Nickel-based ethylene polymerization catalysts have unique features, being able to produce macromolecules with a variable content of branches, resulting in polymers ranging from semicrystalline plastics to elastomers to hyperbranched amorphous waxes and oils. In addition to Brookhart's α-diimine catalysts, iminopyridine Ni(II) complexes are among the most investigated systems. We report that Ni(II) complexes bearing aryliminopyridine ligands with bulky substituents both at the imino moiety and in the 6-position of pyridine afford either hyperbranched low molecular weight polyethylene oils or prevailingly linear crystalline polyethylenes or both depending on the ligand structure and the reaction conditions. The formation of multiple active species in situ is suggested by analysis of the post-polymerization catalyst residues, showing the partial reduction of the imino function. Some related arylaminopyridine Ni(II) complexes were also synthesized and tested, showing a peculiar behavior, i.e. the number of branches of the produced polyethylenes increases while ethylene pressure increases.

PEBAX-2533/metal salt/Al salt membranes were prepared for mixed olefin/paraffin separation. PEBAX-2533 with 80% ether group and 20% amide group was suggested as the polymer matrix for comparison of separation performance according to the functional group ratio in copolymer PEBAX. In addition, Al salts were used to stabilize metal ions for a long time as additives. High permeance was expected with the proportion of high ether groups since these functional groups provided relatively permeable regions. As a result, the PEBAX-2533 composite membrane showed a selectivity of 5 (propylene/propane) with 10 GPU. However, the permeance of membrane was not unexpectedly improved and the selectivity was reduced. The result was analyzed by SEM, FT-RAMAN and TGA, including FT-IR. The reduction in separation performance was determined by FT-IR. From these results, in order to stabilize the metal ions interacting with the polymer through Al(NO3)3, it was concluded that specific ratio of amide group was needed in PEBAX as polymer matrix.

Olefin metathesis of ethyl linoleate (EL) was investigated under different conditions of substrate amount, temperature, and catalyst. Second-generation Grubbs catalyst (G2) was used in experiments at 20 and 50 ºC for 24 and 48h, whereas first-generation Grubbs catalyst (G1) and [RuCl₂(PPh₃)₂perhydroazepine] (LN) were used in experiments at 50 ºC for 24h, with the latter also being investigated in the presence or absence of SnCl₂ as co-catalyst. Catalytic products were analyzed for GC-MS and discussed in terms of relative percent of the metathesis products. With G2 as catalyst, GC-MS chromatograms were similar in all the amounts of EL investigated at 50 ºC for 24h, except for ethyl hexadec-9-enoate (compound K), which was obtained with different percentage as a function of EL amount (55% for 2 and 5 mL and 65% for 8 mL). An α,ω-dicarboxylic acid with m/z = 444.00 (compound L) was produced from the experiments at 50 ºC for 24h with similar percentage as a function of EL amount. However, the relative percentage of L changed with the increase of EL volume in the experiments at 20 ºC (ca. 18, 27, and 28%, with 2, 5, and 8 mL of EL, respectively). The olefin metathesis of EL conducted by G1 reached lower selectivity than that conducted by G2 for 24h at 50 ºC. Several intense peaks reached with G1 were similar to those obtained with G2, in addition to new peaks of medium intensity. Compound L showed higher m/z, similar to that presented with G2, but with lower relative proportion in the mixture. LN was inert for olefin metathesis of EL; however, it was activated in the presence of SnCl₂ at 50 ºC for 24h. Different compounds and selectivity as a function of the catalyst type and reaction conditions were obtained.

New ligand platforms of the type p- or m-Ph{-CR(3,6-tBu2Flu)(Cp)}2 (para-, R = Me (2a), H (2b); meta-, R = Me (2c)) were synthesized via nucleophilic addition of the 3,6-tBu2-fluorenyl-anion onto the parent phenylene-bridged difulvenes (1a‒c). The corresponding discrete homodinuclear zirconium and hafnium bis(dichloro ansa-metallocene) complexes, Ph[{-CR(3,6-tBu2Flu)(Cp)}MCl2]2 (p-, R = Me (3a-Zr2, 3a-Hf2), R = H (3b-Zr2); m-, R = Me (3c-Zr2) were prepared by salt metathesis reactions. An attempt to generate in situ a heterodinuclear complex 3a-Zr-Hf was also undertaken. For the first time, Atmospheric Pressure PhotoIonization (APPI) mass-spectrometric data were obtained for all dinuclear compounds and found to be in excellent agreement with the simulated ones. Preliminary studies on the catalytic performances of these dinuclear complexes, upon activation with MAO, in ethylene homopolymerization and ethylene/1-hexene copolymerization revealed a few differences as compared to those of the monometallic analogues. In particular, slightly lower molecular weights and greater formation of short methyl and ethyl branches were obtained with the dinuclear systems.

There is currently much interest in avoiding precious metals in Catalysis. The devel-opment of nickel catalysts to replace palladium in the Mizoroki-Heck reaction is a relevant case in this line of research since both elements share many chemical features. This contri-bution focuses on -Phenyl elimination in alkylnickel complexes. This is the microscopic reverse of olefin insertion (or carbometallation), a fundamental step of the Heck cycle that is usually considered irreversible and selectivity-determining. However, the potential reversibil-ity of carbometallation is generally concealed by the facile beta-hydrogen elimination that follows. Where -hydrogen elimination is hindered, beta-aryl elimination may ensue. We have previously shown that cationic 2-methyl-2-phenylpropyl (neophyl) palladium com-plexes supported by bidentate ligands experience -Ph elimination, which can be seen as an example of olefin de-insertion. In this contribution, we report that -phenyl elimination can also occur in their nickel analogs, in which case fast hydrolyses of the resulting phenyl product can follow the reaction. We investigated the mechanism of these processes and compared their feasibility for nickel and palladium catalysts using DFT calculations. These results are relevant information for the design of nickel-based catalysts for the Heck reac-tion.

Mn-promoted bulk iron catalysts with high specific surface area (82-211 m2.g-1) were synthesized by coprecipitation followed by drying under supercritical conditions. The catalysts were tested in the CO2 hydrogenation reaction. The Mn-promoted iron catalysts showed better textural properties than the bare Fe2O3 catalyst, allowing better dispersion of the active phase, easier reduction of iron oxide, better carburization of iron oxides and higher catalytic activity than the bare Fe2O3 catalyst. The best activity results were obtained by catalyst promotion with a very low amount of Mn (Mn/Fe ratio of 0.05). Upon steady-state conditions (T=340 ºC, total pressure of 20 bar and H2/CO2=3), this catalyst showed high CO2 conversion (44.2%) and selectivity to C2-C4 hydrocarbons (68%, olefin to paraffin ratio of 0.54), while the selectivity to C5+ hydrocarbons, CH4 and CO was about 3.2, 38.5 and 5%, respectively. A close correlation was found between catalyst textural properties and CO2 conversion. The most active MnFe-0.05 catalyst shows high stability during 72 h of reaction related to low amount of soft coke formation and catalyst activation through the formation of χ-Fe5C2 phase during the on-stream reaction.

In the past few years, micromodels have become a useful tool for visualizing flow phenomena in porous media with pore structures, e.g., the multifluid dynamics in soils or rocks with fractures in natural geomaterials. Micromodels fabricated using glass or silicon substrates incur high material cost; in particular, the microfabrication-facility cost for making a glass or silicon-based micromold is usually high. This may be an obstacle for researchers investigating the two-phase-flow behavior of porous media. A rigid thermoplastic material is a preferable polymer material for microfluidic models because of its high resistance to infiltration and deformation. In this study, cyclic olefin copolymer (COC) was selected as the substrate for the micromodel because of its excellent chemical, optical, and mechanical properties. A delicate micromodel with a complex pore geometry that represents a two-dimensional (2D) cross-section profile of a fractured rock in a natural oil or groundwater reservoir was developed for two-phase-flow experiments. Using an optical visualization system, we visualized the flow behavior in the micromodel during the processes of imbibition and drainage. The results show that the flow resistance in the main channel (fracture) with a large radius was higher than that in the surrounding area with small pore channels when the injection or extraction rates were low. When we increased the flow rates, the extraction efficiency of the water and oil in the mainstream channel (fracture) did not increase monotonically because of the complex two-phase-flow dynamics. These findings provide a new mechanism of residual trapping in porous media.

Cyclic olefin copolymer (COC) is a novel type of thermoplastic polymer gaining the attention of the scientific community in electronic, optoelectronic, biomedicine and packaging applications. Despite the benefits in the use of COC like undoubted optical transparency, chemical stability, good water-vapor barrier and biocompatibility, its original hydrophobicity restricts its wider applicability and optimization of its performances. Presently, we report on the optical, and morphological properties of the films of COC covered with Ti in selected areas. The layer of Ti on COC was deposited by pulsed lased deposition processing. The Ti/COC film was characterized by UV-Vis spectroscopy indicating that its transmittance in the visible region decreased by about 20% with respect to the pristine polymer. The quality of the deposited Ti was assessed with the morphology by scanning electron (SEM) and atomic force microscopies (AFM). The modification of the wettability was observed by the sessile drop method indicating a reduction of the native hydrophilicity.