Abstract
A series of titanium and zirconium complexes with ligands based on di-isopropyl phosphorus-phenylamine and their derivatives were synthesized and characterized. These catalysts were utilized to catalyze the copolymerization of ethylene with N-acetyl-O-(dec-9-enyl)-L-tyrosine ethyl ester with high catalytic activity of 6.63 × 104 g P (mol Ti)−1 h−1 after activation by methylaluminoxane (MAO). The effects of ligand structure, metal atoms (Ti, Zr) and polymerization conditions were investigated in detail. The obtained polymers were characterized by 13C-NMR, DSC, FT-IR, and GPC. The results showed that the obtained copolymer had a high comonomer incorporation rate of 2.56 mol % within the copolymer chain. The melting temperature of the copolymer was up to 138.9 °C, higher than that of the obtained homopolyethylene.
Highlights
Ziegler-Natta catalysts and metallocene catalysts can catalyze the copolymerization of olefins efficiently [1,2,3,4]
We report the copolymers of ethylene with N-acetyl-O-(dec-9-enyl)-L-tyrosine ethyl ester prepared by non-metallocene catalysts with [N, Si, N, P]-type ligands based on diisopropyl phosphorus-phenylamine and their derivatives
The obtained [N, Si, N, P] non-metallocene catalysts (Cat.1–6) were used for ethylene copolymerization, with MAO used as cocatalyst
Summary
Ziegler-Natta catalysts and metallocene catalysts can catalyze the copolymerization of olefins efficiently [1,2,3,4]. They utilized palladium/alkylphosphine-sulfonate catalysts to synthesize copolymers of ethylene with polar monomers featured with higher weight average molecular weight of 1.77 × 105 g/mol by tuning the substituent groups of the phosphorus atom constituent of the ligand [11]. Fujita [12] demonstrated the molecular tailoring of polymer can be realized by changing the ligand structure He prepared Al-PEs by a bis(phenoxy-imine) zirconium complex with methylalumoxane, which confirmed that the stereo-controlling ability of the non-metallocene catalysts can be enhanced. Non-metallocene catalysts with [N, N, O] [18], [N, N, N] [19] and [N, N, O, O] [20,21] ligands were synthesized and carried out for homopolymerization of ethylene and copolymerization of ethylene with α-olefins or polar monomers such as acrylonitrile. We report the copolymers of ethylene with N-acetyl-O-(dec-9-enyl)-L-tyrosine ethyl ester prepared by non-metallocene catalysts with [N, Si, N, P]-type ligands based on diisopropyl phosphorus-phenylamine and their derivatives
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