Beiträge der Radiotracertechnik zur Rationalisierung einer großtechnischen Anlage zur Caprolactamproduktion

This paper reviews ways in which radioactive tracer techniques can he used to improve the efficiency of a caprolactam production plant, Residence time spectra and material distributions in different parts of the plant were measured by application of sodium 24, bromine 82 and technetium 99m. The investigations led to improved cumeneoxidators and gave useful informations on the catalytic decomposition of the phenolic tar and the hydrogenation process of phenol. It could he shown that the construction of the lactam extractor must he varied and the results of the tracerexperiments made in the distillation unit contributed to a higher quality of the final product.     

Oxidative Stabilization of Poly(norbornene) Polymers Prepared by Ring Opening Metathesis Polymerization

Polymers prepared by ring opening methathesis polymerization contain double bonds along the backbone and are susceptible to oxidation during high temperature processing or device operation. To overcome this, we report a simple method to improve the oxidative stability of ROMP based polymers by inclusion of a small percentage of monomer functionalized with a radical scavenger in the feedstock. The oxidation induction temperature was improved from 111°C up to 262°C when 8 mol% of the functionalized comonomer was included in the feedstock. Modest improvements in the thermal decomposition temperature were also observed.     

Cu/Ni助催化剂对TiO2光催化制取苯酚性能的影响

以TiO₂纳米粒子为主催化剂, 采用“浸渍-还原法”构筑了铜、镍共负载的二氧化钛基光催化系统。以苯为起始原料, H₂O₂为氧化剂, 研究了Cu/Ni助催化剂对TiO₂可见光催化制取苯酚性能的影响并对Cu/Ni助催化剂的作用机制进行了探讨。结果表明, 在可见光照射下, 纯TiO₂纳米粒子对苯氧化制取苯酚反应没有催化活性。铜、镍的引入可以明显地增强TiO₂可见光催化制取苯酚的活性。当使用负载有铜、镍的TiO₂作为催化剂时, 苯酚的产率可达到18%。结果还表明Cu、Ni之间存在着很强的协同作用。在该协同作用下, Cu、Ni共负载的TiO₂纳米粒子表现出了较单一金属负载的TiO₂纳米粒子高得多的光催化活性。     

Effect of HAP on Stability and Plugging Property of LPFR Dispersion

To improve the stability and plugging property of low-solubility phenol formaldehyde resin (LPFR) in the injection water from Daqing Oilfield, hydrophobically associating polymers (HAP) as a stabilizing agent were used. The size and zeta potential of LPFR, LPFR/HAP molecule aggregates, and turbidity and plugging properties of LPFR dispersions were measured in deionized water, simulation water, and injection water, respectively. The results show that the hydrophobic grouping on the HAP molecule has a similar molecular structure as LPFR, and HAP and LPFR can form complex molecule aggregates in the injection water. The zeta potential of LPFR/HAP molecule aggregates is larger than that of LPFR molecule aggregates. Therefore, the repulsive force operating between LPFR/HAP complex molecule aggregates is increased. HAP enhances the stability of LPFR in the injection water and plugging property of LPFR dispersion in porous medium.     

Synthesis,identification and study of electrical conductivity of the doped copolymer carbazole–phenol formaldehyde

The copolymer carbazole–phenol formaldehyde doped with 4 (4-hydroxy-phenyl azo)-benzene sulfonic acid (PABS), 2,5-dimethyl benzene sulfonic acid (PXSA) and 4-hydroxy-m-benzene disulfonic acid (PDSA) were prepared. These compounds are identified by FT-IR spectroscopy.The conductivity of copolymer carbazole–phenol formaldehyde doped with 4 (4-hydroxy-phenyl azo)-benzene sulfonic acid (PABS), 2,5-dimethyl benzene sulfonic acid (PXSA) and 4-hydroxy-m-benzene disulfonic acid (PDSA) was studied as a function of weight of the dopant compounds; an increase of conductance of the copolymer by doping with PABS is noted; the conductance became equal to 0.000595 ohm⁻¹ for 0.1 g higher conductance for the copolymer when it is doping with PABS.     

Dendrimers Functionalized with Palladium Complexes of N-, N,N-, and N,N,N-Ligands

Pyridine, pyridine imine, and bipyridine imine ligands functionalized by a phenol have been synthesized and characterized, in many cases by X-ray diffraction. Several of these N-, N,N-, and N,N,N,-ligands have been grafted onto the surface of phosphorhydrazone dendrimers, from generation 1 to generation 3. The complexation ability of these monomers and dendrimers towards palladium(II) has been assayed. The corresponding complexes have been either isolated or prepared in situ. In both cases, the monomeric and dendritic complexes have been tested as catalysts in Heck couplings and in Sonogashira couplings. In some cases, a positive dendritic effect has been observed, that is, an increase of the catalytic efficiency proportional to the dendrimer generation.     

Detection of oxygen addition peaks for terpendole E and related indole–diterpene alkaloids in a positive‐mode ESI‐MS

This report describes that a regular positive electrospray ionization mass spectrometry (MS) analysis of terpendoles often causes unexpected oxygen additions to form [M + H + O]⁺ and [M + H + 2O]⁺, which might be a troublesome in the characterization of new natural analogues. The intensities of [M + H + O]⁺ and [M + H + 2O]⁺ among terpendoles were unpredictable and fluctuated largely. Simple electrochemical oxidation in electrospray ionization was insufficient to explain the phenomenon. So we studied factors to form [M + H + O]⁺ and [M + H + 2O]⁺ using terpendole E and natural terpendoles together with some model indole alkaloids. Similar oxygen addition was observed for 1,2,3,4‐tetrahydrocyclopent[b]indole, which is corresponding to the substructure of terpendole E. In tandem MS experiments, a major fragment ion at m/z 130 from protonated terpendole E was assigned to the substructure containing indole. When the [M + H + O]⁺ was selected as a precursor ion, the ion shifted to m/z 146. The same 16 Da shift of fragments was also observed for 1,2,3,4‐tetrahydrocyclopent[b]indole, indicating that the oxygen addition of terpendole E took place at the indole portion. However, the oxygen addition was absent for some terpendoles, even whose structure resembles terpendole E. The breakdown curves characterized the tandem MS features of terpendoles. Preferential dissociation into m/z 130 suggested the protonation tendency at the indole site. Terpendoles that are preferentially protonated at indole tend to form oxygen addition peaks, suggesting that the protonation feature contributes to the oxygen additions in some degrees. © 2014 The Authors. Journal of Mass Spectrometry published by John Wiley & Sons, Ltd.     

Magnetic Titanium Dioxide Nanocomposites for Surface‐Enhanced Resonance Raman Spectroscopic Determination and Degradation of Toxic Anilines and Phenols

Mesoporous M‐TiO₂ NCs, functionalized by PATP, can capture toxic anilines and phenols by azo coupling. Loading these nanodevices with Ag NPs offers the possibility for a sensitive quantitative determination of target compounds by SERRS spectroscopy, which allows multiplex detection because of the specific vibrational fingerprints. Sensitivity and selectivity can be further enhanced by concentrating the hybrid particles by an external magnet and compound‐specific binding (anilines versus phenols). The bound toxic compounds can be degraded by TiO₂‐assisted photocatalysis after removal of the loaded hybrid particles from the sample solution with an external magnet. The degradation process can be enhanced in the presence of plasmonic Ag nanostructures.