采用热处理方法提高MEH-PPV单层聚合物有机发光二极管发光性能的研究

对以MEH－PPV为发光层的单层聚合物有机发光二极管（OLED）器件在最佳条件下进行真空热处理，并用金相显微镜观察施加电压后器件的阴极表面形貌。发现处理后的器件阴极表面的气泡及黑斑明显减少。器件的发光性能显著提高。与未经处理的器件相比，最大相对发光强度提高了一个数量级、启亮电压降低了2．0V，半寿命提高了12．7倍。初步分析表明热处理方法提高器件发光性能的主要原因在于有效地减少了器件在工作过程中由于焦耳热产生的某些气体，从而减少阴极表面气泡及黑斑的出现，另一方面，热处理方法也增强了有机发光层与阴极接触界面的结合力，提高电子注入水平。     

Synthesis and copolymerization of new phosphorus‐containing acrylates

Two phosphorus‐containing acrylate monomers were synthesized from the reaction of ethyl α‐chloromethyl acrylate and t‐butyl α‐bromomethyl acrylate with triethyl phosphite. The selective hydrolysis of the ethyl ester monomer with trimethylsilyl bromide (TMSBr) gave a phosphonic acid monomer. The attempted bulk polymerizations of the monomers at 57–60 °C with 2,2′‐azobisisobutyronitrile (AIBN) were unsuccessful; however, the monomers were copolymerized with methyl methacrylate (MMA) in bulk at 60 °C with AIBN. The resulting copolymers produced chars on burning, showing potential as flame‐retardant materials. Additionally, α‐(chloromethyl)acryloyl chloride (CMAC) was reacted with diethyl (hydroxymethyl)phosphonate to obtain a new monomer with identical ester and ether moieties. This monomer was hydrolyzed with TMSBr, homopolymerized, and copolymerized with MMA. The thermal stabilities of the copolymers increased with increasing amounts of the phosphonate monomer in the copolymers. A new route to highly reactive phosphorus‐containing acrylate monomers was developed. A new derivative of CMAC with mixed ester and ether groups was synthesized by substitution, first with diethyl (hydroxymethyl)phosphonate and then with sodium acetate. This monomer showed the highest reactivity and gave a crosslinked polymer. The incorporation of an ester group increased the rate of polymerization. The relative reactivities of the synthesized monomers in photopolymerizations were determined and compared with those of the other phosphorous‐containing acrylate monomers. Changing the monomer structure allowed control of the polymerization reactivity so that new phosphorus‐containing polymers with desirable properties could be obtained. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2207–2217, 2003     

Penta-Coordinate Phosphorus Intermediates Analysis on Phospho-related Proteins

In this paper, based on known crystal structures of square pyramid （SP） and trigonal bipyramid （TBP） penta coordinated phosphorus compounds containing amino acid side chains, such as amino, carboxyl, hydroxyl or thiol, a software for survey the P（5）-structure of phosphorylated proteins was derived. By this software, it was found that 382 of 398 phosphorus related kinases （96%） from current PDB could go through the penta-coordinated phosphorus transition state or intermediate.     

Synthesis of aromatic poly(thioether ketone)

Aromatic poly(thioether ketone)s were prepared by the direct polycondensation of aromatic dicarboxylic acids with aryl compounds containing ether or sulfide structures using phosphorus pentoxide/methanesulfonic acid (PPMA) as a condensing agent and solvent. Polycondensation proceeded smoothly and produced aromatic poly(thioether ketone)s with inherent viscosities up to 0.73 dL/g. The synthesis of substituted aryl ketones by the reaction of substituted benzoic acids with aryl compounds in PMMA was studied in detail to demonstrate the feasibility of the reaction for polymer formation. The thermogravimetry of the aromatic poly(thioether ketone)s showed a 10% weight loss in air and nitrogen at around 450 and 460°C, respectively. © 1992 John Wiley & Sons, Inc.     

Electrochemically induced processes in the formation of phosphorus acid derivatives. 2. The role of polymerization processes in the electrosynthesis of the esters of phosphorus acids from white phosphorus

The mechanism of the electrosynthesis of phosphate esters from white phosphorus was investigated. It was shown that the reaction takes place by two paths, i.e., monomeric (with the participation of dissolved phosphorus) and polymeric (with the participation of phosphorus on the surface of an emulsion drop). It was established that in an alcohol solution of tetraethylammonium iodide the main part of the final product is formed through an intermediate polymeric compound. It was noticed that by studying the dynamics of the accumulation of the dissolved product during electrolysis it is possible to trace the mechanism of reaction of the phosphorus at the individual stages of the process.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420028 Kazan'. V. I. Ul'yanov-Lenin Kazan' State University, 420028 Kazan'. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1328–1333, June, 1992.     

动态广义球对称含荷黑洞的统计熵

利用改进了的brickwall膜模型,计算了动态广义球对称含荷黑洞的熵,研究结果表明,对于动态黑洞,将黑洞熵表示为与视界面积成正比时,则比例系数总与动态黑洞的视界速度有关 关键词： 广义球对称黑洞 黑洞熵 brick-wall膜模型 WKB近似     

Thermal properties of poly(styrene) containing brominated aryl phosphate additives

General purpose poly(styrene) is a large volume commodity polymer widely used in a range of applications. For many of these the presence of an additive to impart some flammability resistance is required. Most commonly, brominated aromatics are used for this purpose. As the polymer undergoes combustion these compounds decompose to generate bromine atoms and/or hydrogen bromide which escape to the gas phase and trap flame propagating radicals. While these species are effective in inhibiting flame propagation they present the opportunity for loss of halogen to the atmosphere. For this reason, the use of these compounds is being limited in some parts of the world. Phosphorus compounds, on the other had, impart a flame retarding influence by promoting char formation at the surface of the burning polymer. This prevents heat feedback to the polymer and consequent pyrolysis to generate fuel fragments. The combination of both bromine and phosphorus present in a single compound might generate a superior flame-retarding additive in that both modes of retardancy might be promoted simultaneously. Should this be the case smaller amounts of additive might be necessary to achieve a satisfactory level of flame retardancy. A series of such additives, brominated aryl phosphates, has been synthesized and fully characterized spectroscopically. Blends of these additives, at various levels, with poly(styrene) have been examined by DSC, TG and in the UL-94 flame test. The flammability of the polymer is dramatically diminished by the presence of the additive.     

Recent studies on phosphorus-bridging carbonyl derivatives: organophosphorus analogs of aldehydes and ketones

Reactions of disodium tetracarbonylferrate, Na₂Fe(CO)₄, with sterically hindered dialkylaminodichlorophosphines, R₂NPCl₂ (R₂N=diisopropylamino, dicyclohexylamino, and 2,2, 6, 6-tetramethylpiperidino) in diethyl ether lead to the air-stable phosphorus-bridging carbonyl derivatives (R₂NP)₂COFe₂(CO)₆ as the major products. The phosphorus-bridging carbonyl group in (i-Pr₂NP)₂COFe₂(CO)₆ has been found to undergo the following types of reactions: 1)Reduction, 2)Acylation, 3)Extrusion of the carbonyl group. The mechanisms of the reactions have been considered.This work was presented at the Workshop «The Modern Problems of Heteroorganic Chemistry» held on the ship «Nikolai Bauman» during the period May 8–13, 1993.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1858–1867, November, 1993.     

炭黑填充聚乙烯材料电阻—温度特性研究

研究了炭黑／聚乙烯导电复合材料的ＰＴＣ特性及在不同条件下的电阻变化。发现ＰＴＣ特性与体积膨胀及聚乙烯晶相的熔融有许多一致性。认为材料的体积膨胀及聚乙烯晶相熔融时炭黑颗粒均匀化扩散导致了电阻随温度上升。在较高温度下，炭黑颗粒在分子链段热运动的推动下会发生相对聚集使电阻不断减小，这是材料出现ＮＴＣ现象的原因。材料总的电阻温度特性是体积膨胀、炭黑向聚乙烯熔融区扩散及相互聚集三个因素共同作用的结果。     

Conductive polyethylene-carbon black composites by elongational-flow injection molding Part 3. Study of the structure and morphology

The morphology and structure of high molecular weight linear polyethylene (M _w 450000) filled with carbon black and processed using molds that introduce an elongational flow component during injection molding has been examined using electron microscopy and x-ray diffraction techniques. The study of fracture surfaces reveals the display of shish-kebabs oriented along the injection direction with segregated longitudinal channels of carbon black particles. Molecular and lamellar changes in orientation are, furthermore, studied across the thickness of the moldings. It is shown that addition of carbon black particles to injection-molded polyethylene induces significant changes in lamellar orientation. Thus, while lamellar overgrowth proceeds perpendicular to the fiber axes within carbon free channels, lamellae grow randomly within carbon-enriched regions where flow is less pronounced.