Synthesis and solid state structures of macromolecular cylindrical brushes with varying side chain length

Cylindrical brushes with a macromolecular backbone and well-defined side chains of different length (4≤Pnsc≤38) were synthesized by polymerization of macromonomers. The effect of side chain length on the intermolecular order has been investigated by means of X-ray scattering on the melt-extruded samples. The increase of the side chain molar mass results in an increase of the intermolecular distance d according to d∼(Mnsc)0.476. The contour length of the cylindrical brush polymers per main chain monomer unit, lm, was determined to slightly vary with side chain molar mass Mnsc according to lm∼(Mnsc)0.059. The resulting values are much less than the maximum extension, lm=0.25 nm, which is found to be almost independent of side chain molar mass. Also, supermolecular structure formation of a random copolymer brush prepared by radical copolymerization of methacryloyl end functionalized polyvinylpyridine and polymethylmethacrylate macromonomers has been observed and is interpreted as a consequence of intramolecular phase separation.