Recycling and Separation of Homogeneous Catalyst from Aqueous Multicomponent Mixture by Organic Solvent Nanofiltration.

Organic solvent nanofiltration (OSN) has evolved to an established recycling method for homogeneous catalysts. However, commercial availability has not circumvented the need for classification and the scoping of possible applications for specific solvent mixtures. Therefore, Evonik's DuraMem® 300 was assessed for the recycling of magnesium triflate at two transmembrane pressures from a mixture of ethanol, ethyl acetate and water. Catalyst retention up to 98% and permeability of up to 4.44·10-1∙L∙bar-1∙m-2∙h-1 were possible when less than 25% ethyl acetate was in the mixture. The retention of some of the components in the ternary mixture was observed while others were enriched, making the membrane also suitable for fractioning thereof.

Highly Active N,O Zinc Guanidine Catalysts for the Ring-Opening Polymerization of Lactide.

New zinc guanidine complexes with N,O donor functionalities were prepared, characterized by X-Ray crystallography, and examined for their catalytic activity in the solvent-free ring-opening polymerization (ROP) of technical-grade rac-lactide at 150 °C. All complexes showed a high activity. The fastest complex [ZnCl2 (DMEGasme)] (C1) produced colorless poly(lactide) (PLA) after 90 min with a conversion of 52 % and high molar masses (Mw =69 100, polydispersity=1.4). The complexes were tested with different monomer-to-initiator ratios to determine the rate constant kp . Furthermore, a polymerization with the most active complex C1 was monitored by in situ Raman spectroscopy. Overall, conversion of up to 90 % can be obtained. End-group analysis was performed to clarify the mechanism. All four complexes combine robustness against impurities in the lactide with high polymerization rates, and they represent the fastest robust lactide ROP catalysts to date, opening new avenues to a sustainable ROP catalyst family for industrial use.

Concerning the Role of Supercritical Carbon Dioxide in SN 1 Reactions.

A series of SN 1-type reactions has been studied under various conditions to clarify the role of supercritical carbon dioxide (scCO2 ) as reaction medium for this kind of transformations. The application of scCO2 did not result in higher yields in any of the experiments in comparison to those under neat conditions or in the presence of other inert compressed gases. High-pressure UV/Vis spectroscopic measurements were carried out to quantify the degree of carbocation formation of a highly SN 1-active alkyl halide as a function of the applied solvent. No measureable concentration of carbocations could be detected in scCO2 , just like in other low polarity solvents. Taken together, these results do not support the previously claimed activating effect via enhanced SN 1 ionization due to the quadrupolar moment of the supercritical fluid.

Comprehensive monitoring of a biphasic switchable solvent synthesis.

Biphasic reactions were investigated in a specially designed high pressure set-up that allows simultaneous fibre-optic ATR IR and ATR UV-Vis measurements in both phases. The scope of quantitative spectroscopic measurements is tested on the absorption of CO(2) in hexanol and a biphasic switchable solvent synthesis. For both systems, all substances including dissolved and gaseous CO(2) can be quantified and a constant total mass balance over all phases can be achieved for every component in the reaction system. This confirms that the quantification methods are applicable and the reactor can be applied to gain further insight into the microkinetics and transport phenomena of multiphase reactions.

Ceramic microreactors for heterogeneously catalysed gas-phase reactions.

The high surface to volume ratio of microchannel components offers many advantages in micro chemical engineering. It is obvious, however, that the reactor material and corrosion phenomena play an important role when applying these components. For chemical reactions at very high temperatures or/and with corrosive reactants involved, microchannel components made of metals or polymers are not suited. Hence, a modular microreactor system made of alumina was developed and fabricated using a rapid prototyping process chain. With exchangeable inserts the system can be adapted to the requirements of various reactions. Two heterogeneously catalysed gas-phase reactions (oxidative coupling of methane, isoprene selective oxidation to citraconic anhydride) were investigated to check the suitability of the system at temperatures of up to 1000 degrees C. Apart from the high thermal and chemical resistance, the lack of any blind activity was found to be another advantage of ceramic components.