Solvent-free low-dimensional polymer electrolytes for lithium-polymer batteries

The development of solvent-free low-dimensional polymer electrolytes intended for use in solvent-free lithium batteries operating at ambient or sub-ambient temperatures is described. The synthetic routes to the amphiphilic polymers I having 5-alkoxy-3,4-phenylene units connected with oligoethoxy segments via polyester-ether or pure polyether links (abbrev. CmOn, m = 12, 16, 18, n = 1-5) and to the copolymers CmO1-CmOn are described. The structures, thermal properties and SAXS long spacings of their complexes with lithium salts (type A) and with long chain n-alkane or alkyl side chain intercalation (type B) are discussed. However, high ambient conductivities (10(-4)-10(-3) S cm(-1)) are observed in type C systems when a second copolymer based on polytetramethylene oxide segments (II) is incorporated as a microphase between the lamellae of I and serving as an ion bridge or "glue". DC polarization between Li electrodes also gives ambient conductivities >/=ca.10(-3) S cm(-1). In type D systems the I/II interface is stabilized by including a copolymer III, promoting high reproducibility in performance. Copolymers I of CmO1-CmO5 having CmO1 in excess give optimum conductivities with low temperature-dependence. This, together with molecular modeling, suggests uncoupled ion mobilities by hopping between small aggregates in the interlamellar spaces.     

氧化锌微晶的制备和形貌控制

本文在溶液体系中合成了多种形貌的氧化锌(ZnO)微晶。所得花状、雪花状、棒状、多刺球状和棱柱状氧化锌微晶用粉末X射线衍射(XRD)和扫描电镜(SEM)进行了鉴定和表征,考察了反应条件如溶剂、温度及pH值对ZnO微粒尺寸和形貌的影响,初步探讨了不同形貌ZnO微粒的生长机理。该文对制备形貌可控的氧化物具有一定的指导意义。     

Thermodynamic evaluation of a partial charge model assumptionfor the dissolved silica system

The Partial Charge Model was developed to predict the hydroxylation, polymerization, and precipitation of ions. The purpose of this study is to evaluate the Partial Charge Model for describing the polymerization of silica in aqueous solutions. The Partial Charge Model predicts the stability of ions and complexes based on the assumption that the stable species will have the same electronegativity as the mean electronegativity of the solution. The silica system was chosen for model validation because of the rare availability of self-consistent thermodynamic data on many dissolved but polymerized silicate anions, including both linear and cyclical species. The electronegativity of each species was calculated using the Partial Charge Model and the results were plotted against the stability constants for the ions. The silicate anions segregated into groups on the plot based on the number of charges per silicon atom in the polymer. Plots of the log of the stability constant versus the change in electronegativity produced a linear relationship for the silica polymers containing one negative charge per silicon atom, which resulted in an r ² of 0.9978. Thus, the Partial Charge Model successfully describes the thermodynamics of silica polymerization in aqueous solution for species that are sufficiently alike, but was not accurate for all silica species.     

甘氨酸与氯化碱金属在水中的焓相互作用参数

氨基酸在混合溶液中的热力学性质及相互作用的研究不论对溶液化学还是生命科学都是十分重要的．对此国内已有不少的研究h，’1．利用偿效应的方法研究氨基酸与电解质间的相互作用是很有效的卜一句，但大多数的工作都是在低浓度下研究一个氨基酸分子和一个电解质离子对间的相互作用烩．本文测定了甘氨酸在水中和在LICI、NaCI、KCI的水溶液中的溶解偿，计算出甘氨酸与各个公在水中的偿对相互作用参数和三相互作用参数，并由此讨论了甘氨酸与这些盐的对分子相互作用和三分子相互作用．1实验部分试剂：甘氨酸为ARfa，K甲醇一水重结晶．LI…     

Standard enthalpy of formation of lanthanum oxybritholites

Lanthanum-bearing silicate-oxyapatites or britholites, Ca_10–xLax(PO₄)_6–x(SiO₄)_xO with 1≤x≤6, have been synthesized by solid state reaction at high temperature. They were characterized by X-ray diffraction and IR spectroscopy. Using two microcalorimeters, the heat of solution of these compounds have been measured at 298 K in a solution of nitric and hydrofluoric acid. A strained least squares method was applied to the experimental results to obtain the solution enthalpies at infinite dilution, and the mixing enthalpy in two steps. In the first step the mixing enthalpy obtained is referenced to the britholite monosubstituted and to the oxysilicate. The mixing enthalpy referenced to the oxyapatite and to the oxysilicate is then extrapolated. In order to determine the enthalpies of formation of all the terms of the solution, thermochemical cycles were proposed and complementary experiments were performed. The results obtained show a decrease of the enthalpy of formation with the amount of Si and La introduced in the lattice. This was explained by the difference in the bond energies of (Ca–O, P–O) and (La–O, Si–O).     

阳离子无皂含氟丙烯酸酯的合成与表面性能

在合成甲基丙烯酸全氟辛酰氧基乙酯(FA)基础上,用半连续法制备了无皂阳离子含氟丙烯酸酯乳液。当乳液的粒径在100~200 nm、ζ电位大于40 mV时,乳液较稳定。阳离子亲水单体甲基丙烯酰氧乙基三甲基氯化铵(DMC)在含氟丙烯酸酯中质量分数为0.10~0.18、固含量小于20%时乳液的稳定性好,且随DMC含量的增加稳定性提高;含氟丙烯酸酯乳胶膜的附着力与耐磨性好,乳胶膜的透湿率随DMC的增加而增加。随热处理温度的提高,膜表面自由能下降;经160℃热处理后膜发生了交联,表面自由能为18 mN/m,与聚四氟乙烯(PTFE)的表面能相近,DMC含量对膜表面自由能影响不大。XPS分析也表明膜表面氟含量随热处理温度的提高而增加。     

Fe/Zn double metal cyanide catalyzed ring-opening polymerization of propylene oxide: 2. Characterization of active structure of double metal cyanide catalysts

Double metal cyanide (DMC) complexes based on Zn₃[Fe(CN)₆]₂ were synthesized using different molar ratios of ZnCl₂ to K₃[Fe(CN)₆] and special complexing agents. IR spectroscopy, electron spectroscopy for chemical analysis, X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and other analytical techniques were employed to characterize these catalysts. The morphology and structure of these DMC catalysts were attributed to the different complexing agents as well as to the different molar ratios of ZnCl₂ to K₃[Fe(CN)₆]. In addition, the catalytic activity was strongly correlated with the morphology and noncrystalline content of DMC catalysts. High-activity catalysts could be prepared by controlling the structure of DMC catalysts by incorporating complexing agents. The active species of DMC catalysts for ring-opening polymerization are Zn²⁺, [Fe(CN)₆]^3–, Cl^–, and the compound of their ligands.     

Synthesis of a model cyclic triblock terpolymer of styrene,isoprene, and methyl methacrylate

The synthesis of a model cyclic triblock terpolymer [cyclic(S‐b‐I‐b‐MMA] of styrene (S), isoprene (I), and methyl methacrylate (MMA) was achieved by the end‐to‐end intramolecular amidation reaction of the corresponding linear α,ω‐amino acid precursor [S‐b‐I‐b‐MMA] under high‐dilution conditions. The linear precursor was synthesized by the sequential anionic polymerization of S, I, and MMA with 2,2,5,5‐tetramethyl‐1‐(3‐lithiopropyl)‐1‐aza‐2,5‐disilacyclopentane as an initiator and amine generator and 4‐bromo‐1,1,1‐trimethoxybutane as a terminator and carboxylic acid generator. The separation of the unreacted linear polymer from the cyclic terpolymer was facilitated by the transformation of the unreacted species into high molecular weight polymers by the evaporation of the reaction solvent and the continuation of the reaction under high‐concentration conditions. The intermediate materials and the final cyclic terpolymer, characterized by size exclusion chromatography, vapor pressure osmometry, thin‐layer chromatography, IR and NMR spectroscopy, exhibited high molecular weight and compositional homogeneity. Dilute‐solution viscosity measurements were used as an additional proof of the cyclic structure. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1476–1483, 2002     

Precipitation polymerization of aniline in the presence of water‐soluble organic acids

The precipitation polymerization of aniline in the presence of organic acids, including toluene‐4‐sulfonic acid, phenylphosphonic acid, 4‐aminophenylphosphonic acid, and acetophosphonic acid, led in one step to conductive polyaniline. The polyaniline showed very good affinity for water and was easily modified to be water‐soluble. In comparison with the widely studied postpolymerization of doped polyaniline, this reaction allowed reasonably good conductivity to be achieved at a lower acid/polyaniline ratio. Moreover, the easy in situ incorporation of the dopant into the polymer structure caused high stability of the created salt; that is, no dedoping was observed after it was washed with water, methanol, or other solvents. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3562–3569, 2002