from first principles PP-I-1

OY-II-4Self-Immobilizing Catalysts for Ethylene Polymerization Based onDerivatives of bis(Phenoxy-Imine) Titanium Halide ComplexesIvancheva N.I. 1 , Sanieva D.V. 1 , Molev O.V. 1 , Fedorov S.P. 1 , Oleinik I.V. 2 , Ivanchev S.S. 11 St. Petersburg Department of Boreskov Institute of Catalysis SB RAS,St. Petersburg, Russia2 Vorozhtzov Institute of Organic Chemistry SB RAS, Russiaivanchev@SM2270.spb.eduThe catalysis features and ethylene polymerization mechanism are studied for the following10 functionalized bis(phenoxy-imine) titanium(IV) chloride complexes functionalized with anoxyallyl group containing different number of СН 2 units and located in the para- (1-6) ormeta- (7-10) position in the phenyl ring with respect to the imine nitrogen:1. n=1, R 1 =CMe 2 (Ph), R 2 =H2. n=2, R 1 =CMe 2 (Ph), R 2 =H3. n=3, R 1 =CMe 2 (Ph), R 2 =H4. n=1, R 1 = R 2 =CMe 2 (Ph)5. n=2, R 1 = R 2 =CMe 2 (Ph)6. n=3, R 1 = R 2 =CMe 2 (Ph)7. n=1, R 1 =CMe 2 (Ph), R 2 =H8. n=2, R 1 =CMe 2 (Ph), R 2 =H9. n=1, R 1 = R 2 =CMe 2 (Ph)10. n=2, R 1 = R 2 =CMe 2 (Ph)Figure 1. Kinetic plot of ethylenepolymerization using the catalyst system 1.The kinetic plots of ethylene polymerization (Fig. 1) indicate the transition from the initiallyhomogeneous to heterogeneous polymerization mechanism after the catalyst systemimmobilization on the synthesized polyethylene (PE).The duration of the process stage following the homogeneous mechanism and the overallpolymerization kinetics are determined by the bis(phenoxy-imine) complex structure. Thecatalyst immobilization onto the resulting polymer is experimentally confirmed by theappearance of an intrinsic band in FTIR spectra of the obtained PE.The study of ethylene polymerization kinetic features as a function of the catalyst structurerevealed a significant role of the substituents in the phenoxy-group and oxyallyl groupposition in the phenyl ring bound to the imine nitrogen.GPC characterization of the progressive changes of PE obtained at the homogeneous andheterogeneous stages of the polymerization allowed us to clarify the polymerizationmechanisms at these steps as a function of the applied catalyst structure.The characterized catalyst systems demonstrated significant activity and can be effectivelyapplied in the production of polyethylenes for various purposes.91