Preparation and Performance of the Hyperbranched Polyamine as an Effective Shale Inhibitor for Water-Based Drilling Fluid

Seeking effective solutions to control and mitigate the interaction between drilling fluids and clay formations has been a challenge for many years, and various shale inhibitors have shown excellent results in problematic shale formations around the world. Herein, the hyperbranched polyamine (HBPA) inhibitor with a higher ratio of amine groups and obvious tendentiousness in protonation was successfully synthesized from ethylenediamine, acryloyl chloride and aziridine by five steps, in which the metal-organic framework (MOF) was employed as a catalyst for ring-open polycondensation (ROP). The structure and purity were confirmed by nuclear magnetic resonance hydrogen spectroscopy and high-performance liquid chromatography (HPLC) respectively. The HBPA displays more excellent performance than EDA and KCl widely applied in the oil field. After aging at 80°C and 180°C, the YP of a slurry system containing 25 wt.% bentonite and 2 wt.% HBPA are just 8.5 Pa and 5.5 Pa (wt.%: percentage of mass), respectively. The swelling lengths of 2 wt.% HBPA are estimated to be 1.78 mm, which falls by 70% compared with that of freshwater. Under a hot rolling aging temperature of 180°C, the HBPA system demonstrates a significant inhibition with more than 85% shale cuttings recovery rate and is superior to conventional EDA and KCl. Mechanism analysis further validates that the HBPA can help to increase the zeta potential.

Well-controlled Organocatalytic Ring-opening Polymerization of Seven-membered Cyclic Carbonates with Cyclohexyl Fusion

Developing green and well-controlled polymerization methods is of great significance for the preparation of biomedical polymer materials.In this contribution,an efficient organocatalytic ring-opening polymerization(ROP)of a class of seven-membered cyclic carbonates(T6DO,T6HDO,C6DO,C6HDO)containing cis-or trans-cyclohexane structure was established.Organic catalyst 1,5,7-triazabicyclo[4.4.0]dec-5-ene(TBD)promoted living polymerization of these cyclic carbonates to deliver polycarbonate and block copolymer products with predictable molecular weights and narrow dispersity.The robust TBD-mediated ROP at 90°C showcased turnover frequency(TOF)up to 10^(3)h^(−1).The resulting amorphous polycarbonates displayed good thermal stability.

A mini review on strategies for heterogenization of rhodium-based hydroformylation catalysts

Hydroformylation has been widely used in industry to manufacture high value-added aldehydes and alcohols, and is considered as the largest homogenously catalyzed process in industry. However, this process often suffers from complicated operation and the difficulty in catalyst recycling. It is highly desirable to develop a heterogeneous catalyst that enables the catalyst recovery without sacrificing the activity and selectivity. There are two strategies to afford such a catalyst for the hydrofromylation： immobilized catalysts on solid support and porous organic ligand （POL）-supported catalysts. In the latter, high concentration of phosphine ligands in the catalyst framework is favorable for the high dispersion of rhodium species and the formation of Rh-P multiple bonds, which endow the catalysts with high activity and stability respectively. Besides, the high linear regioselectivity could be achieved through the copolymerization of vinyl functionalized bidentate ligand （vinyl biphephos） and monodentate ligand （3vPPh3） into the catalyst framework. The newly-emerging POL-supported catalysts have great perspectives in the industrial hydroformylation.

Noble metal nanoclusters and their in situ calcination to nanocrystals： Precise control of their size and interface with Ti02 nanosheets and their versatile catalysis applications

In this work, we present a new versatile strategy to prepare noble metal （Au, Ag and Cu） nanoclusters on TiO2 nanosheets in large scales with exposed （001） facets with controlled size, crystalline interface, and loading amount. By precise in situ calcination, the metal （M = Au, Ag, and Cu） nanocrystals with controllable size and better crystalline interface with the TiO2 support have been prepared. The potential application of the as-prepared Au, Ag, and Cu nanoclusters on TiO2 nanosheets as potential heterogeneous catalysts for organic synthesis, such as catalytic reduction of 4-nitrophenol to 4-aminophenol, has been demonstrated. After calcination, Au, Ag, and Cu nanocrystals were found to be proficient cocatalysts for photocatalytic H2 evolution, particularly the Au cocatalyst. Based on precise high-resolution transmission electron microscopy （HRTEM） and inductively coupled plasma optical emission spectrometry （ICP-OES） analyses, the flexible control of their size and loading amount as well as their intimate contact with the TiO2 nanosheet enhanced the photocatalytic H2 evolution activity and the sensitivity of the photocurrent response of the film. Furthermore, this aqueous-directed synthesis of metal nanoclusters on a support will generate further interest in the field of nanocatalysis.

Stereoselective Ring-opening Polymerization of rac-Lactide by Bulky Chiral and Achiral N-heterocyclic Carbenes

Despite the extraordinary success has been achieved in metal catalyst-promoted stereoselective ring-opening polymerization（ROP） of rac-lactide（rac-LA）, well-controlled stereoselective rac-LA ROP by organic catalyst still remains a scientific challenge. Here we report our investigations into organocatalytic stereoselective ROP of rac-LA by utilizing novel bulky chiral and achiral N-heterocyclic carbenes（NHC）, 1,3-bis-（1′-naphthylethyl）imidazolin-2-ylidene. The effect of polymerization conditions（e.g. solvent, temperature, alcohol initiator） on ROP behavior by these bulky NHCs has been fully studied, leading to the formation of isotactic-rich stereoblock polylactide（Pi = 0.81） under optimized conditions with high activity（Conv. = 98% in 30 min） and narrow molecular weight dispersity（D = 1.05）.

A theoretical study on the mechanisms of intermolecular hydroacylation of aldehyde catalyzed by neutral and cationic rhodium complexes

In this paper, we used density functional theory(DFT) computations to study the mechanisms of the hydroacylation reaction of an aldehyde with an alkene catalyzed by Wilkinson's catalyst and an organic catalyst 2-amino-3-picoline in cationic and neutral systems. An aldehyde's hydroacylation includes three stages: the C–H activation to form rhodium hydride(stage I), the alkene insertion into the Rh–H bond to give the Rh-alkyl complex(stage II), and the C–C bond formation(stage III). Possible pathways for the hydroacylation originated from the trans and cis isomers of the catalytic cycle. In this paper, we discussed the neutral and cationic pathways. The rate-determining step is the C–H activation step in neutral system but the reductive elimination step in the cationic system. Meanwhile, the alkyl group migration-phosphine ligand coordination pathway is more favorable than the phosphine ligand coordination-alkyl group migration pathway in the C–C formation stage. Furthermore, the calculated results imply that an electron-withdrawing group may decrease the energy barrier of the C–H activation in the benzaldehyde hydroacylation.