Syndiospecific Copolymerization of Styrene with para-Methoxystyrene Catalyzed by Functionalized Fluorenyl-Ligated...

The development of efficient catalysts for the copolymerization of nonpolar monomers with polar monomers remains a great challenging task in polymer synthesis. A one-pot reaction of anhydrous LnCl₃ with pyridyl-methylene-functionalized octamethylfluorenyl lithium OctFlu-CH₂PyLi in a 1:1 molar ratio, followed by alkylation with 2 equiv of LiCH₂SiMe₃ in THF afforded the fluorenyl-ligated rare-earth metal bis(alkyl) complexes (OctFlu-CH₂Py)Ln(CH₂SiMe₃)₂(THF) [Ln = Sc (1), Y (2)]. Both complexes were isolated as neutral species and were characterized by NMR spectrum and elemental analysis. Complex 2 was subjected to single-crystal X-ray diffraction, which showed that the whole modified fluorenyl ligand was coordinated to Y³⁺ in the η⁵/κ¹ mode to form a constrained geometry configuration. In the presence of excess AlBu₃, and on activation with 1 equiv of [Ph₃C][B(C₆F₅)₄] in toluene, complexes 1 and 2 became active for both styrene (St) and para-methoxystyrene (pMOS) polymerization, giving polymers with high syndiotacticity (rrrr > 99%) without solvent extraction. Moreover, the ternary catalyst system composed of complex 2/AlBu₃/[Ph₃C][B(C₆F₅)₄] was highly effective for the syndiospecific copolymerization of styrene with pMOS, producing random copolymers with high molecular weights and narrow molecular weight distributions. The contents of pMOS in the copolymers could be easily tuned in a wide range (11-93 mol %) by simply changing the pMOS-to-St feed ratios.