Jean-Francois Lahitte

Towards green membranes: preparation of cellulose acetate ultrafiltration membranes using methyl lactate as a biosolvent

Ultrafiltration membranes were prepared using cellulose acetate (CA) as a polymer, LiCl and CaCl2 as porogens and methyl-(S)-lactate as a solvent. CA, methyl lactate and the porogens used in this work are obtained from renewable resources; they are biodegradable, non-toxic and non-volatile organic compounds. Flat sheet ultrafiltration membranes were prepared by the phase inversion technique. A molecular weight cut-off between 15 and 35 kDa (polyethylene glycol) and pure water permeability between 13 and 177 litres h− 1m− 2 bar− 1 were obtained. These parameters are in the ideal range for water treatment industry. Improvement of pollutant degree and ecotoxicity of the process was evaluated by ‘green’ metrics by the P (pollutants, persistent and bioaccumulative) and E (ecotoxicity) parameters. Both of these variables were recorded as zero using our method. This study represents a step ahead towards the production of ultrafiltration polymeric membranes by a ‘greener’ process than current methods.

Macromonomers as well-defined building blocks in macromolecular engineering

The present work compares the efficiency of different polymerization methods to design well-defined comb-shaped structures based on macromonomers. Anionic polymerization remains the method of choice and allows the control of polymerization degree of the main chain and the length of the grafts. The presence of an active chain end on the backbone enabled the synthesis of a new type of hyperbranched polymers by reaction, with appropriate low molar multifunctional compounds. Free radical polymerization is less efficient for the controlled homopolymerization of macromonomers but less sensitive to the presence of impurities. It requires in most cases long fractionation procedures to access well defined comb-shaped fractions characterized by high molar masses. The controlled free radical polymerization constitutes an interesting alternative. The homopolymerization of macromonomers with late transition metal catalysts was also examined and comb-shaped polymers characterized by a syndiotactic backbone and atactic grafts could be obtained.

Transition metal-based homopolymerisation of macromonomers

Abstract Since their first utilisation in 1958 for the synthesis of graft copolymers, macromonomers have raised increasing interest because of their ability to provide an easy access to a large number of (co)polymers of different chemical natures and various controlled topologies (comb-like, bottlebrush, star-like, graft copolymers...) exhibiting very different solution or solid-state properties compared to their linear homologues. During the first decades, the (co)polymerisation of macromonomers was based on poorly controlled free radical polymerisations. Therefore, it was difficult to obtain polymers in a controlled manner. With the appearance of Ring Opening Metathesis Polymerisation (ROMP) or of new free radical processes such as Atom Transfer Radical Polymerisation (ATRP) that allow control of molar masses, and of Ziegler–Natta-type polymerisation that allows control of the tacticity of the polymacromonomer backbone, these processes have been increasingly utilised for macromonomer (co)polymerisations. In this paper, a review of the results published in the literature regarding the homopolymerisation of macromonomers in the presence of transition metal is presented.

Wet Air Oxidation of Formic Acid Using Nanoparticle-Modified Polysulfone Hollow Fibers as Gas–Liquid Contactors

Catalytic wet air oxidation (CWAO) using membrane contactors is attractive for remediation of aqueous pollutants, but previous studies of even simple reactions such as formic acid oxidation required multiple passes through tubular ceramic membrane contactors to achieve high conversion. This work aims to increase single-pass CWAO conversions by using polysulfone (PS) hollow fibers as contactors to reduce diffusion distances in the fiber lumen. Alternating adsorption of polycations and citrate-stabilized platinum colloids in fiber walls provides catalytically active PS hollow fibers. Using a single PS fiber, 50% oxidation of a 50 mM formic acid feed solution results from a single pass through the fiber lumen (15 cm length) with a solution residence time of 40 s. Increasing the number of PS fibers to five while maintaining the same volumetric flow rate leads to over 90% oxidation, suggesting that further scale up in the number of fibers will facilitate high single pass conversions at increased flow rates. The high conversion compared to prior studies with ceramic fibers stems from shorter diffusion distances in the fiber lumen. However, the activity of the Pt catalyst is 20-fold lower than in previous ceramic fibers. Focusing the Pt deposition near the fiber lumen and limiting pore wetting to this region might increase the activity of the catalyst.

Membrane Reactor Based on Hybrid Nanomaterials for Process Intensification of Catalytic Hydrogenation Reaction: an Example of Reduction of the Environmental Footprint of Chemical Synthesis from a Batch to a Continuous Flow Chemistry Process

Membrane processes represent a well matured technology for water treatment with low environmental footprints compared to other type of processes. We have now combined this technology with nanomaterials, ionic liquids (negligible vapor pressure), and poly(ionic liquids) in order to enlarge the field of applications while benefiting from the advantages of membranes. We have modified flat sheet water filtration membrane and used it as both catalytic support and reactor with the advantages to make the reaction and the separation of products in only one step. For this purpose, catalytic metallic nanoparticles of palladium (diameter of ca. 2 nm) were synthesized in a gel-poly(ionic liquid) layer grafted at the surface of polymeric filtration membranes by UV-photografting method. The so obtained catalytic membrane was successfully applied in the hydrogenation of trans-4-phenyl-3-buten-2-one in forced flow-through configuration, which gave full conversion in a few seconds (2.6 s) showing advantages over the batch reactor process (in that case, palladium nanoparticles were synthesized in the ionic liquid [MMPIM][NTf2] (1,2-dimethyl-3-propylimidazolium bis-(trifluoromethylsulfonyl)imide)). Nevertheless, the catalytic membrane used in submerged mode no more prevailed over the batch reactor. Catalytic nanoparticles remain highly active in the membrane after 12 cycles of reaction without need of recuperation. Results were compared to one obtains with a similar system in batch reactor conditions, showing high efficiency of our process in term of selectivity and reactivity, combined to an important compactness, the productivity of the catalytic hollow fiber membrane reactor and permitting to operate at larger scale with promising results in an environmental friendly way in term of energy and product (metal, solvent) consuming.