Heterocene Catalysts for Copolymerization of Hex-1-ene and Polar Vinyl Monomers

The paper proposes a series of promising Zr(IV) complexes and experimentally confirms that, when activated with minimal amounts of modified metylaluminoxane MMAO-12 ([Al]/[Zr] ~20–40), these complexes are able to initiate copolymerization of hex-1-ene with polar vinyl monomers FG-(CH₂)₈CH=CH₂ [where FG is a functional group selected from C(O)NMe₂, CH₂OSiMe₃, C(O)OⁱPr, and CH₂OH]. The prepared copolymers were characterized by ¹H and ¹³C NMR spectroscopy, size exclusion chromatography, and differential scanning calorimetry. Isotactic copolymers of hex-1-ene with 10-undecen-1-ol with polar comonomer content up to 32.2 mol % have been synthesized for the first time. An investigation of the adhesive properties of the prepared copolymers has shown that incorporating 10-undecen-1-ol enhances the adhesive fracture energy by a factor of 32 compared to the respective homopolymer.