Study on the structure and property of metallocene ethylene/1-heptene and ethylene/1-octene copolymers

Polyolefin elastomers are typically copolymers of ethylene with 1-butene, 1-hexene, or 1-octene. Other types of comonomers have not been widely applied industrially. The cost of 1-heptene obtained from Fischer-Tropsch synthesis is only half that of 1-octene, making it a viable economical substitute. This work utilized 1-heptene from Fischer-Tropsch synthesis and 1-octene from ethylene oligomerization as research subjects. Eight metallocene POEs based on 1-heptene and 1-octene were synthesized using Me2Si(C5Me4)(NtBu)]TiCl2 (Ti-CGC) catalyst. The copolymers' molecular structures and physical properties were characterized using HT-GPC, Temperature Rising Elution Fractionation (TREF),13C-NMR, DSC, Melt Index (MI), and Tensile tests. Compared to 1-heptene, 1-octene more effectively reduces the melting point and crystallinity, while 1-heptene's stronger comonomer insertion capability facilitates the production of copolymers with higher comonomer content. Similar ternary sequence distributions and molecular dynamics indicate that ethylene/1-heptene and ethylene/1-octene copolymers possess comparable chain microstructures. Both ethylene/1-heptene copolymers and ethylene/1-octene copolymers exhibit excellent toughness and mechanical properties. Although the activity and insertion capacity of ethylene and 1-heptene decrease at low comonomer concentrations, they significantly improve at higher comonomer concentrations. Thus, Fischer-Tropsch synthesis of metallocene ethylene/1-heptene copolymers can effectively reduce raw material costs and be a cost-effective alternative to ethylene/1-octene copolymers.