Cationic crosslinking of solid dgeba resins with ytterbium(III) trifluoromethanesulfonate as initiator

Solid bisphenol-A epoxy resin of medium molecular mass was cured using a Lewis acid initiator (ytterbium(III) trifluoromethanesulfonate) in three different proportions (0.5, 1 and 2 phr). A kinetic study was performed in a differential scanning calorimeter. The complete kinetic triplet was determined (activation energy, pre-exponential factor, and integral function of the degree of conversion) for each system. A kinetic analysis was performed with an integral isoconversional procedure (free model), and the kinetic model was determined both with the Coats-Redfern method (the obtained isoconversional value being accepted as the effective activation energy) and through the compensation effect. All the systems followed the same isothermal curing model simulated from non-isothermal ones. The growth-of-nuclei Avrami kinetic model A_3/2 has been proposed as the polymerization kinetic model. The addition of initiator accelerated the reaction especially when 2 phr was added. 0.5 and 1 phr showed very few kinetic differences between them.     

Synthesis and characterization of chromocenes containing bulky cyclopentadienyl ligands

Two equivalents of K[Cp′] (Cp′=C₅(i-Pr)₃H₂, C₅(i-Pr)₄H, C₅(t-Bu)₂H₃) react with CrCl₂ in THF to give the corresponding chromocenes, Cp′₂Cr, in good yield. Despite the presence of bulky substituents on the rings that could affect their properties, the complexes are extremely air- and moisture-sensitive, and possess a low-spin ground state. The low-spin paramagnetic nature of each chromocene was confirmed by magnetic susceptibility measurements. The solid-state structure of [C₅(i-Pr)₃H₂]₂Cr was obtained using single crystal X-ray analysis. It displays rigorously parallel rings, with an average Cr–C(ring) distance of 2.17(1)Å; the chromium resides on a crystallographically imposed inversion center. The orientation of the isopropyl groups minimizes unfavorable steric interactions between the rings.