Topics in Catalysis

, Volume 52, Issue 9, pp 1203–1210 | Cite as

Polymerization of α-olefins and Hydrogenolysis of the Resulting Polyolefins with Hafnium Hydrides Supported on Silica

  • Géraldine Tosin
  • Catherine C. Santini
  • Jean-Marie Basset
Original Paper


The reaction of Hf(CH2tBu)4 with a silica surface treated at 800 °C affords the unique single site (≡SiO)Hf(CH2tBu)3,1, ((≡SiO) = silica surface ligand). Reaction of 1, with dihydrogen at temperatures (θ) ranging from 100 °C to 250 °C leads to different surface hydrides. At θ ≤ 100 °C, there is formation of [(≡SiO)Hf(CH2tBu)(H)2], 2. For 100 ≤ θ ≤ 200 °C, 2 affords, [(≡SiO)2Hf(H)2], 3, and [(≡SiO)3SiH]. For 150 ≤ θ ≤ 250 °C, 3, is totally converted into [(≡SiO)3Hf(H)], 4, and [(≡SiO)2Si(H)2]. These different surface hafnium hydrides 24, which are obtained simultaneously but in various proportions were referred to as [Hf]θ–H, (θ = 75, 100, 125, 150 and 250 °C). [Hf]150–H is the most active catalyst in α olefin (ethylene, propene, isobutylene) polymerization at 25 °C and in polyolefin depolymerization at 150 °C under H2 atmosphere. Although, there is a clear correlation between the catalytic activity both in polymerization and in depolymerization, and the amount of 3 and 4, it is not possible to establish which between the mono and the bis-hydride is the most active.


Supported hafnium hydride Silica Polymerization Depolymerization 


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Copyright information

© Springer Science+Business Media, LLC 2009

Authors and Affiliations

  • Géraldine Tosin
    • 1
  • Catherine C. Santini
    • 1
  • Jean-Marie Basset
    • 1
  1. 1.Université de Lyon, ICL, LC2P2, Equipe Chimie Organométallique de surface (LCOMS), UMR 5265 CNRS-CPE LyonVilleurbanne CedexFrance

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