A novel linear-hyperbranched multiblock polyethylene was prepared from ethylene monomer alone via chain walking and chain shuttling polymerization in the presence of chain transfer agent (ZnEt 2 ). In the binary catalyst system, R-diimine nickel(II) bromide complex (CatA) produced chain segments with hyperbranched architecture via chain walking, and ansa-ethylenebis(1-η 5 -indenyl)zirconium dichloride (CatB) yielded linear chain segments, while ZnEt 2 facilitated chain exchanges between two active metal centers. The resultant multiblock polyethylene featured a narrow weight distribution and useful combining properties of linear and branched polyethylene. Further, polymers were expediently prepared in an effective and economical polymerization process from ethylene monomer alone.
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