Directed C-H Halogenation Reactions Catalysed by PdII Supported on Polymers under Batch and Continuous Flow Conditions.

A new generation of N-heterocyclic carbene palladium(II) complexes containing vinyl groups in different positions in the backbone of the N-heterocycle have been developed. The fully characterised monomers were copolymerised with divinylbenzene to fabricate robust polymer supported NHC-PdII complexes and these polymers were applied as heterogeneous catalysts in directed C-H halogenation of arenes with a pyridine-type directing group. The catalysts demonstrated medium-high catalytic activity with up to 90 % conversion and 100 % selectivity in chlorination. They are heterogeneous and recyclable (at least six times) with no significant leaching of palladium in batch mode catalysis. The best catalyst was also applied under continuous flow conditions where it disclosed an exceptional activity (90 % conversion) and 100 % selectivity for the mono-halogenated product for at least six days, with no leaching of palladium, no loss of activity and an ability to maintain the original oxidation state of PdII .

Membrane Separation of the Base-Catalyzed Depolymerization of Black Liquor Retentate for Low-Molecular-Mass Compound Production.

One way of valorizing the lignin waste stream from the pulp and paper industries is depolymerizing it into low-molecular-mass compounds (LMMC). However, a common problem in the depolymerization of Kraft lignin is the low yields of small aromatic molecules obtained. In the present work, the combination of the repeated depolymerization of lignin and the separation of LMMC from depolymerized lignin to upgrade them into value-added chemicals was studied. In so doing, we investigated the possibility of depolymerizing black liquor retentate (BLR). The base-catalyzed depolymerization of BLR was performed using a continuous flow reactor at 170-210 °C, with a 2 min residence time. The results obtained indicate that BLR can be depolymerized effectively under the experimental conditions. Depolymerized lignin LMMC can be successfully separated by a GR95PP membrane, and thus be protected from repolymerization. Through combining membrane filtration with base-catalyzed depolymerization, more than half of the lignin could be depolymerized into LMMC. Around 46 mg/g of lignin monomers (guaiacol, vanillin, acetovanillone, and acetosyringone), which can potentially be upgraded to high-valued chemicals, were produced. On the basis of our results, we suggest use of a recycling Kraft lignin depolymerization and filtration process for maximizing the production of LMMC under mild alkaline conditions.