992.
Most research on copolymers with fluorinated monomers has focused on the relationship between fluorinated monomer content
and the corresponding surface structure. However, the influence of the non-fluorinated block on the surface structure of the
copolymer film is unknown. Various molecular weight poly(butyl methacrylates) (PBMA) end-capped with 2-perfluorooctylethyl
methacrylate (FMA) units (PBMA-
ec-FMA) have been synthesized by atom transfer radical polymerization (ATRP). The effect of the PBMA block length on the surface
structure and properties of the polymers both in the solid state and in solution was investigated using various techniques.
X-ray photoelectron spectroscopy (XPS), sum frequency generation (SFG) vibrational spectroscopy and X-ray diffraction (XRD)
analyses indicated that longer PBMA blocks enhanced both the enrichment of the fluorinated moieties and the order of the packing
orientation of the perfluoroalkyl side chains on the surface. This enhancement was attributed mainly to the molecular aggregate
structure of the end-capped polymers with long PBMA blocks in the solution and to the interfacial structure at the air/liquid
interface, which favors the -(CF
2)
7CF
3 moieties self-assembling on the polymer surface during film formation. This observation suggests that the polyacrylate block
structure in fluorinated diblock copolymers, in addition to the fluorinated monomer content, plays an important role in structure
formation on the solid surface.
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