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Kinetics of the Coordination Polymerization of -olefins Catalyzed by Nickel Diimine Complexes
Peleška, Jan ; Kratochvíla, Jan (referee) ; Pinkas,, Jiří (referee) ; Petrůj, Jaroslav (referee) ; Cihlář, Jaroslav (advisor)
This Ph.D. thesis is focused on kinetic study of propene and hex-1-ene coordination polymerizations initiated by complex [(2-tBuC6H4)N=C(1,8-naphtalenediyl)C=N(2-tBuC6H4)]NiBr2 activated by simple organoaluminium compounds and on product properties. In first three parts proper activators are chosen in model polymerizations. The attention is paid to the reproducibility of polymerizations and analytical methods. The fourth part is focused on propene polymerization kinetics with the aim to define optimal reaction conditions, especially polymerization temperature and time. The four part concerns also properties of polymers. The fifth and sixth parts deal with hex-1-ene polymerization kinetics conducted at various activator/initiator molar ratios and various catalytic precursor concentrations, to find out kinetic orders with respect to catalyst and cocatalyst concentration. Last part is oriented on detail mechanistic investigation of nickel diimine complexes activation process. Results of measurements in presence or absence of monomer enabled to propose new interpretation of UV-vis spectra based on concrete structures of absorbing species.

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