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Rigid Postmetallocene Catalysts for Propylene Polymerization: Ligand Design Prevents the Temperature-Dependent Loss of Stereo- and Regioselectivities

Georgy P. Goryunov, Mikhail I. Sharikov, Andrei N. Iashin, Jo Ann M. Canich, Sarah J. Mattler, J.R. Hagadorn, Dmitry V. Uborsky, Alexander Z. Voskoboynikov

2021ACS Catalysis19 citationsDOI

Abstract

Energy- and cost-efficient production of polyolefins in solution processes is achieved, inter alia, by conducting polymerizations at high temperatures. Such processes using single-site catalysts (SSCs) based on group 4 complexes are widely used for the production of ethylene copolymers [e.g., linear low-density polyethylene (LLDPE)], but their implementation in the isotactic polypropylene (iPP) segment remains hampered by the challenge of producing high-melting iPP at high temperatures. Known SSCs (mostly metallocenes), when used to produce iPP, suffer from a rapid decline in performance when the process temperature is increased; just a few are reported to produce high-melting iPP at >100 °C. Herein, we report a family of highly active group 4 postmetallocene catalysts featuring a tridentate pyridine-2,6-bis(phenylenephenolate) ligand framework, the rigidity of which results in minimal temperature-dependent losses in the selectivity of propylene insertions and in the melting points of iPP produced at 70 and 100 °C (up to 160.6 and 160.5 °C, respectively).

Topics & Concepts

TacticityLinear low-density polyethyleneCatalysisMaterials sciencePolyethylenePolymerizationEthylenePyridinePolymer chemistrySelectivityLigand (biochemistry)Coordination polymerizationCopolymerChemical engineeringPolymerChemistryOrganic chemistryRadical polymerizationComposite materialBiochemistryEngineeringReceptorOrganometallic Complex Synthesis and CatalysisCarbon dioxide utilization in catalysisSynthetic Organic Chemistry Methods