Skip to Main content Skip to Navigation
Journal articles

Zirconocene-catalyzed stereoselective cyclocopolymerization of 2-methyl-1,5-hexadiene with propylene

Abstract : The copolymerization of 2-methyl-1,5-hexadiene (MHD) with propylene has been studied with different single-site group 4 metal catalysts. Systems based on ansa-zirconocene precursors such as rac-{Me2Si(2-Me-4-Ph-Ind}ZrCl2 (1) and C1- or CS-symmetric ansa-{CpCR2Flu}ZrCl2 (2 and 3, respectively), once activated by MAO, are highly active (20–600 kgpol gcat−1 h−1 at 60–70 °C) and yield copolymers in which MHD is cyclopolymerized as methylene-(1-methyl)-1,3-cyclopentane (MMCP) units. 13C NMR studies revealed, depending on the symmetry of the precatalyst used, either highly isotactic (1, 2) or syndiotactic (3) polypropylene (PP) backbones, with isolated MMCP units. Fully trans-diastereoselective cyclopolymerization of MHD was observed with 1/MAO, while a mixture of trans and cis MMCP rings was observed with 2 and 3/MAO. The amount of MMCP units in PP (0.2–1.6 mol%) can be controlled by the amount of MHD in the feed. In contrast, the constrained geometry catalyst system based on {C5Me4SiMe2NtBu}TiCl2 (4) and MAO showed a much lower productivity (ca. 3 kgpol gcat−1 h−1 at 60 °C) and yielded a regioirregular, atactic copolymer in which MHD is simply vinyl-inserted in quite moderate amounts (0.2 mol%).
Document type :
Journal articles
Complete list of metadata
Contributor : Muriel Cadieu Connect in order to contact the contributor
Submitted on : Friday, October 24, 2014 - 11:55:46 AM
Last modification on : Friday, December 10, 2021 - 3:52:06 PM
Long-term archiving on: : Sunday, January 25, 2015 - 10:17:11 AM


Zirconocene-Catalyzed Stereose...
Files produced by the author(s)



Manuela Bader, Gabriel Theurkauff, Katty den Dauw, Christian Lamotte, Olivier Lhost, et al.. Zirconocene-catalyzed stereoselective cyclocopolymerization of 2-methyl-1,5-hexadiene with propylene. Polymer Chemistry, Royal Society of Chemistry - RSC, 2014, 5 (19), pp.5560-5568. ⟨10.1039/C4PY00612G⟩. ⟨hal-01077258⟩



Record views


Files downloads