(Co)polymerization of ethylene via nonmetallocene catalysts with diphenyl phosphoroso schiff‐base ligand

Ruthenium(II) complexes of Schiff base derived from cycloalkylamines (cycloalkyl ¼ cyclopentyl (1a), cyclohexyl (1b), cycloheptyl (1c), and cyclooctyl) (1d) were synthesized: [RuCl(CyPen-Salen)(PPh 3) 2 ] (2a), [RuCl(CyHex-Salen)(PPh 3) 2 ] (2b), [RuCl(CyHep-Salen)(PPh 3) 2 ] (2c), and [RuCl(CyOct-Salen)(PPh 3) 2 ] (2d). The Schiff base-Ru II complexes 2a-d were characterized by elemental analysis, FTIR, UV-Vis, 1 H-, 13 C and 31 P NMR, and cyclic voltammetry. The complexes 2a-d were evaluated as catalytic precursors for ROMP of norbornene (NBE) and for ATRP of methyl methacrylate (MMA). The syntheses of polynorbornene (polyNBE) via ROMP with complexes 2a-d as pre-catalysts were evaluated under different reaction conditions ([HCl]/[Ru], [EDA]/[Ru], [NBE]/[Ru], and temperature). The highest yields of polyNBE were obtained with [NBE]/[HCl]/[Ru] ¼ 5000/25/1 M ratio in the presence of 5 mL of EDA for 60 min at 50 C. MMA polymerization via ATRP was conducted using the complexes 2a-d in the presence of ethyla-bromoisobutyrate (EBiB) as initiator. The catalytic tests were evaluated as a function of the reaction time using the initial molar ratio of [MMA]/[EBiB]/[Ru] ¼ 1000/2/1 at 85 C. The linear correlation of ln([MMA] 0 /[MMA]) and time indicates that the concentration of radicals remains constant during the polymerization and that the ATRP of MMA mediated by 2a-d proceeds in a controlled manner. Molecular weights increased linearly with conversion, however, the experimental molecular weights were higher than the theoretical ones.

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(Co)polymerization of ethylene via nonmetallocene catalysts with diphenyl phosphoroso schiff‐base ligand

Cited by 4 publications

References 37 publications

Ethylene polymerization over TiSSP composite-supported MAO with bis[N-(3-tert-butylsalicylidene) cycloheptylamine] titanium dichloride complex

Ethylene polymerization over TiSSP composite-supported MAO with bis[N-(3-tert-butylsalicylidene) cycloheptylamine] titanium dichloride complex

Zirconium Complexes

Ruthenium(II) complexes of Schiff base derived from cycloalkylamines as pre-catalysts for ROMP of norbornene and ATRP of methyl methacrylate

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