Novel poly(aryl ether nitrile ketone) foams and the influence of copolymer structure on the foaming result

Novel poly(aryl ether nitrile ketone) foams were prepared through the batch foaming method with supercritical CO₂ as the blowing agent. Both temperature‐induced and pressure‐induced foaming methods were conducted to examine the influence of nitrile groups on the foaming result. The results indicated that nitrile groups influenced the foaming result by affecting both the viscoelasticity and CO₂ absorption of the polymers. In addition, the CO₂ solubility of the polymers increased with increasing CN content presumably because of the Lewis acid–base nature of the interaction between the CO₂ molecules and the nitrile groups. The cell growth process was assessed by analyzing the influence of foaming temperature and foaming time on the cell morphology. Nanocellular foams with a minimum size of 30–50 nm were achieved by the temperature‐induced foaming method. Moreover, highly expanded foams with a maximum expansion ratio of 23.6 were obtained by the pressure‐induced foaming method. © 2018 Society of Chemical Industry     

Solvent-Aided Crystallization for Biodiesel Purification

The application of solvent-aided crystallization (SAC) is based on the addition of a solvent, here 1-butanol, to crude biodiesel to catalyze the purification process by separating biodiesel from contaminants via crystallization process. Response surface methodology was applied to optimize the process parameters of SAC, represented by biodiesel purity. The purified biodiesel was analyzed by means of gas chromatography-mass spectrometry for the composition of the present fatty acid methyl ester (FAME). Under the predicted optimum process conditions within the experimental ranges for the highest biodiesel purity, the predicted biodiesel purity was 99.375 %.     

Vicious cycle during chemical degradation of sulfonated aromatic proton exchange membranes in the fuel cell application

Weak phase separation and vulnerable linking groups between aromatic units are common setbacks of sulfonated aromatic proton exchange membranes (PEMs) from durability point of view. In this study, sulfonated poly(ether ether ketone) (SPEEK) membranes were exposed to Fenton's solution for a specific time, ranging from 10 to 60 minutes. Chemical structure and morphology evolution, decay in mechanical and thermal stability, and H₂ permeability of SPEEK membranes were evaluated during the chemical degradation. Less-entangled polymeric chains with lower average molecular weight of degraded SPEEK samples diminished mechanical rigidity. In addition, reduction of aromatic rings in each repeat unit led to higher thermal decomposition rate. Furthermore, randomly distributed micro-defects in the SPEEK morphology and an increase in water sorption can reduce the fatigue strength of membranes in the wet-dry cycles. Eventually, hydrogen cross-over rate was gradually increased, and henceforth, accelerated destructive radical formation and degradation can be predicted.     

Synthesis and properties of sulfonated poly(arylene ether ketone sulfone) containing amino groups/functional titania inorganic particles hybrid membranes for fuel cells

In this work, the organic-inorganic hybrid membranes were prepared. The synthesis and properties of the hybrid membranes were investigated. The sulfonated poly(arylene ether ketone sulfone) containing amino groups (Am-SPAEKS) was synthesized by nucleophilic polycondensation. The sol-gel method was used to prepared functional titania inorganic particles (L-TiO₂). The ¹H NMR and FT-IR were performed to verified the structure of Am-SPAEKS and L-TiO₂. The organic-inorganic hybrid membranes showed both good thermal stabilities and mechanical properties than that of Am-SPAEKS. The L-Am-15% membrane exhibited the highest Young's modulus (2262.71 MPa) and Yield stress (62.09 MPa). The distribution of L-TiO₂ particles was revealed by SEM. Compared to Am-SPAEKS, the hybrid membranes showed higher proton conductivities. The L-Am-15% exhibited the highest proton conductivity of 0.0879 S cm⁻¹ at 90 °C. The results indicate that the organic-inorganic hybrid membranes have potential for application in proton exchange membrane fuel cells.     

Comparison of co-current and counter-current flow in a bifunctional reactor containing ammonia synthesis and 2-butanol dehydrogenation to MEK

In this study, a multi-tubular thermally coupled packed bed reactor in which simultaneous production of ammonia and methyl ethyl ketone (MEK) takes place is simulated. The simulation results are presented in two co-current and counter-current flow modes. Based on this new configuration, the released heat from the ammonia synthesis reaction as an extremely exothermic reaction in the inner tube is employed to supply the required heat for the endothermic 2-butanol dehydrogenation reaction in the outer tube. On the other hand, MEK and hydrogen are produced by the dehydrogenation reaction of 2-butanol in the endothermic side, and the produced hydrogen is used to supply a part of the ammonia synthesis feed in the exothermic side. Thus, 30.72% and 31.88% of the required hydrogen for the ammonia synthesis are provided by the dehydrogenation reaction in the co-current and counter-current configurations, respectively. Also, according to the thermal coupling, the required cooler and furnace for the ammonia synthesis and 2-butanol dehydrogenation conventional plants are eliminated, respectively. As a result, operational costs, energy consumption and furnace emissions are considerably decreased. Finally, a sensitivity analysis and optimization are applied to study the effect of the main process parameters variation on the system performance and obtain the minimum hydrogen make-up flow rate, respectively.     

α-羟基环己基苯基甲酮合成工艺研究进展

α-羟基环己基苯基甲酮（光引发剂184）是一种高效光引发剂，因其引发效率高、稳定性好、耐黄变等优势，在电子、涂料、印刷等领域得到广泛的应用。本文根据起始原料不同对α-羟基环己基苯基甲酮的合成方法进行分类，并归纳了不同合成方法的特点。重点介绍了以环己基苯基甲酮为中间体的合成工艺以及其他合成α-羟基环己基苯基甲酮的工艺路线。目前，工业上最常用的Friedel-Crafts酰基化法合成光引发剂184的工艺路线，因为产生的三废多且有毒有害，不符合绿色化工的要求，而将逐渐被淘汰。以格氏反应法合成环己基苯基甲酮继而再合成α-羟基环己基苯基甲酮的工艺路线，因其收率高、污染少等优点而有望成为合成α-羟基环己基苯基甲酮的重要发展方向之一。最后，指出了α-羟基环己基苯基甲酮合成工艺研究的趋势。     

Characterization of four diol dehydrogenases for enantioselective synthesis of chiral vicinal diols

Enantiopure vicinal diols are important building blocks used in the synthesis of fine chemicals and pharmaceutical compounds. Diol dehydrogenase (DDH) mediated stereoselective oxidation of racemic vicinal is an efficient way to prepare enantiopure vicinal diols. In this study, four new bacterial DDHs (AnDDH from Anoxybacillus sp. P3H1B, HcDDH from Hazenella coriacea, GzDDH from Geobacillus zalihae and LwDDH from Leptotrichia wadei) were mined from the GenBank database and expressed in E. coli T7. The four DDHs were purified and biochemically characterized for oxidation activity toward (R)-1-phenyl-1,2-ethanediol, with the optimal reaction condition of pH9.0 (AnDDH), 10.0 (HcDDH) and 11.0 (GzDDH and LwDDH) and the temperatures at 40℃ (AnDDH), 50℃ (HcDDH) and 60℃ (GzDDH and LwDDH), respectively. The four enzymes were stable at the pH from 7.0 to 9.0 and below 40℃. Kinetic parameters of four DDHs showed that the HcDDH from Hazenella coriacea had high activity toward a broad range of vicinal diols. A series of racemic vicinal diols were successfully resolved by recombinant E. coli (HcDDH-NOX) resting cells co-expression of an NADH oxidase (NOX), affording (S)-diols and (1S, 2S)-trans-diols in ≥ 99% ee. The synthetic potential of HcDDH was proved by E. coli (HcDDH-NOX) via kinetic resolution of racemic trans-1,2-indandiol on a 100 ml scale reaction, (S, S)-trans-1,2-indandiol was prepared in 46.7% yield and >99% ee. In addition, asymmetric reduction of four α-hydroxy ketones (10-300 mmol·L^-1) by E. coli (HcDDH-GDH) resting cells resulted in >99% ee and 69-98% yields of (R)-vicinal diols. The current research expands the toolbox of DDHs to synthesize chiral vicinal diols and demonstrated that the mined HcDDH is a potential enzyme in the synthesis of a broad range of chiral vicinal diols.     

二（二烷基甲基）胺萃钯机理研究

本文报告了二(二烷基甲基)胺(7203)从盐酸体系中萃取钯的机理研究。应用等摩尔系列法、饱和法和斜率法测得pH=2.0时萃合物组成为[R_2HNHHPdCI_4]。并通过紫外-可见光谱法研究。证实二(二烷基甲基)胺萃取钯的机理为阴离子交换反应,其萃取方程式为     

Urinary mercury in people living near point sources of mercury emissions

As part of the European Mercury Emissions from Chlor Alkali Plants (EMECAP) project, we tested the hypothesis that contamination of ambient air with mercury around chlor alkali plants using mercury cells would increase the internal dose of mercury in people living close to the plants. Mercury in urine (U-Hg) was determined in 225 individuals living near a Swedish or an Italian chlor alkali plant, and in 256 age- and sex-matched individuals from two reference areas. Other factors possibly affecting mercury exposure were examined. Emissions and concentrations of total gaseous mercury (TGM) around the plants were measured and modeled. No increase in U-Hg could be demonstrated in the populations living close to the plants. This was the case also when the comparison was restricted to subjects with no dental amalgam and low fish consumption. The emissions of mercury to air doubled the background level, but contributed only about 2 ng/m(3) to long-term averages in the residential areas. The median U-Hg levels in subjects with dental amalgam were 1.2 microg/g creatinine (micro/gC) in Italy and 0.6 microg/gC in Sweden. In individuals without dental amalgam, the medians were 0.9 microg/gC and 0.2 microg/gC, respectively. The number of amalgam fillings, as well as chewing, fish consumption, and female sex were associated with higher U-Hg. The difference between the countries is probably due to higher fish consumption in Italy, demethylated methyl mercury (MeHg) being partly excreted in urine. Post hoc power calculations showed that if the background mercury exposure is low it may be possible to demonstrate an increase in U-Hg of as little as about 10 ng/m(3) as a contribution to ambient mercury from a point source.