Introduction of titanium species into fluorine-modified SiO2- supported Cr-V bimetallic catalyst for ethylene polymerization and ethylene/1-hexene copolymerization

Chromium-vanadium (Cr-V) bimetallic catalysts are prepared by the introduction of vanadium into the Phillips catalyst which is one of the most significant industrial ethylene polymerization catalysts for tuning the Phillips catalyst performances and improving polyethylene properties. In the present work, titanium species were introduced into the fluorine-modified chromium-vanadium bimetallic catalysts (Cr-V-F) and the prepared catalysts were systematically explored. The element content results of multi-component catalysts showed that a competitive inhibition interaction existed between chromium and vanadium, whereas chromium was more preferable to attach to the Ti-SiO2 than vanadium. In addition, ethylene homopolymerization and ethylene/1-hexene copolymerization were carried out and examined with different catalysts. The introduction of titanium into fluorine-modified bimetallic catalysts enhanced the molecular weight (MW) and broadened the molecular weight distribution (MWD) of polyethylene. The MW of the titanium- and fluorine-modified bimetallic catalysts (Cr-V-F/Ti) firstly rose up and then dropped down with the increasing of the Al/Cr molar ratio. The Cr-V-F/Ti catalysts showed slightly depressed hydrogen response and incorporation of 1-hexene. The short-chain branch distribution (SCBD) results, which were characterized by TREF/SSA, showed that the introduction of the titanium species increased the SCB content in low MW fractions and decreased the SCB content in the high Mw fractions of ethylene/1-hexene copolymers obtained from (Cr-V-F/3Ti)600 in contrast to that from (Cr-V-F)600.

Keywords:

Ethylene polymerization , bimetallic catalyst , titanium modification , fluorine modification , short-chain branch distribution