Synthesis and properties of optically active aromatic polyimides derived from optically pure 1,1'-bi-2-naphthol

A series of new optically active aromatic polyimides containing axially dissymmetric 1,1'-binaphthalene-2,2-diyl units were prepared from optically pure (R)-(+)-or (S)-(-)-2,2'-bis(3,4-dicarboxyphenoxy)-1,1'-binaphthalene dianhydrides and various aromatic diamines via a conventional two-step procedure that included ring-opening polycondensation and chemical cyclodehydration. The optically pure isomer of dianhydride was prepared by a nucleophilic substitution of optically pure (R)-(+)or (S)-(-)1,1'-bi-2-naphthol with 4-nitrophthalonitrile in aprotic polar solvent and subsequent hydrolysis of the resultant tetranitrile derivatives, followed by the dehydration of the corresponding tetracarboxylic acids to obtain the dianhydrides. These polymers were readily soluble in common organic solvents such as N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and m-cresol, etc., and have glass transition temperatures of 251-296 degrees C, and 5% weight loss occurs not lower than 480 degrees C. The specific rotations of the optically active polyimides ranged from +196 degrees to +263 degrees, and the optical stability and chiroptical properties of them were also studied. (C) 1997 John Wiley & Sons, Inc.

Cure processing modeling and cure cycle simulation of epoxy-terminated poly(phenylene ether ketone) .2. Chemorheological modeling

Chemorheology and corresponding models for an epoxy-terminated poly(phenylene ether ketone) (E-PEK) and 4,4'-diaminodiphenyl sulfone (DDS) system were investigated using a differential scanning calorimeter (DSC) and a cone-and-plate rheometer. For this system, the reported four-parameter chemorheological model and modified WLF chemorheological model can only be used in an isothermal or nonisothermal process, respectively. In order to predict the resin viscosity variation during a stepwise temperature cure cycle actually used, a new model based on the combination of the four-parameter model and the modified WLF model was developed. The combined model can predict the resin viscosity variation during a stepwise temperature cure cycle more accurately than the above two models. In order to simplify the establishment of this model, a new five-parameter chemorheological model was then developed. The parameters in this five-parameter model can be determined through very few rheology and DSC experiments. This model is practicable to describe the resin viscosity variation for isothermal, nonisothermal, or stepwise temperature cure cycles accurately. The five-parameter chemorheological model has also successfully been used in the E-PEK systems with two other curing agents, i.e., the diamine curing agent with the addition of a boron trifluride monoethylamine (BF3-MEA) accelerator and an anhydride curing agent (hexahydrophthalic acid anhydride). (C) 1997 John Wiley & Sons, Inc.

A preliminary study on chemistry of phenoxynaphthacenequinones

A preliminary study on the chemistry of 6-phenoxy-5,12-naphthacenesuinone derivatives was reported, It was found that the main product was 6-(N,N-dimethylamino)-5,12-naphthacenequinone when a reaction of 6-chloro-5,12-naphthacenequinone with 4-hydroxyazobenzenes in DMF was carried out under certain reaction conditions. When the reaction of 6-[4-(4-hydroxyphenyl)isopropyl)phenoxy]-5, 12-naphthacenequinone and epichlorohydrin was carried out in an acetone/DMF(V/V=2/1) mixed solvent and in the presence of K2CO3 and KI, a new phenoxynaphthacenequinone derivative,6,6'-[1-methylethylidenebis(4,1-phenyleneoxy)]bis(5,12-naphthacenequinone), was obtained.

KCl-LiCl共晶熔体中Nd~(3+)和Ho~(3+)的电化学行为

用循环伏安法和恒电流电解后的电位时间曲线法，研究了ＬｉＣｌＫＣｌ熔体中Ｎｄ３＋和Ｈｏ３＋在Ｍｏ电极上的电化学行为。结果表明，Ｎｄ３＋和Ｈｏ３＋在Ｍｏ电极上的还原都为一步３电子可逆过程。其扩散系数分别为：１１３×１０－６和２１４２×１０－５ｃｍ２·ｓ－１（４５０℃），４５０℃下Ｈｏ３＋／Ｈｏ电极对的标准氧化还原电位为２９８７Ｖ（ｖｓ·Ｃｌ／Ｃｌ－１），并讨论了实验值较理论值偏负的原因。

萃取色谱分离-原子发射光谱测定超高纯氧化铽和氧化镝中痕量稀土杂质

研究了２＿乙基己基膦酸单２＿乙基己酯萃取色谱分离＿原子发射光谱测定超高纯Ｔｂ４Ｏ７和Ｄｙ２Ｏ３中痕量稀土杂质，方法可用于纯度（质量分数ｗ）为９９９９９９％～９９９９９９９％Ｔｂ４Ｏ７和Ｄｙ２Ｏ３的分析。在铽和镝的样品中其它稀土杂质的回收率分别为７３％～１３３％和９５％～１２０％，６次测定平均值的相对标准偏差分别为５８％～２２％和７９％～２０％，分离周期为９ｈ和１２ｈ。

Cryoimmobilized enzyme for biosensor construction

A new immobilization material and an immobilization method for a glucose sensor with HEFc (hydroxyethylferrocene) as mediator is described. In the course of three months, the enzyme electrode shows almost no deterioration in its response characteristics. The response time is less than 30 s. The electrode has a wide linear range up to 10 mmol l(-1) with good repeatability. The kinetic parameters have also been calculated.

Luminescence of Pb2+ and energy transfer from Pb2+ to rare earth ions in silicate oxyapatites

The Pb2+ luminescence in a series of silicate oxyapatites Me(2)(Y, Gd)(8)(SiO4)(6)O-2, Me(4)Y(6)(SiO4)(6)O (Me = Mg: Ca, Sr) is reported and discussed in relation to the crystal structure. The maximum wavelengths of the excitation (S-1(0)-P-3(1)) and emission (P-3(1)-S-1(0)) bands of Pb2+ are independent of the Mc:Y ratio (2:8 or 4:6) but they have lower energies in MgY-oxyapatites than in CaY- and SrY-oxyapatites. The Stokes shift of Pb2+ luminescence amounts to 11 100 to 11 400 cm(-1): which does not depend strongly on the host composition. There exists a mutual energy transfer between Pb2+ and Gd3+ in Sr2Gd8(SiO4)(6)O-2. At last, the dependence of the energy transfer efficiency of Pb2+-Sm3+, Tb3+: Dy3+ in Sr-2(La: Gd)(8)(SiO4)(6)O-2 and Ca-2(Y, Gd)(8)(SiO4)(6)O-2 on their doping concentrations was studied in more detail.

Probe beam deflection study of the ion exchange between Prussian blue film or indium hexacyanoferrate film and electrolyte solutions

Probe beam deflection(PBD) technique together with electrochemical techniques such as cyclic voltammetry was used to study the ion exchange in prussian blue(PB) film and its analogue indium hexacyanoferrate (InHCF) chemically modified electrodes, The ion exchange mechanism of PB was verified as following: K2Fe2+FeI(CN)(6)(-e--K+)reversible arrow(+e-+K+)KFe(3+)Fe(I)(CN)(6)(-xe--xK+)reversible arrow(+xe-+xK+) [Fe3+FeI(CN)(6)](x)[KFe3+FeI(CN)(6)](1-x) where on reduction in contact with an acidic KCl electrolyte, H+ enter PB film before K+. Both the cations and anions participate concurrently in the redox process of InHCF, meanwhile K+ ion plays a major role in the whole charge transfer process of this film with increasing radii of anions.

Crystal structure dependence of the luminescence of rare earth ions (Ce3+, Tb3+, Sm3+) in Y2SiO5

The luminescence properties of Ce3+, Tb3+, Sm3+ and energy transfer from Ce3+ to Tb3+ were studied in two modifications of Y2SiO5 (low temperature X(1) type and high temperature X(2) type). The Ce3+ cation shows lower emission energy and larger Stokes shift in X(1)-Y2SiO5 than in X(2)-Y2SiO5, and the emission intensities of Ce3+, Tb3+, Sm3+ in the former are weaker than those in the latter. There exists an energy transfer from Ce3+ to Tb3+ in both types of Y2SiO5, and the transfer efficiency in X(2) type is higher than that in X(1) type. All of these results are discussed in relation to the crystal structure of Y2SiO5.

含羧基的聚乙烯醇胺肟螯合纤维的合成及对钯的吸附

利用（６０）ＣＯγ射线预辐照接枝和胺肟化反应合成了含羧基的聚乙烯醇胺肟（ＰＶＡＡＯ－ＡＡ）螯合纤维。预辐照剂量和接枝单体的比率对接枝率、胺肟基因含量和吸附容量有影响。研究了ＰＶＡＡＯ－ＡＡ螯合纤维对钯的吸附性能。

偏转法研究普鲁士蓝及六氰亚铁铟膜与电解质溶液间的离子效应

用现场偏转法结合循环伏安法研究了普鲁士蓝（ＰＢ）及六氰亚铁铟（ＩｎＨＣＦ）膜的电化学氧化还原过程。证实了ＰＢ膜的离子交换的机理为：且酸性条件下还原ＰＢ膜是Ｈ~＋先于Ｋ~＋进入膜内。还原态的ＩｎＨＣＦ膜氧化时，溶液中的阴阳离子同时参与了该反应，但随着阴离子的增大，Ｋ~＋成为该反应的主要参与者。

COMPATIBILIZATION OF HIGH-DENSITY POLYETHYLENE/POLYISOPRENE BLENDS WITH POLYETHYLENE/POLYISOPRENE THREAD-THROUGH COPOLYMERS

The compatibilization of high density polyethylene (HDPE)/polyisoprene (PI) blends with polyethylene/polyisoprene (PE/PI) ''thread-through'' copolymers was investigated. The proliferating structure of PE/PI with segments chemically identical to HDPE and PI, respectively, is different from that of graft copolymers. Studies showed that the dispersed domain size in the blends was significantly reduced and interfacial adhesion was improved by the compatibilization action of the copolymer. In the differential scanning calorimetry (DSC) analysis, the crystallization peak of HDPE in the blends became broad with adding the copolymer and fractionated crystallization appeared in the HDPE/PI blend compatibilized with the copolymer at a weight ratio of 30/70 while it appeared in the blend without copolymer at a weight ratio of 20/80. DMA results showed that by adding the copolymer, both the glass transition temperature (T-g) of the PI component and the alpha-relaxation of HDPE shifted to lower temperature, demonstrating the enhanced penetration of the two components. Mechanical properties of the blends were improved, especially the elongation at break, by the presence of the copolymers. The characteristic yielding at the fractured surface of the blends compatibilized with the copolymer indicates the fractural behavior of the material changed from brittle to tough.

NMR-STUDY OF MISCIBILITY AND MORPHOLOGY OF POLYIMIDE POLYIMIDE BLENDS

The miscibility and morphology of polyimide/polyimide blends, PEI-E/PTI-E(a)) and PBPI-E/IPTI-E(a)), have been studied by means of C-13 CPMAS NMR technique. The results indicate that PEI-E/PTI-E blends are miscible on a molecular level, but molecular aggregation exists in pure PBPI-E specimen as well as PBPI-E/PTI-E blends with high content of PBPI-E, which vanishes in the blends with high content of PTI-E. When the content of PBPI-E is higher than that of PTI-E, the addition of PTI-E to PBPI-E has almost no effect on the size of the PBPI-E rigid domains, but has a large effect on the populations of the PBPI-E rigid domains. It is the intermolecular charge-transfer interaction that plays a critical role in the miscibility of PEI-E/PTI-E and PBPI-E/PTI-E blends.

SYNTHESIS OF A POLYETHYLENE-GRAFT-POLYSTYRENE COPOLYMER AND ITS COMPATIBILIZATION FOR LINEAR LOW-DENSITY POLYETHYLENE/POLY(PHENYLENE OXIDE) BLENDS

Based on unsteady diffusion kinetics, polyethylene(PE)-graft-polystyrene (PS) copolymers were designed and synthesized with a heterogeneous high yield titanium-based catalyst by copolymerization of ethylene with a PS-macromonomer using 1-hexene as a short chain agent to promote the incorporation of the PS-macromonomer. The presence of 1-hexene facilitated the diffusion of the PS-macromonomer, giving rise to the significantly increased incorporation of the PS-macromonomer. Compatibilization of blends of linear low density polyethylene (LLDPE)/poly(phenylene oxide) (PPO) with the PE-g-PS copolymer were investigated using scanning electron microscopy (SEM) and dynamic mechanical analysis (DMA).

STUDIES ON STRUCTURE OF EO/THF RANDOM COPOLYETHER(I) - NMR-STUDIES ON SOLUTION ACTION AND COMPLEX

The special action of TEO solution was investigated by 1D, 2D-NMR in CDCl3. For the present measurements, when the concentration of TEO was higher in CDCl3, the chemical shift difference (Delta delta) and the peak number of C-13 NMR spectrum were changed with increasing the solution concentration, At lower concentration(< 3% V/V ), the peaks will be closed together for -CH2O- resonance carbon and it is not the appearance of the narrowed, When temperature was changed, the Delta delta value was contrary to the solvent effect, So, the shifts of the resonance carbon in the NMR spectra indicated clearly that the complex formation for the system of CDCl3, and TEO molecular interaction were affected by the experiment temperature and the solution concentration.