Synthesis and properties of noncoplanar rigid‐rod aromatic polyhydrazides and poly(1,3,4‐oxadiazole)s containing phenyl or naphthyl substituents

Two new phenyl‐ and naphthyl‐substituted rigid‐rod aromatic dicarboxylic acid monomers, 2,2′‐diphenylbiphenyl‐4,4′‐dicarboxylic acid ( 4 ) and 2,2′‐di(1‐naphthyl)biphenyl‐4,4′‐dicarboxylic acid ( 5 ), were synthesized by the Suzuki coupling reaction of 2,2′‐diiodobiphenyl‐4,4′‐dicarboxylic acid dimethyl ester with benzeneboronic acid and naphthaleneboronic acid, respectively, followed by alkaline hydrolysis of the ester groups. Four new polyhydrazides were prepared from the dicarboxylic acids 4 and 5 with terephthalic dihydrazide (TPH) and isophthalic dihydrazide (IPH), respectively, via the Yamazaki phosphorylation reaction. These polyhydrazides were amorphous and readily soluble in many organic solvents. Differential scanning calorimetry (DSC) indicated that these hydrazide polymers had glass transition temperatures in the range of 187–234 °C and could be thermally cyclodehydrated into the corresponding oxadiazole polymers in the range of 300–400 °C. The resulting poly(1,3,4‐oxadiazole)s exhibited T_g's in the range of 252–283 °C, 10% weight‐loss temperature in excess of 470 °C, and char yield at 800 °C in nitrogen higher than 54%. These organo‐soluble polyhydrazides and poly(1,3,4‐oxadiazole)s exhibited UV–Vis absorption maximum at 262–296 and 264–342 nm in NMP solution, and their photoluminescence spectra showed maximum bands around 414–445 and 404–453 nm, respectively, with quantum yield up to 38%. The electron‐transporting properties were examined by electrochemical methods. Cyclic voltammograms of the poly(1,3,4‐oxadiazole) films cast onto an indium‐tin oxide (ITO)‐coated glass substrate exhibited reversible reduction redox with E_onset at ?1.37 to ?1.57 V versus Ag/AgCl in dry N,N‐dimethylformamide solution. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6466–6483, 2006     

Viscometric study of gelatin in dilute aqueous solutions

The viscosities of aqueous solutions of gelatin at different temperatures were carefully measured in a common glass‐capillary Ubbelohde viscometer at dilute to extremely dilute concentrations. The adsorption effect that occurred in the viscosity measurements was theoretically analyzed and discussed. A theory based on Langmuir isotherms could adequately describe the existing data. Some structural information was obtained by the use of an iterative fitting procedure to treat the reduced viscosity data, which disclosed that individual gelatin chains underwent a coil‐to‐helix transition as the solution cooled from 40 to 15 °C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1804–1812, 2006     

Sulfonated poly(aryl ether ether ketone ketone)s containing fluorinated moieties as proton exchange membrane materials

A series of sulfonated poly(aryl ether ether ketone ketone)s statistical copolymers with high molecular weights were synthesized via an aromatic nucleophilic substitution polymerization. The sulfonation content (SC), defined as the number of sulfonic acid groups contained in an average repeat unit, could be controlled by the feed ratios of monomers. Flexible and strong membranes in sodium sulfonate form could be prepared by the solution casting method, and readily transformed to their proton forms by treating them in 2 N sulfuric acid. The polymers showed high T_gs, which increased with an increase in SC. Membranes prepared from the present sulfonated poly(ether ether ketone ketone) copolymers containing the hexafluoroisopropylidene moiety (SPEEKK‐6F) and copolymers containing the pendant 3,5‐ditrifluoromethylphenyl moiety (SPEEKK‐6FP) had lower water uptakes and lower swelling ratios in comparison with previously prepared copolymers containing 6F units. All of the polymers possessed proton conductivities higher than 1 × 10^?2 S/cm at room temperature, and proton conductivity values of several polymers were comparable to that of Nafion at high relative humidity. Their thermal stability, oxidative stability, and mechanical properties were also evaluated. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2299–2310, 2006     

Preparation and Characterization of a Cobalt‐Containing Mono‐Phosphine Ligand and its Coordinated Molybdenum Complex

A cobalt‐containing monodentate phosphine [(μ₂‐PPh₂CH₂PPh₂‐κ²P)Co₂(CO)₄][μ₂‐η²‐PhC≡CP(i‐Pr)₂] 2f , was prepared from the reaction of (μ₂‐PPh₂CH₂PPh₂‐κ²P)Co₂(CO)₆ 1 with PhC≡CP(i‐Pr)₂. It was accompanied by an oxidized compound, [(μ₂‐PPh₂CH₂PPh₂‐κ²P)Co₂(CO)₄][μ₂‐η²‐PhC≡CP(=O)(i‐Pr₂)] 2fo during the chromatographic process. Further reaction of 2f with Mo(CO)₆ resulted in the formation of a 2f ‐ligated molybdenum complex 4 , [(μ₂‐PPh₂CH₂PPh₂‐κ²P)Co₂(CO)₄][μ₂‐η²‐PhC≡CP(i‐Pr₂)‐κP]‐Mo(CO)₅.     

新型稀土电子输运材料Tb(AcA)3·phen

Kido等人在文献[1]中报导,在研究有机电致发光(OEL)器件时发现,斓系化合物不能很好地传输载流子.但是,我们在实验中却现Tb(AcA)3phen·不仅是一种很好的OEL发射材料.而且具有很强的电子输运能力.     

Variation of geometric invariant theory quotients

Geometric Invariant Theory gives a method for constructing quotients for group actions on algebraic varieties which in many cases appear as moduli spaces parameterizing isomorphism classes of geometric objects (vector bundles, polarized varieties, etc.). The quotient depends on a choice of an ample linearized line bundle. Two choices are equivalent if they give rise to identical quotients. A priori, there are infinitely many choices since there are infinitely many isomorphism classes of linearized ample line bundles. Hence several natural questions arise. Is the set of equivalence classes, and hence the set of non-isomorphic quotients, finite? How does the quotient vary under change of the equivalence class? In this paper we give partial answers to these questions in the case of actions of reductive algebraic groups on nonsingular projective algebraic varieties. We shall show that among ample line bundles which give projective geometric quotients there are only finitely many equivalence classes. These classes span certain convex subsets (chambers) in a certain convex cone in Euclidean space, and when we cross a wall separating one chamber from another, the corresponding quotient undergoes a birational transformation which is similar to a Mori flip.     

Na2SnO3系催化剂在甲烷氧化偶联反应中的催化性能及表面碱性的探讨

1982年Keller和Bhasin以金属氧化物为催化剂从甲烷制得少量乙烯和乙烷的工作引起了各国研究工作者的重视,此后报道了许多有研究价值的催化剂,其中添加碱金属对提高催化性能所起的作用引起了普遍的关注.Lunsford等首先用添加Li~+的MgO作催化剂,发现催化剂表面碱性增强的同时,生成C_2烃类产物的选择性明显增加.随后Iwamatu等在MgO中添加Na~+及Rb~+盐,Jones等在Mn~(4+)/SiO_2中添加Na~+,Otsuka等在Sm_2O_3中添加LiCl作为甲烷氧化偶联催化剂进行了研究,这些结果均表明,因添加碱金属使催化剂呈现     

合成丙交酯中微量水分分析

合成丙交酯中微量水分分析徐溢，柳胜春（重庆大学化工学院分析教研室６３００４４）关键词丙交酯，微量水，定量分析丙交酯是人工合成骨材料聚乳酸的合成中间体，其性能决定着合成产品的品质，要获得高质量的合成材料，对中间体的分析和监测十分重要。一般要求丙交酯中间...