Microphase separation
drives the structure formation in block copolymers.
Here, functional metallopolymer-grafted diblock copolymers consisting
of polystyrene-block-polyisoprene (PS-b-PI) as polymer backbone featuring low molar mass polyferrocenyldimethylsilane
(PFS) and polyvinylferrocene (PVFc) are synthesized via an iterative
anionic grafting-to polymerization strategy. PS-b-PI block copolymers having about 30 mol % 1,2-polyisoprene moieties
are subjected to platinum-catalyzed hydrosilylation reaction for the
introduction of chlorosilane groups. The Si–Cl moieties are
shown to efficiently react with the active metallopolymers yielding
block-selective metallopolymer-grafted copolymers with 34 vol % PVFc and 43 vol % PFS as evidenced by 1H NMR spectroscopy as well as size exclusion chromatography.
The microphase separation of the functional metallopolymer-grafted
block copolymers is evidenced via TEM measurements revealing fascinating
morphologies. The structure formation of the PVFc-grafted block copolymers
is studied in more detail by TEM, small-angle X-ray scattering, wide-angle
X-ray scattering, and atomic force microscopy measurements evidencing
a lamellar morphology featuring a spherical substructure for the PVFc
segments inside the polyisoprene lamellae.
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