ZnO/SiO_2-modified rare-earth-metal ternary catalyst bearing quaternary ammonium salts for synthesis of high molecular weight poly (propylene carbonate)

A modified rare-earth-metal catalyst system combined with quaternary ammonium salts（QASs） as cocatalysts was investigated in the alternating copolymerization of CO_2/propylene oxide（PO） to produce poly（propylene carbonate）（PPC）. In the presence of ZnO/SiO_2, the ZnEt_2-glycerine-Y（CCl_3OO）_3 catalyst presented higher activity for CO_2/PO copolymerization, as well as a higher molecular weight of polycarbonate, while maintaining the high carbonate content originating from the neat ZnEt_2-glycerine-Y（CCl_3OO）_3 catalyst. In the presence of QASs bearing different halide anions（F., Cl., and Br.）, the type of the halide anion had a strong influence on the activity of the catalyst for CO_2/PO alternating copolymerization. Only tetramethylammonium fluoride（TMAF） could promote the alternating copolymerization without increasing the by-product. Combined the ZnO/SiO_2 catalyst and TMAF, the catalytic activity for CO_2/PO polymerization increased dramatically compared to the basic ternary catalyst system. The improved catalyst system produced a polymer with a high carbonate unit level equivalent to that of the polycarbonate produced by the basic ZnEt_2-glycerine-Y（CCl_3OO）_3 catalyst system.

A sequential continuous flow synthesis and purification process of calcium dibutyryladenosine cyclophosphate

Calcium dibutyryladenosine cyclophosphate is a widely used cardiovascular drug.The traditional batch synthesis process suffers from long reaction times,tedious operations,and unstable yields.Herein,a sequential continuous flow synthesis combined with a multistage in-line purification process of calcium dibutyryladenosine cyclophosphate was developed.The acylation reaction was completed in a continuous coil reactor at 160℃ in 20 min.And the high toxic solvent pyridine was replaced by acetonitrile.Furthermore,the multistage in-line purification process was integrated into the homemade 3D circular cyclone-type micromixer chip.Combining with the membrane phase separators,the residence time of the purification step was 30 s.The isolated yield of this sequential continuous process was 92%with 99%purity.

Two-step continuous flow process of sodium tanshinone ⅡA sulfonate using a 3D circular cyclone-type microreactor

A sustainable and practical process is presented for the direct synthesis of sodium tanshinone IIA sulfonate(STS).Our approach was inspired by the well-established and industrially applied batch synthetic route for STS production.We constructed a telescoped two-step continuous flow platform.This involved a continuous tanshinone IIA sulfonation and in-line salt formation.For the setup,we constructed a 3D circular cyclone-type microreactor using femtosecond laser micromachining.Compared to the 68%yield for 2 h in batch,the two-step continuous flow had an STS yield of 90%,achieved for a total residence time of<3.0 min under optimal conditions.The proposed continuous flow method vastly simplified the operation and improved procedural safety,while significantly reducing the required acid content and wastewater production.

Computational fluid dynamics simulation and experimental study on mixing performance of a three-dimensional circular cyclone-type microreactor

Microchannels enable the fast and efficient mixing of multiphase fluids.In this study, a millimeter-scale three-dimensional(3D) circular cyclone-type microreactor was designed for the mixing.The flow characteristics and mixing intensity were simulated by computational fluid dynamics simulations at a flow rate range of 12–96 m L/min using a water/ethyl acetate system.In the 3D variable-diameter structure,the microreactor induced paired opposite vortices and abruptly changed the local pressure to achieve a stable turbulent effect within the theoretical range of laminar flow.Tracer injection simulations indicated that sufficient mixing units successfully promote fluid dispersion.Diazo-coupling experiments showed a segregation index of X_S= 0.00,039 within a residence time of 9 s.Extraction experiments on the nbutanol/succinic acid/water system showed that the 3D circular cyclone-type microreactor achieved 100%extraction efficiency(E) in 4.25 s, and the overall volume mass transfer coefficient(K_La) reached 0.05–1.5s^(-1) in 12–96 m L/min.The isolated yield of the phase transfer alkylation and oxidation reactions in the 3D circular cyclone-type microreactor achieved 99% within 36 s, which was superior to the coil microreactor and batch reactor.

Gas phase ethylene polymerization over SiO_(2)-supported organosilyl chromate UCC S-2 catalyst using a high-speed stirred-autoclave reactor

Although an important industrial catalyst for producing high density polyethylene,the SiO_(2)-supported organosilyl chromate UCC S-2 catalyst has not been fully investigated compared with the SiO_(2)-supported oxo chromium Phillips catalyst.In this work,gas phase ethylene polymerization by S-2 catalysts(Cat-1,Cat-2,and Cat-3)was carried out in a high-speed stirredautoclave reactor.The effects of temperature,time,and pressure on kinetics,activity,and product properties were studied.All kinetics were typical built-up types with slow decay.Compared to the simple physical mixtures of Cat-1 and Cat-2,Cat-3 showed higher activity and its product had a broader molecular weight distribution,indicating new active species induced during blending of Cat-1 and Cat-2 in n-hexane.The innovation by a simple catalyst technology created a new application to meet market demands.