End-functional polyolefins for block copolymer synthesis.

Polyolefins that contain polar functionalities are highly desired because they could extend the range of applications of these low production cost materials by modifying surface and other interfacial properties. Block copolymers containing polyolefin and polar segments are among the most sought-after architectures because of their ability to span the phase boundaries. This review focusses on the end-functionalisation of polyolefins by catalytic olefin polymerisation processes, almost invariably by metal-catalysed routes, followed by the growth polar blocks by various polymerisation techniques.

Polyolefin-Polar Block Copolymers from Versatile New Macromonomers.

A new metallocene-based polymerization mechanism is elucidated in which a zirconium hydride center inserts α-methylstyrene at the start of a polymer chain. The hydride is then regenerated by hydrogenation to release a polyolefin containing a single terminal α-methylstyrenyl group. Through the use of the difunctional monomer 1,3-diisopropenylbenzene, this catalytic hydride insertion polymerization is applied to the production of linear polyethylene and ethylene-hexene copolymers containing an isopropenylbenzene end group.