Ethylene/propylene and ethylene/propylene/5-ethylidene-2-norbornene copolymerizations on metallocene/(2,6-tBu2PhO-)AliBu2 catalyst systems

• Published in: Polymer (Guilford) Vol. 220; p. 123559
• Main Authors: Faingol'd, E.E., Saratovskikh, S.L., Panin, A.N., Babkina, O.N., Zharkov, I.V., Garifullin, N.O., Shilov, G.V., Bravaya, N.M.
• Format: Journal Article
• Language: English
• Published: Kidlington Elsevier Ltd 02.04.2021; Elsevier BV
• Subjects: 5-Ethylidene-2-norbornene; Catalyst; Catalysts; Chemical synthesis; Copolymerization; Copolymers; Elastic properties; Elongation; EPDM; EPM; Ethylene; Isobutylaluminum aryloxide; Mechanical properties; Melting points; Metallocene; Metallocenes; Molecular weight; Polymers; Properties; Propylene; Rubber; Tensile strength; Terpolymerization; Terpolymers; Propylene; EPM; EPDM; Ethylene; 5-Ethylidene-2-norbornene; Copolymerization; Rubber; Properties; Metallocene; Isobutylaluminum aryloxide; Catalyst
• ISSN: 0032-3861; 1873-2291
• DOI: 10.1016/j.polymer.2021.123559

This work explores new catalytic systems for the synthesis of ethylene-propylene (EPM) and ethylene-propylene-diene (EPDM) copolymers. We present the results on ethylene/propylene copolymerization and terpolymerization of ethylene/propylene/5-ethylidene-2-norbornene with different metallocenes activated by (2,6-tBu2PhO-)AliBu2. Metallocenes employed are EtInd2TiMe2, rac-EtInd2ZrMe2, rac-EtInd2HfMe2, rac-Et(2-MeInd)2ZrMe2, rac-Me2Si(2-MeInd)2ZrMe2. The data encompasses catalytic performance of the systems and copolymers properties: composition, molecular weight, thermo-physical, and mechanical characteristics. The highest copolymerization activities were observed for zirconocenes, the lowest — for rac-EtInd2HfMe2. On the other hand, rac-EtInd2HfMe2 shows the best incorporation of both propylene and 5-ethylidene-2-norbornene, yielding polymers with high molecular weights, low crystallinities and melting points. This catalyst system demonstrated the possibility of producing terpolymers with propylene content up to 39 wt % and 5-ethylidene-2-norbornene up to 18 wt %. Copolymers of ethylene with propylene with the highest tensile strength and elongation at break are obtained on rac-Me2Si(2-MeInd)2ZrMe2, while terpolymer with good elastic properties is formed on rac-EtInd2ZrMe2 and rac-EtInd2HfMe2. Copolymers with the best relaxation properties were synthesized on rac-EtInd2HfMe2. [Display omitted] •Catalyst systems: different metallocenes with iso-butylaluminum aryloxide as а non-traditional activator.•Ethylene/Propylene (E/P) copolymerization and E/P/5-Ethyledene-2-norbornene (ENB) terpolymerization.•E/P and E/P/ENB copolymer elastomeric characteristics, stress-strain tests.