title: Isospecific propylene polymerization with in situ generated bis(phenoxy-amine)zirconium and hafnium single site catalysts.
abstract: Bis(phenoxy-imine) Zr and Hf complexes were activated with (i)Bu3Al or (i)Bu2AlH in conjunction with Ph3CB(C6F5)4 and tested as catalysts for propylene polymerization with emphasis on the enantioselectivity of the isospecific species and the single site polymerization characteristics. The isoselective species was identified as the in situ generated bis(phenoxy-amine) complex whose isoselectivity was sensitive to subtle changes in ligand structure. By employing specific substituents at certain key positions the isotacticity reached an extremely high level comparable to high-end commercial isotactic polypropylenes (Tm > 160 °C). Single site polymerization characteristics depended upon the efficiency and selectivity of the in situ imine reduction which is sensitive to the substituent on the imine nitrogen and the reaction conditions. By using (i)Bu2AlH as a reducing agent, quantitative imine reduction can be achieved with a stoichiometric amount of the reducing agent. This lower alkylaluminum loading is beneficial for the catalyst and significantly enhances the polymerization activity and the molecular weight of the resultant polymer.
authors.affiliation: Mitsui Chemicals Singapore R&D Centre, Pte. Ltd. 50 Science Park Road, #06-08 The Kendall, Singapore Science Park II, Singapore 117406. haruyuki.makio@mitsui-chem.co.jp
authors.forename: Haruyuki
authors.initials: H
authors.lastname: Makio
authors.forename: Aitha Vishwa
authors.initials: AV
authors.lastname: Prasad
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Terao
authors.forename: Junji
authors.initials: J
authors.lastname: Saito
authors.forename: Terunori
authors.initials: T
authors.lastname: Fujita
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D000588:Amines / Q000737:chemistry*; D002384:Catalysis; D006195:Hafnium / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010636:Phenols / Q000737:chemistry*; D058105:Polymerization; D015040:Zirconium / Q000737:chemistry*
chemical_list: D000475:Alkenes; D000588:Amines; D009942:Organometallic Compounds; D010636:Phenols; C042329:phenoxy radical; C013658:propylene; D015040:Zirconium; D006195:Hafnium