High Temperature High Pressure Tandem Polymerization of Ethylene for Synthesis of Ethylene‐1‐Hexene Copolymers from Single Reactor with SNS‐Cr and CGC‐Ti Catalysts

Ethylene‐1‐hexene copolymers are synthesized from ethylene using the tandem catalyst system of bis(2‐dodecylsulfanyl‐ethyl)amine‐CrCl 3 (SNS‐Cr) and [( η 5 ‐C 5 Me 4 )SiMe 2 ( t BuN)]TiCl 2 (CGC‐Ti), with MAO as co‐catalyst. The tandem polymerization is carried out in a high‐temperature high‐pressure solution process. SNS‐Cr trimerizes ethylene and generates 1‐hexene with high selectivity. CGC‐Ti copolymerizes ethylene with 1‐hexene and produces the ethylene‐1‐hexene copolymers. A short period of pre‐trimerization is effective in increasing the 1‐hexene content in copolymer and producing chains with uniform microstructure. The products prepared by this tandem system at high temperature and high pressure exhibit competitive mechanical properties with a commercial ethylene‐1‐octene copolymer.