Highly ordered alignment of a vinyl polymer by host-guest cross-polymerization

Chain alignment can significantly influence the macroscopic properties of a polymeric material, but no general and versatile methodol. has yet been reported to obtain highly ordered cryst. packing of polymer chains, with high stability. Here, we disclose a strategy that relies on ordered crosslinks' to produce polymeric materials that exhibit a cryst. arrangement. Divinyl crosslinkers (2,5-divinyl-terephthalate) were first embedded, as substitutional ligands, into the structure of a porous coordination polymer (PCP), [Cu(terephthalate)triethylenediamine0.5]n. A representative vinyl monomer, styrene, was subsequently polymd. inside the channels of the host PCP. The polystyrene chains that form within the PCP channels also crosslink with the divinyl species. This bridges together the polymer chains of adjacent channels and ensures that, on selective removal of the PCP, the polymer chains remain aligned. Indeed, the resulting material exhibits long-range order and is stable to thermal and solvent treatments, as demonstrated by X-ray powder diffraction and transmission electron microscopy