Influence of Polar Modifiers on Microstructure of Polybutadiene Obtained by Anionic Polymerization. Part 2: Lewis Base (σ) Amine-Ether and Ether-Type Polar Modifiers

The influence of Lewis base (σ complex) amine-ether and ether-type polar modifiers on the microstructure of polybutadiene obtained by anionic polymerization was studied. Analysis of FT-IR-ATR, ¹H, and ¹³C NMR spectral data for polybutadienes obtained in the presence of the complexing agents showed that increase of concentration of all tested polar modifiers very strongly promoted formation of 1,2 butadiene isomeric structures, especially increasing the content of vinyl–vinyl and vinyl–trans-1,4 diads.     

A Novel One-Dimensional Copper(II) Complex of a Carboxymethylated Tricyclic Azacrown Ether Derivative Linked by Hydrogen Bonding

The complex [CuL]·H₂O(H₂L=4,13-dioxa-1,7,10,16-tetraaza-1,16:7,10-bis(ethylene)-9,18-diacetic acid cyclooctadecane-8,17-dione) has been synthesized and structurally characterized. It crystallizes in the triclinic system, space group P1 with a=9.0111(7), b=9.4371(7), c=14.3092(11)Å, a=89.846(2), β=81.871(2), γ=65.616(2)°, V=1095.05(14)&Aringsup3;, and Z=1. The structure of the complex consists of two different CuL coordination moieties in which six-coordinated copper ions each have different coordination environments. In both CuL moieties, copper ions are coordinated to two tertiary nitrogen and four oxygen atoms, two from the crown ether ring and two from the pendant carboxylate groups. These two different CuL moieties are linked alternately by water molecules to form an infinite one-dimensional chain structure through hydrogen bonding between the water molecule and the uncoordinated oxygen atom of the carboxyl group.     

Isobaric Vapor-Liquid Equilibria and Densities for the System Ethyl 1,1-Dimethylethyl Ether + 2-Propanol

Vapor-liquid equilibrium (VLE) data at 50, 75, and 94 kPa have been determined for the binary system ethyl 1,1-dimethylethyl ether + 2-propanol, in the temperature range 323-344 K. The measurements were made in an equilibrium still with circulation of both the vapor and liquid phases. Excess volumes have been also determined from density measurements at 298.15 K. The system exhibits positive deviation from ideal behavior and azeotropic behavior in the range of experimental pressures. The excess volume of the system is negative over the whole mole fraction range. The activity coefficients and boiling points of the solutions were well correlated with the mole fraction by the Wohl, Wilson, UNIQUAC, NRTL equations and predicted by the UNIFAC group contribution method. Excess volume data were correlated using the Redlich-Kister expansion.     

CRYSTALLIZATION IN PARTIALLY MOLTEN ORIENTED BLENDS OF POLYCONDENSATES AS REVEALED BY X-RAY STUDIES*

Oriented fibers or films of binary polymer blends from polycondensates were investigated by two-dimensional (2D) wide-angle X-ray scattering (WAXS) during the finishing process of microfibrillar reinforced composite (MFC) preparation, that is, heating to a temperature between the melting temperatures of the two components, isothermal annealing, and subsequent cooling. It is shown that the crystallization behavior in such MFC from polycondensates depends not only on the blend composition, but also on thermal treatment conditions. Poly(ethylene terephthalate)/polyamide 12 (PET/PA12), poly(butylene terephthalate)/poly(ether ester) (PBT/PEE), and PET/PA6 (polyamide 6) composites were prepared in various compositions from the components. Materials were investigated using rotating anode and synchrotron X-ray source facilities. The effect of the annealing time on the expected isotropization of the lower melting component was studied in the PET/PA6 blend. It was found that PA6 isotropization took place after 2 h; shorter (up to 30 min) and longer (up to 8 h) melt annealing results in oriented crystallization due to different reasons. In PET/PA12 composites, the effect of PA12 transcrystallization with reorientation was confirmed for various blend compositions. The relative strength of the effect decreases with progressing bulk crystallization. Earlier presumed coexistence of isotropic and highly oriented crystallites of the same kind with drawn PBT/PEE blend was confirmed by WAXS from a synchrotron source.

     

[K(15-C-5)2]2[Ni(i-mnt)2]·2H2O的合成与结构分析

研究了15-冠-5与K2[Ni(i-mnt)2]{i-mnt=异丁二腈烯二硫醇阴离子,[S2C2(CN)2]2-}的反应,得到的配合物[K(15-C-5)2]2[Ni(i-mnt)2]·2H2O(1)通过元素分析、红外光谱、X射线单晶衍射进行了结构分析。配合物为三斜晶系,空间群P-1。晶体学结构数据:a=1.2674(5)nm,b=1.6317(7)nm,c=1.7771(7)nm,α=102.397(7)°,β=104.828(8)°,γ=93.659(7)°,V=3.442(2)nm3Z=2,F(000)=1412,R1=0.0727,wR2=0.1283。(1)中的[Ni(i-mnt)2]基团通过配体i-mnt的氮原子与两个[K(15-C-5)2]基团之中的钾原子成键,形成稳定的中性配合物。     

TAME合成原料及产品的气相色谱分析

采用SE- 30毛细柱、FID、程序升温气相色谱法分析了TAME合成原料及产品的C5组成 ,解析出 C5的8个组分 ;采用 GDX1 0 4填充柱、TCD对含醚产品进行了分析 ,解析出水、甲醇及 TAME。为试验研究和工业生产提供了一种快速准确的方法。     

Reactivity studies of phenylcalcium iodide towards THF yielding phenyl-free cage compounds - Crystal structures of [{(thf)Ca(O-CHCH2)2}4 · CaO · CaI2] and [(CaO)4 · 4 (thf)3CaI2]

THF proved to be the favoured solvent for the direct synthesis of phenylcalcium iodide. However, ether degradation is the major side reaction in this solvent. Zinc-mediated degradation of THF leads to the formation of the cage compound [{(thf)Ca(O-CHCH₂)₂}₄ · CaO · CaI₂] (1) besides the zincate [(thf)₆Ca] [ZnEt₂Ph₂]. The structure of 1 shows an oxygen-centered Ca₆ octahedron with iodine atoms bound to two opposite corners. Heating of phenylcalcium iodide in THF solution for several hours yields [(CaO)₄ · 4 (thf)₃CaI₂] (2) with a central Ca₄O₄ heterocubane unit. NMR monitoring of the reaction shows that the phenyl groups are converted to benzene due to α-deprotonation of THF.     

甲醇合成二甲醚催化剂的制备与催化性能

采用沉淀法制备CuO-ZnO-Al2O3/ZSM-5和CuO-ZnO-Al2O3-Cr2O3/ZSM-5两种催化剂,用于甲醇脱水制备二甲醚（DME）。用微反-色谱装置对催化剂进行活性评价,用XRD对催化剂进行结构表征。在本实验条件下,以铜锌氧化物的质量分数之比为1∶1,以及铬的质量百分含量为1%,350℃煅烧的催化剂的活性最高。     

Drei Säulensysteme zur Analyse von niederen Alkoholen,Etheralkoholen und Aldehyden in Reinigungsmitteln

Zusammenfassung Es wird eine flüssigkeits-chromatographische Methode vorgestellt, welche die Identifizierung und quantitative Bestimmung von niederen Alkoholen und deren Ethylenoxid-Addukten sowie von niederen Polyolen, Aldehyden und von Harnstoff in wäßrigen Lösungen erlaubt. Die Methode kommt ohne Anreicherungs-oder Derivatisierungsschritte aus, so daß Substanzverluste vor der eigentlichen Chromatographie vermieden sind. Sie wird angewendet bei der Analytik von Reinigungsmitteln unbekanter Zusammensetzung und in der Produktkontrolle.

---

Three column systems for the analysis of short-chain alcohols, ether-alcohols and aldehydes in cleansing agents

Summary A HPLC method is described which allows the identification and determination of short-chain alcohols and their ethylene oxide adducts as well as of short-chain polyols, aldehydes and urea in aqueous solutions.The method does not necessitate the use of concentration or derivatization techniques; the possible loss of substances before running the chromatogram is thereby avoided. The method is used in the analysis of cleansing agents of unknown composition and for product control.

Herrn Dr. Bruno W. Werdelmann zum 60. Geburtstag gewidmet.     

Synthesis of monohydroxy-functionalized triphenylene discotics: green chemistry approach

This paper presents an environmentally benign procedure for the preparation of monohydroxy-functionalized triphenylenes using simple ionic reagents. Pyridinium hydrochloride, pyridinium hydrobromide, N-methyl pyridinium iodide, N-ethyl pyridinium bromide, and 1-n-butyl-3-methyl imidazolium bromide have been employed to prepare various monohydroxypentaalkoxytriphenylenes, which are valuable precursors for the synthesis of a variety of discotic monomers, dimers, oligomers, and polymers.