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251.
Joubert J Delbecq F Sautet P Le Roux E Taoufik M Thieuleux C Blanc F Copéret C Thivolle-Cazat J Basset JM 《Journal of the American Chemical Society》2006,128(28):9157-9169
The nature and structure of grafted organometallic complexes on gamma-alumina are studied from a combination of experimental data (mass balance analysis, IR, NMR) and density functional theory calculations. The chemisorptive interactions of two complexes are analyzed and compared. The reaction of [Zr(CH2tBu)4] with alumina dehydroxylated at 500 degrees C gives {[(AlsO)2Zr(CH2tBu)]+[(tBuCH2)(Als)]-}, a bisgrafted cationic complex as major surface species. The DFT calculations show that the reaction with surface hydroxyls is very exothermic and that alkyl transfer on Al atoms is favored. In contrast, [W(CtBu)(CH2tBu)3] reacts with an alumina treated under identical conditions to give selectively a monografted neutral surface complex, [(AlsO)W(CtBu)(CH2tBu)2]. This was inferred by the evolution of 1 equiv of tBuCH3 per grafted W and the presence of remaining hydroxyls. The calculations show that the reaction of [W(CtBu)(CH2tBu)3] with surface hydroxyls is in fact less exothermic and has a considerably higher activation barrier than the one of the Zr complex. Additionally, the transfer of an alkyl ligand onto an adjacent Al center is disfavored, and hence cationic species are not formed. Some ligands of this monoaluminoxy surface complex interact with remaining surface hydroxyls, which explains the complexity of the experimental NMR and IR data. 相似文献
252.
Dawie Joubert 《Macromolecular Symposia》2002,178(1):69-80
The properties of ethylene copolymers, terpolymers and multipolymers prepared with even and uneven carbon number linear and branched α-olefins were compared. The most likely microstructures of ethylene/linear α-olefin copolymers was assigned by considering co-unit bulkiness, average crystallizable sequence lengths and thermal properties. The higher α-olefins were found to be more effective at decreasing density, but peak melting temperatures were higher. In terpolymers where lower α-olefins such as 1-butene and 1-pentene were used as comonomers, density was decreased more than the mathematical average expected from the ratio of comonomers in the terpolymers. Peak melting temperatures were also lower. Based on NMR evidence and the microstructures of the different copolymers the rationale for this occurrence could be ascribed to decreased clustering for these terpolymers. Branched α-olefins produced ethylene co- and terpolymers with significantly decreased densities as compared to the linear α-olefins. Impact strength of these polymers was also substantially higher, even at low comonomer content. Thermal evidence indicates that the microstructure of the co- and terpolymers containing branched α-olefins are very similar to that of the copolymers prepared with linear α-olefins of the same carbon number. 相似文献