Metathesis as a versatile tool in oleochemistry

Olefin metathesis, awarded with the Nobel Prize in Chemistry 2005 for Chauvin, Grubbs and Schrock, has emerged as a powerful tool for organic as well as polymer chemistry. In oleochemistry, this reaction is well known and has been applied for many decades. Examples include the functionalization of the double bonds of different oleochemicals or the (direct) polymerization of plant oils via metathesis. More recent developments, particularly the development of better and more robust catalysts, allow for highly efficient cross‐metathesis reactions opening new possibilities for the direct introduction of chemical functionalities. Within this contribution, the development of metathesis in oleochemistry will be discussed, covering self‐metathesis as well as more recent developments in the field of cross‐metathesis that lead to desired platform chemicals.     

Ring‐opening polymerization of D,L‐lactide by rare earth 2,6‐dimethylaryloxide

Ring‐opening polymerization of D,L ‐lactide (LA) has been successfully carried out by using rare earth 2,6‐dimethylaryloxide (Ln(ODMP)₃) as single component catalyst or initiator for the first time. The effects of different rare earth elements, solvents, monomers and catalyst concentration as well as polymerization temperature and time on the polymerization were investigated. The results show that La(ODMP)₃ exhibits higher activity to prepare poly(D,L ‐lactide) (PLA) with a viscosity molecular weight of 4.5 × 10⁴ g mol^?1 and the conversion of 97 % at 100 °C in 45 min. The catalytic activity of Ln(ODMP)₃ has following sequence: La > Nd > Sm > Gd > Er > Y. A kinetic study has indicated that the polymerization is first order with respect to both monomer and catalyst concentration. The apparent activation energy of the polymerization of LA with La(ODMP)₃ is 69.6 kJ mol^?1. The analyses of polymer ends indicate that the LA polymerization proceeds according to ‘coordination–insertion’ mechanism with selective cleavage of the acyl–oxygen bond of the monomer. Copyright © 2004 Society of Chemical Industry     

Übergangene Nachbarn; Erlangung der Parteistellung; Sachlichkeitsgebot

Die Regelung über die Erlangung der Parteistellung übergangener Nachbarn durch Geltendmachung von Einwendungen bis l?ngstens drei Monate nach dem angezeigten Baubeginn ist wegen der Anknüpfung an einen untauglichen Zeitpunkt verfassungswidrig.     

Performance evaluation of a water/silicone oil two‐phase partitioning bioreactor using Rhodococcus erythropolis T902.1 to remove volatile organic compounds from gaseous effluents

BACKGROUND: In the framework of biological processes used for waste gas treatment, the impact of the inoculum size on the start‐up performance needs to be better evaluated. Moreover, only a few studies have investigated the behaviour of elimination capacity and biomass viability in a two‐phase partitioning bioreactor (TPPB) used for waste gas treatment. Lastly, the impact of ethanol as a co‐substrate remains misunderstood. RESULTS: Firstly, no benefit of inoculation with a high cellular density (>1.5 g L^?1) was observed in terms of start‐up performance. Secondly, the TPPB was monitored for 38 days to characterise its behaviour under several operational conditions. The removal efficiency remained above 63% for an inlet concentration of 7 g isopropylbenzene (IPB) m^?3 and at some time points reached 92% during an intermittent loading phase (10 h day^?1), corresponding to a mean elimination capacity of 4 × 10^?3 g L^?1 min^?1 (240 g m^?3 h^?1) for a mean IPB inlet load of 6.19 × 10^?3 g L^?1 min^?1 (390 g m^?3 h^?1). Under continuous IPB loading, the performance of the TPPB declined, but the period of biomass acclimatisation to this operational condition was shorter than 5 days. The biomass grew to approximately 10 g L^?1 but the cellular viability changed greatly during the experiment, suggesting an endorespiration phenomenon in the bioreactor. It was also shown that simultaneous degradation of IPB and ethanol occurred, suggesting that ethanol improves the biodegradation process without causing oxygen depletion. CONCLUSION: A water/silicone oil TPPB with ethanol as co‐substrate allowed the removal of a high inlet load of IPB during an experiment lasting 38 days. Copyright © 2008 Society of Chemical Industry     

Multi-site phase transfer catalyst assisted radical polymerisation of glycidyl methacrylate using potassium peroxydisulphate as initiator – a kinetic study

In this work, the kinetics and mechanism of free-radical polymerisation of glycidyl methacrylate (GMA) using potassium peroxydisulphate (PDS) as water soluble initiator in the presence of synthesized 1, 4-Bis (tributyl methyl ammonium) benzene dichloride (TBMABDC) as multi-site phase transfer catalyst (MPTC) was studied. The polymerisation reactions were carried out under inert and unstirred conditions at constant temperature of 60 ± 1°C in cyclohexane/water biphase media. The role of concentrations of monomer, initiator, catalyst and volume fraction of aqueous phase, solvent polarity and temperature on the rate of polymerisation (Rp) was ascertained. The order with respect to monomer and initiator was found to be unity. The order with respect to catalyst was found to be 0.51. The rate of polymerisation is independent of ionic strength and pH of the medium. However, an increase in the polarity of solvent has slightly increased the Rp value. Based on the results obtained, a suitable kinetic scheme has been proposed to account for the experimental observations and its significance discussed.     

单微乳液中制备Ag/TS-1及丙烯气相环氧化

采用N2H4还原含AgNO3的单微乳液制备了Ag／TS-1催化剂。TEM表征结果表明，Ag高度分散于TS-1之上。以H2、O2存在下的丙烯气相环氧化为探针反应，考察了Ag／TS-1的催化性能。结果表明，采用Ag／TS-1为催化剂，Ag的负载量为1％（质量分数，下同），823 K焙烧后，373 K下反应30 min时，丙烯转化率为1．69％，环氧丙烷（Propylene oxide，PO）选择性为93．2％。当Ag的负载量超过2％时，反应过程中生成大量的热，造成PO的选择性下降。采用Ag的负载量为8％的Ag／TS-1催化剂，消除热效应后，丙烯的转化率为2．46％．PO的选择性为79．2％。     

MIP-CGP工艺专用催化剂CGP-1的开发与应用

阐述了生产汽油组分满足欧Ⅲ排放标准并多产丙烯的催化裂化工艺（简称MIP-CGP）专用催化剂（简称CGP-1）的研究开发与工业应用结果。CGP-1催化剂的基质具有良好的容炭性能，使活性组元受到良好保护，其优势作用在第二反应区得以充分发挥，具有更高的氢转移活性和强的汽油小分子烯烃裂化活性。中国石化九江分公司和镇海炼化公司的MIP-CGP工业试验标定结果表明，与常规FCC相比，采用CGP-1催化剂的MIP-CGP技术在生产烯烃体积分数小于18％的汽油组分的同时，丙烯产率达到8％以上。此外，汽油诱导期大幅提高，抗爆指数增加；总液体收率有所提高，干气产率下降，焦炭选择性良好。     

Inverted Solution Processable OLEDs Using a Metal Oxide as an Electron Injection Contact.

A new type of bottom‐emission electroluminescent device is described in which a metal oxide is used as the electron‐injecting contact. The preparation of such a device is simple. It consists of the deposition of a thin layer of a metal oxide on top of an indium tin oxide covered glass substrate, followed by the solution processing of the light‐emitting layer and subsequently the deposition of a high‐workfunction (air‐stable) metal anode. This architecture allows for a low‐cost electroluminescent device because no rigorous encapsulation is required. Electroluminescence with a high brightness reaching 5700 cd m^–2 is observed at voltages as low as 8 V, demonstrating the potential of this new approach to organic light‐emitting diode (OLED) devices. Unfortunately the device efficiency is rather low because of the high current density flowing through the device. We show that the device only operates after the insertion of an additional hole‐injection layer in between the light‐emitting polymer (LEP) and the metal anode. A simple model that explains the experimental results and provides avenues for further optimization of these devices is described. It is based on the idea that the barrier for electron injection is lowered by the formation of a space–charge field over the metal‐oxide–LEP interface due to the build up of holes in the LEP layer close to this interface.     

镁钴铝类水滑石催化合成安息香甲醚

采用共沉淀法制备了镁钴铝类水滑石化合物(MgCoAl-HTLcs),并用 X 射线衍射、扫描电子显微镜、NH_3程序升温脱附等方法对 MgCoAl-HTLcs 进行了表征,并以 MgCoAl-HTLcs 为催化剂催化苯甲醛与甲醇反应合成安息香甲醚,研究了n(Mg):n(Co):n(Al)、催化剂用量、原料配比、反应温度、反应时间对合成反应的影响。表征结果显示,MgCoAl-HTLcs 的晶相完整,表面主要为弱酸、弱碱性。催化合成安息香甲醚的适宜条件为:MgCoAl-HTLcs 催化剂用量0.10 g(约为原料总质量的0.23%),n(Mg):n(Co):n(Al)=0.4:1.6:1.0,V(苯甲醛):V(甲醇)=3:50,反应温度50℃,反应时间150 min。在此条件下,苯甲醛的平衡转化率达77.49%,安息香甲醚选择性接近100%。为洁净合成安息香甲醚开辟了一条新的途径。     

Optimal and self‐tuning fusion Kalman filters for discrete‐time stochastic singular systems

Based on the optimal fusion estimation algorithm weighted by scalars in the linear minimum variance sense, a distributed optimal fusion Kalman filter weighted by scalars is presented for discrete‐time stochastic singular systems with multiple sensors and correlated noises. A cross‐covariance matrix of filtering errors between any two sensors is derived. When the noise statistical information is unknown, a distributed identification approach is presented based on correlation functions and the weighted average method. Further, a distributed self‐tuning fusion filter is given, which includes two stage fusions where the first‐stage fusion is used to identify the noise covariance and the second‐stage fusion is used to obtain the fusion state filter. A simulation verifies the effectiveness of the proposed algorithm. Copyright © 2008 John Wiley & Sons, Ltd.