Neodymium tris-diarylphosphates: Systematic study of the structure-reactivity relationship in butadiene and isoprene polymerisation

作者：Nifant'ev Ilya E^*; Tavtorkin Alexander N; Korchagina Sof'ya A; Gavrilenko Inna F; Glebova Nataliya N; Kostitsyna Nataliya N; Yakovlev Vladimir A; Bondarenko Galina N; Filatova Marina P

来源：Applied Catalysis A: General , 2014, 478: 219-227.

DOI：10.1016/j.apcata.2014.04.007

• Neodymium polymerisation
• Structure-activity relationship
• Aryl phosphate
• Structurally rigid ligand
• 1,3-Butadiene
• Polybutadiene
• Isoprene
• Polyisoprene

The catalytic properties of neodymium tris-phosphates with various diarylphosphate ligands in the stereoregular 1,4-cis-polymerisation of butadiene and isoprene were studied. The considerable variability of the diaryl phosphate structure allowed for the systematic investigation of the dependence of the catalytic properties of neodymium tris-diarylphosphates on the electronic and steric properties of the ligand. Electron-withdrawing substituents (F, Cl, Br) in the aryl moiety increased the catalyst activity of tris-diarylphosphate. Neodymium aryl phosphates containing lipophilic bulky ligands provided the synthesis of polydienes with a monomodal molecular-weight distribution. The optimal catalytic properties demonstrated that the neodymium aryl phosphate prepared from bis(2,6-dimethy1-4-tert-butylpheny1)phosphoric acid showed high activity and ensured a monomodal MWD of polydienes (M-w/M-n similar to 2 for polybutadiene and M-w/M-n similar to 3 for polyisoprene) in various conditions.

• 出版日期2014-5-20