Direct Synthesis of Partially Chain-Straightened Propylene Oligomers and P-MA Co-Oligomers Using Axially Flexible Shielded Iminopyridyl Palladium Complexes.

In this study, a series of partially chain-straightened propylene oligomers and functional propylene−methyl acrylate (P-MA) co-oligomers were synthesized with 8-alkyl-iminopyridyl Pd(II) catalysts. The molecular weight and polar monomer incorporation ratio could be tuned by using Pd(II) catalysts with various 8-alkyl-naphthyl substituents (8-alkyl: H, Me, and n-Bu). In propylene oligomerization, all the 8-alkyl-iminopyridyl Pd(II) catalysts convert propylene to partially chain-straightened (119−136/1000 C) oligomers with low molecular weights (0.3−1.5 kg/mol). Among the catalysts, Pd1 with non-substituent (H) on the ligand showed the highest activity of 5.4 × 104 g/((mol of Pd) h), generating oligomers with the lowest molecular weight (Mn: 0.3 kg/mol). Moreover, polar-functionalized propylene-MA co-oligomers with very high incorporation ratios (22.8−36.5 mol %) could be obtained in the copolymerization using these 8-alkyl-iminopyridyl Pd(II) catalysts. Additionally, Pd1 exhibited the best performance in propylene-MA copolymerization as it displayed the highest MA incorporation ratio of up to 36.5 mol%. All the three catalysts are capable of generating partially chain-straightened P-MA co-oligomers and the activities decrease gradually while the molecular weight increases with the increasing steric hindrance of the alkyl substituent (H < Me < n-Bu). Compared to Pd4 with the rigid 8-aryl substituent, the flexible 8-alkyl-iminopyridyl Pd(II) catalysts (Pd1-3) not only showed much higher activities in the propylene oligomerization, but also yielded P-MA co-oligomers with significantly higher incorporation ratios in the propylene co-oligomerization.