Polymerization of Ethylene with Catalyst Mixture in the Presence of Chain Shuttling Agent

Roberto Martins, Letícia Quinello, Giuliana Souza and Maria Marques
Instituto de Macromoléculas Eloisa Mano IMA (UFRJ) Cidade Universitária. Av. Horácio Macedo, 2.030. Centro de Tecnologia. Prédio do Bloco J. Rio de Janeiro. RJ. Brasil fmarques@ima.ufrj.br
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Mixture of two catalysts in one reactor for ethylene/α-olefin copolymerization in the solution process can result in the combination of microstructures related to both catalysts in the polymer framework. Thus, novel polymer configuration is synthesized, which is characterized by containing sequences of monomers produced with each catalyst in the same polymer chain. Adding a reversible transfer agent (CSA) to the binary system enables the production of new block copolymers with enhanced properties. Late transition metal catalysts, such as α-diimine nickel catalyst when activated with methylaluminoxane (MAO) show high activity towards olefin polymerization and produces highly branched homopolymers. On the other hand, C2 symmetry metallocene catalysts produce linear polyethylenes. This paper describes the synthesis of ethylene homopolymer with amorphous and crystalline blocks using a binary mixture containing a nickel catalyst with α-diimine ligand, which produces ф highly branched polyethylene (soft PE) and a metallocene (rac-ethylene bis(H4-indenyl)ZrCl2) that converts ethylene into polyethylene with high activities and melting temperatures (hard PE). The influence of polymerization temperature and CSA concentration were investigated. The polymeric materials were characterized by density, thermal properties, X-ray diffractometry and dynamic-mechanical properties.

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