Journal of Molecular Catalysis A-Chemical, Vol.383, 121-127, 2014
Preparation of linear low-density polyethylene from ethylene by tandem catalysis of iron and titanium non-metallocene catalysts
A non-metallocene titanium complex of beta-carbonylenamine derived [O-NS]TiCl3 (2), which can form a tandem catalytic system with difluoro-substituted 2,6-bis(imino)pyridyl iron complex (1), was firstly used as in situ copolymerization catalyst to prepare linear low-density polyethylene (LLDPE) with ethylene as the sole monomer stock and MMAO as the only cocatalyst. During the reaction, 1/MMAO oligomerized ethylene to linear alpha-olefins with high activity and selectivity, while 2/MMAO copolymerized ethylene with the in situ generated alpha-olefins to LLDPE with high activity (up to 6 x 10(6) g/mol Ti h atm). The influences of reaction conditions upon catalytic activity and polymer structures and properties have been researched. The polymers were characterized by differential scanning calorimetry (DSC), high temperature gel permeation chromatography (GPC) and high temperature C-13 NMR spectroscopy and proved to be LLDPE with ethyl, butyl as well as longer branches. The branching degrees were tuned efficiently from 4.6 to 39.3/1000C by different reaction conditions such as reaction temperature, Fe/Ti molar ratio and Al/(Fe + Ti) molar ratio. The melting points, degree of crystallinity and molecular weights also changed correspondingly with reaction conditions. (C) 2013 Elsevier B.V. All rights reserved.
Keywords:Tandem catalysis;In situ copolymerization;Linear low-density polyethylene;Non-metallocene;Branching degree