Preparation and Properties of Poly(Macromonomer)S as a Regular Multi-Branched Polymer

Well-defined multi-branched polystyrenes of controlled branch length and numbers were prepared by the radical polymerizations of ω-vinylbenzyl and ω-methacryloyl polystyrene (PSt) macromonomers of different molecular weights. Intrinsic viscosity measurement and polarization microscopic observation revealed that the poly(macromonomer)s (PMs) of small branch numbers behave like a rigid spherical molecule in solution, while PMs possessing large branch numbers and sufficient branch length behave like a rodlike molecule and form mesomorphic liquid crystalline phase in solution above a certain polymer volume fraction and also in bulk. Miscibility of the PMs with linear PSt depended on the branching architecture of PMs and the molecular weight of linear PSt.