Synthesis and gas permeability of novel fluorinated poly(phenylene-co-naphthalimide)s

A new class of high-performance polymers [poly(phenylene-co-naphthalimide)s] was prepared through the Ni(0) catalytic coupling of N-(4-chloro-2-trifluromethylphenyl)-5-chloro-1,8-naphthalimide and 2,5-dichlorobenzophenone. The resulting copolymers exhibited high molecular weights (high inherent viscosities) and a combination of desirable properties such as good solubility in dipolar aprotic solvents, film-forming capability, and mechanical properties. The glass-transition temperatures of the copolymers ranged from 320 to 403 degrees C and increased as the content of the naphthalimide moiety increased. Tough polymer films, obtained via casting from N-methylpyrrolidone solutions, had tensile strengths of 64-107 MPa and tensile moduli of 3.4-4.7 GPa. The gas permeability coefficients of the copolymers were measured for H-2, CO2, O-2, CH4, and N-2. They showed oxygen permeability coefficients and permeability selectivity of oxygen to nitrogen (permeability coefficient for O-2/permeability coefficient for N-2) in the ranges of 1.39-4.31 and 4.92-5.38 barrer, respectively.

Ordering-induced micro-bands in thin films of a main-chain liquid crystalline chloro-poly(aryl ether ketone)

Micro-banded textures developed from thin films of a main-chain thermotropic liquid crystalline chloro-poly(aryl ether ketone) in the melt were investigated using transmission electron microscopy (TEM). selective area electron diffraction, and atomic force microscopy techniques. The micro-banded textures were formed in the copolymer thin films after annealing at temperatures between 320 and 330degreesC, where a highly ordered smectic crystalline phase is formed without mechanical shearing. The micro-banded textures displayed a sinusoidal-like periodicity with a spacing of 150 nm and an amplitude of 2 rim. The long axis of the banded texture was parallel to the b-axis of an orthorhombic unit cell. In the convex regions, the molecular chains exhibited a homeotropic alignment, i.e. the chain direction was parallel to the film normal. In the concave re-ions, the molecular chains possessed a tilted alignment. In addition to the effects of annealing temperatures and times, the thickness of the film played a vital role in the formation of the banded texture. A possible formation mechanism of this banded texture vas also suggested and discussed. It was suggested that the micro-bands were formed during cooling.

固相反应法合成Pt/MoO_3及其电催化作用

采用固相合成的方法制得直接甲醇燃料电池催化甲醇氧化的Pt/MoO3.XRD分析、循环伏安测试表明,Pt/MoO3对甲醇的氧化具有较好的催化作用,氧化峰电位出现在0.63V(vs.SCE),峰电流密度可达78.1mA·cm-2.

Facile synthesis and photoluminescent properties of redispersible CeF3, CeF3 : Tb3+, and CeF3 : Tb3+/LaF3 (core/shell) nanoparticles

CeF3, CeF3:Tb3+, and CeF3:Tb3+/LaF3 (core/shell) nanoparticles were prepared by the polyol method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), UV-vis absorption spectra, photoluminescence (PL) spectra, and lifetimes. The results of XRD indicate that the obtained CeF3, CeF3:Tb3+, and CeF3:Tb3+/LaF3 (core/shell) nanoparticles crystallized well at 200 degrees C in diethylene glycol (DEG) with a hexagonal structure. The TEM images illustrate that the CeF3 and CeF3:Tb3+ nanoparticles are spherical with a mean diameter of 7 nm. The growth of the LaF3 shell around the CeF3:Tb3+ core nanoparticles resulted in an increase of the average size (11 nm) of the nanopaticles as well as in a broadening of their size distribution. These nanocrystals can be well-dispersed in ethanol to form clear colloidal solutions. The colloidal solutions of CeF3 and CeF3:Tb3+ show the characteristic emission of Ce3+ 5d-4f (320 nm) and Tb3+ D-5(4)-F-7(J) (J = 6-3, with D-5(4)-F-7(5) green emission at 542 nm as the strongest one) transitions, respectively. The emission intensity and lifetime of the CeF3:Tb3+/LaF3 (core/shell) nanoparticles increased with respect to those of CeF3:Tb3+ core particles.

Evaluation of bioeffects of a long-term administering ChangLe on rat by proton NMR method and biochemical examination

High resolution H-1 nuclear magnetic resonance ( NMR) spectroscopy has been employed to assess long-term toxicological effects of ChangLe (a kind of rare earth complex applied in agriculture). Male Wistar rats were administrated orally with ChangLe at doses of 0, 0.1, 0.2, 2.0, 10 and 20 mg/kg body weight daily, respectively, for 6 months. Urine was collected at-day 30, 60, go and serum samples were taken after 6 months. Many low-molecular weight metabolites were identified by H-1 NMR spectra of rat urine. A decrease in citrate and an increase in ketone bodies, creatinine, DMA, DMG, TMAO, and taurine in the urine of the rats. receiving high doses were found by H-1 NMR spectra. These may mean that high-dosage of ChangLe impairs the specific region of liver and kidney, such as renal tubule and mitochondria. The decrease in citrate and the increase in succinate and alpha-ketoglutarate were attributed to a combination of the inhibition of certain citric acid enzymes, renal tubular acidosis and the abnormal fatty acid catabolism. The information of the renal capillary necrosis could be derived from the increase in DMIA, DMG and TMAO. The increase in taurine was due to hepatic mitochondria dysfunction. The conclusions were supported by the results of biochemical measure. merits and enzymatic assay.

Hydrothermal syntheses and crystal structures of bimetallic cluster complexes [{Cd(phen)(2)}(2)V4O12]center dot 5H(2)O and [Ni(phen)(3)](2)[V4O12]center dot 17.5H(2)O

The hydrothermal reactions of vanadium oxide starting materials with divalent transition metal cations in the presence of nitrogen donor chelating ligands yield the bimetallic cluster complexes with the formulae [{Cd(phen(2))(2)V4O12].5H(2)O (1) and [Ni(phen)(3)](2)[V4O12] . 17.5H(2)O (2). Crystal data: C48H52Cd2N8O22V4 (1), triclinic. P (1) over bar, a = 10.3366(10), b = 11.320(3), c = 13.268(3) Angstrom, alpha = 103.888(17)degrees, beta = 92.256(15)degrees, gamma = 107.444(14)degrees, Z = 1; C72H131N12Ni2O29.5V4 (2), triclinic. P (1) over bar, a = 12.305(3), b = 13.172(6), c = 15.133(4), alpha = 79.05(3)degrees, beta = 76.09(2)degrees, gamma = 74.66(3)degrees, Z = 1. Data were collected on a Siemens P4 four-circle diffractometer at 293 K in the range 1.59degrees < theta < 26.02degrees and 2.01degrees < 0 < 25.01degrees using the omega-scan technique, respectively. The structure of 1 consists of a [V4O12](4-) cluster covalently attached to two {Cd(phen)(2)}(2+) fragments, in which the [V4O12](4-) cluster adopts a chair-like configuration. In the structure of 2, the [V4O12](4-) cluster is isolated. And the complex formed a layer structure via hydrogen bonds between the V4O12](4-) unit and crystallization water molecules.

The single crystal-like banded textures in the films of a thermotropic liquid crystalline poly(aryl ether ketone) containing a lateral chloro group

The banded textures in the films of a thermotropic liquid crystalline poly(aryl ether ketone) containing a lateral chloro group have been studied by means of transmission electron microscopy(TEM), electron diffraction(ED) and atomic force microscopy (AFM). The crystallization-induced Landed texture without external shear can be formed when the thin films were annealed at the temperature range(320-330 degrees C) of the liquid crystalline state from the melt, The results show that the banded regions have high orientation of single crystal based on the orthorhombic packing and the growing direction of the Lands is along the b axis of the crystals, This kind of single crystal-like bands is due to the different orientation of the packing molecular chains, The molecular chains of the dark bands in the bright field electron micrograph are perpendicular to the film plane, while the ones of the bright Lands are tilt along the b axis with the tilt angle upto +/-20 degrees.

The synthesis of phenyl-capped trianiline and teraaniline by a modified-pseudo-high dilution technique and their UV-Vis spectral studies

Phenyl-capped trianiline and tetraaniline in the leucoemeraldine oxidation state were synthesized through a modified-pseudo-high-dilution technique. The chemical oxidation process of these compounds were studied by UV-Vis spectra. It was found that phenyl-capped trianiline in the leucoemeraldine oxidation state was oxidized to its EB form and then decomposed, Phenyl-capped tetraaniline was oxidized to its EB form and then to the pernigraniline oxidation state.

改进的假高稀技术合成聚苯胺三聚体和四聚体及其紫外光谱的研究

提出了一条合成还原态的苯基封端聚苯胺齐聚物的新方法 :即苯胺二聚体的 Schiff碱或苯胺三聚体的 Schiff碱在酸性溶液中缓慢水解 ,形成聚苯胺二聚体和三聚体的盐酸盐 ,这些盐酸盐与二苯胺或 N-苯基 -对苯二胺反应 ,经苯肼还原 ,生成还原态的苯基封端的聚苯胺三聚体和四聚体 .用红外、核磁、元素分析和基底辅助激光解吸质谱对其进行了表征 ,并用紫外光谱对还原态的三聚体和四聚体的化学氧化过程进行了跟踪研究

Homoepitaxial crystallization in films of a thermotropic liquid crystalline chloro-poly(aryl ether ketone)

The homoepitaxial crystallization in the films of a thermotropic liquid crystalline chloro-ply(aryl ether ketone) is studied by transmission electron microscopy (TEM) and electron diffraction (ED). The homoepitaxy takes place in the temperature range 330-320 degreesC, in which a highly-ordered smectic crystalline phase of the copolymer with a single-crystal-like banded structure is formed during the cooling process from the isotropic melt. The homoepitaxial crystallizations with angles of 32 degrees and 122 degrees between the two b axes are the major populations observed, and possess epitaxial contact planes of (100)(I)-(210)(II) and (010)(I)-(210)(II); respectively.

N,N-二甲基甲酰胺存在下块状TiO_2凝胶的制备

在 Ｎ，Ｎ－二甲基甲酰胺（ＤＭＦ）存在下，研究了钛酸丁酯的水解缩聚过程，考察了酸及 ＤＭＦ用量对水解速率的影响。结果表明，随酸和 ＤＭＦ用量的增加，胶凝时间变长。通过 ＴＧ－ＤＴＡ的测定和Ｘ射线衍射分析，表明ＴｉＯ２胶粉末在５００℃时已转变成锐钛矿结构，６００℃时锐钛矿与金红石结构两相并存，到８００℃时全部转化为金红石结构。

Synthesis of poly(phenylenesulfidephenylenamine) by self-polycondensation of methyl-(4-anilinophenyl) sulfide with antimony pentachloride

Poly(phenylenesulfidephenylenamine)(PPSA) an alternating copolymer and the hybrid structure of poly(phenylene sulfide)(PPS) and polyaniline(PAn), was synthesized by self-polycondensation of methyl-(4-anilino-phenyl) sulfide with antimony pentachloride and by the acid-induced self-polycondensation of methyl-(4-anilino-phenyl) sulfoxide.

Half-sandwich cyclopentandienyl molybdenum and tungsten nitrosyl complexes containing bidentate sulfur ligands

Half-sandwich nitrosyl complexes Cp*M(NO)I-2 (M = Mo, or W) react with dithiocarbamates (NaS2CNMe2 and NaS2CNEt2) in THF to form of complexes: Cp*Mo(NO)I (S2CNMe2) (1), Cp*Mo(NO)I(S2CNEt2) (2), Cp*W(NO)I(S2CNMe2) (3) and Cp*W(NO)I(S2CNEt2) (4) in high yields. Treatments of Cp*M(NO)I-2 (M = Mo, W) or [CpMo(NO)I-2](2) with phosphinodithioate (NaS2PMe2) and phosphorodithioate [(NH4)S2P(OMe)(2)] result in complexes: Cp*Mo(NO)I(S2PMe2) (5a), CpMo(NO)I (S2PMe2) (5b), Cp*Mo(NO)(S2PMe2)(2) (6a), CpMo (NO) (S2PMe2)(2) (6b) and Cp*Mo(NO)I[S2P(OMe)(2)] (7), Cp*W(NO)I(S2PMe2) (8), Cp*W(NO) I[S2P(OMe)](2) (9). Treatment of (5a) and (5b) with an excess of NaS2PMe2 gives (6a) and (6b). The complexes have been characterized by their elemental analyses, i.r., H-1, C-13-n.m.r. and by EI-MS spectrometry.

Optical properties of organo-soluble polyimide thin films and their applications in liquid crystal displays

Three organo-soluble polyimide powders have been synthesized. Their imidization was verified by Fourier transform infrared (FTIR) and thermal gravimetric analysis (TGA) techniques. The amorphous morphology of their thin films were confirmed by X-ray diffraction. Polyimide thin films were prepared by solution casting or spin coating. UV-visible transmission spectra of thin films revealed that they are almost transparent in the range of visible light. With in-plane orientation, revealed by FTIR spectra, negative birefringence (Delta n) of thin films were observed, and refractive indices of the thin films along the film plane (n(TE)) and normal to the plane (n(TM)) were measured by a prism coupler. Because of negative birefringence of the thin films, they tan be substituted for the compensation films for twisted nematic liquid crystal displays (TN-LCDs) to extend their viewing angles. In this paper, a 90 degrees C TN-LCD and 120 degrees C TN-LCD were taken as examples to show the compensation effect of thin films of a qualified polyimide. (C) 1998 Elsevier Science S.A. All rights reserved.