和贮存稳定性的影响。     

Lipase-catalyzed synthesis and properties of estolides and their esters

Eight lipases were screened for their ability to synthesize estolides from a mixture that contained lesquerolic (14-hydroxy-11-eicosenoic) acid and octadecenoic acid. With the exception ofAspergillus niger lipase, all 1,3-specific enzymes (fromRhizopus arrhizus andRhizomucor miehei lipases) were unable to synthesize estolides.Candida rugosa andGeotrichum lipases catalyzed estolide formation at >40% yield, with >80% of the estolide formed being monoestolide from one lesquerolic and one octadecenoic acyl group:Pseudomonas sp. lipase synthesized estolides at 62% yield, but the product mixture contained significant amounts of monoestolide with two lesquerolic acyl groups as well as diestolide. ImmobilizedR. miehei lipase was chosen to catalyze the esterification of mono-and polyestolide, derived synthetically from oleic acid, with fatty alcohols or α,ω-diols. Yields were >95% for fatty alcohol reactions and >60% for diol reactions. In addition, the estolide linkage remained intact through the course of the esterification process. Esterification of estolides improved the estolide’s properties—for example, lower viscosity and higher viscosity index—but slightly raised the melting point. Estolides and, particularly, estolide esters may be suitable as lubricants or lubricant additives.     

Prediction of Experimental Methanol Decomposition Rates on Platinum from First Principles

A microkinetic model for methanol decomposition on platinum is presented. The model incorporates competitive decomposition pathways, beginning with both O–H and C–H bond scission in methanol, and uses results from density functional theory (DFT) calculations [Greeley and Mavrikakis, J. Am. Chem. Soc. 124 (2002) 7193, Greeley and Mavrikakis, J. Am. Chem. Soc. 126 (2004) 3910]. Results from reaction kinetics experiments show that the rate of H₂ production increases with increasing temperature and methanol concentration in the feed and is only nominally affected by the presence of CO or H₂ with methanol. The model, based on the values of binding energies, pre-exponential factors and activation energy barriers derived from first principles calculations, accurately predicts experimental reaction rates and orders. The model also gives insight into the most favorable reaction pathway, the rate-limiting step, the apparent activation energy, coverages, and the effects of pressure. It is found that the pathway beginning with the C–H bond scission (CH₃OH→H₂COH→HCOH→CO) is dominant compared with the path beginning with O–H bond scission. The cleavage of the first C–H bond in methanol is the rate-controlling step. The surface is highly poisoned by CO, whereas COH appears to be a spectator species.     

Synthesis and metal uptake studies on poly(8‐hydroxy‐5‐azoquinolinephenylacrylate‐formaldehyde) resin and its metal complexes

8‐hydroxy‐5‐azoquinolinephenylacrylate‐formaldehyde (8H5AQPA‐F) macromonomer was prepared from acryloylchloride, with condensation products of 8‐hydroxy‐5‐azoquinolinephenol‐formaldehyde, and polymerized in DMF at 70°C using benzoyl peroxide as free radical initiator. Poly(8H5AQPA‐F) was characterized by infrared and nuclear magnetic resonance spectroscopic techniques. Polychelates were obtained in alkaline solution of polymeric ligand, with the aqueous solution of Cu(II) and Ni(II). Elemental analysis of polychelates suggests that the metal to ligand ratio is about 1:2. The polymer metal complexes were also characterized by IR, XRD, magnetic moments, and thermal analysis. The effects of pH and electrolyte on the metal uptake behavior of the resin were also studied. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 797–802, 2007     

Anionic synthesis of poly(epichlorohydrin-g-styrene) and chemical modification of polyepichlorohydrin

Poly(epichlorohydrin-g-styrene) copolymers, P(ECH-g-S)s, have been prepared in solution by two different methods of coupling polyepichlorohydrin, PECH, with polystyrene, PS, containing a functional end group. In the first method, polystyryl carboxylic acid, PSCOOH, prepared from living polystyrene, was converted to the corresponding potassium salt which was coupled with PECH in dimethyl formamide solution usually at 60°C. In the second method, polystyryl potassium, PS^?K⁺, in tetrahydrofuran solution was end-capped with propylene sulphide to form PSCH₂CH(CH₃)S^?K⁺ which was coupled directly with PECH in tetrahydrofuran at 40°C. Grafting by the first reaction was relatively slow but occurred without significant adverse side reactions. The grafting by the second reaction was relatively fast, but side reactions occurred resulting in a cleavage of the graft copolymer. The graft copolymers were purified by fractional precipitation and extraction procedures and were characterized by infra-red and ultra-violet spectroscopy, microanalysis, gel permeation chromatography, differential scanning calorimetry, solution viscometry, dynamic mechanical testing, and electron microscopy. Solution properties of the graft copolymers in benzene-carbon tetrachloride and toluene-cyclohexane mixtures were studied. There was evidence of micelle formation in dilute solutions of the mixed solvents and microphase separation of components in the solid state. Nucleophilic substitution of chlorine atoms in PECH by phenyl acetate (C₆H₅ CH₂COO-) and thiophenoxide (C₆H₅S-) groups was performed.     

纤维素科学与技术研究进展

本文综述纤维素科学与技术的研究进展。阐述了纤维素结构、纤维素的合成、纤维素液晶、功能纤维素、纤维素溶剂、纤维素裂解和纤维素的废物利用等的最新动态。     

Different support effect of M/ZrO2 and M/CeO2 (M = Pd and Pt) catalysts on CO adsorption: A periodic density functional study

CO adsorption over Pd₄ and Pt₄ cluster supported by c-ZrO₂(1 1 1) and CeO₂(1 1 1) catalyst systems was investigated using periodic density functional method in order to clarify the support effect on CO activation. We found that the support increases the CO activation for bridge and three-fold sites but decreases for the atop site. Moreover, it was found that the support changes the site preference for the CO adsorption. Bridge site on both the Pt₄/c-ZrO₂ and Pt₄/CeO₂ show larger CO adsorption energies than those on the other sites while the atop site is energetically preferable on isolated Pt₄ cluster. c-ZrO₂ supported Pd shows the largest CO activation with large charge transfer from the catalyst to the CO molecule. This reveals that ZrO₂ supported Pd can be a good catalyst for CO activation because of its higher probability to the three-fold site CO adsorption. We also found that positively charged M₄ clusters on the support keep their strong electron-donating properties and have enough charge density to contribute to the activation of an adsorbed CO molecule by a charge transfer.     

基于国家电网的财务管理系统的开发与研究

随着社会生产力的不断发展,越来越多的企业认识到了财务工作的重要性。企业要利用现代高效的运作方式来开发和管理组织中最重要、最昂贵的资源,实现财务管理的精细化、自动化,提高财务资源的利用率,促进企业的发展。     

液晶材料取代联苯硼酸化合物的研究

以液晶材料取代联苯硼酸化合物异构体混合物为原料,在相转移催化剂正十六烷基三甲基溴化胺的作用下,于碱性条件下,105~115℃反应3~8 h,得到液晶材料取代联苯化合物,它是生产相应的液晶材料取代联苯硼酸化合物的初始原料。并对其结构进行了质谱确认。     

Sodium alginate–poly(hydroxyethylmethacrylate) interpenetrating polymeric network membranes for the pervaporation dehydration of ethanol and tetrahydrofuran

Interpenetrating polymeric network (IPN) membranes of sodium alginate (NaAlg) and various amounts of poly(hydroxyethylmethacrylate) (PHEMA) have been prepared and tested for the pervaporation dehydration of ethanol and tetrahydrofuran (THF). The presence of hydrophilic PHEMA in the IPN matrix was found to be responsible for increase in membrane selectivity to water. NaAlg–PHEMA IPN membrane containing 20 wt % of PHEMA exhibited a selectivity of 571 to water for the water–ethanol mixture and 857 for water–THF mixture. These data are much better than those observed for the pristine NaAlg membrane. However, flux of the IPN membranes was smaller than that of pristine NaAlg membrane. Comparatively higher flux values were observed for water–THF mixture than for water–ethanol mixture. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3324–3329, 2006