title: Highly ordered alignment of a vinyl polymer by host-guest cross-polymerization.
abstract: Chain alignment can significantly influence the macroscopic properties of a polymeric material, but no general and versatile methodology has yet been reported to obtain highly ordered crystalline packing of polymer chains, with high stability. Here, we disclose a strategy that relies on 'ordered crosslinks' to produce polymeric materials that exhibit a crystalline 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 polymerized 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.
authors.affiliation: Department of Materials Science, University of Milano - Bicocca, Via R. Cozzi 53, 20125 Milan, Italy.
authors.forename: Gaetano
authors.initials: G
authors.lastname: Distefano
authors.forename: Hirohito
authors.initials: H
authors.lastname: Suzuki
authors.forename: Masahiko
authors.initials: M
authors.lastname: Tsujimoto
authors.forename: Seiji
authors.initials: S
authors.lastname: Isoda
authors.forename: Silvia
authors.initials: S
authors.lastname: Bracco
authors.forename: Angiolina
authors.initials: A
authors.lastname: Comotti
authors.forename: Piero
authors.initials: P
authors.lastname: Sozzani
authors.forename: Takashi
authors.initials: T
authors.lastname: Uemura
authors.forename: Susumu
authors.initials: S
authors.lastname: Kitagawa
mesh_terms: D003432:Cross-Linking Reagents / Q000737:chemistry*; D046529:Microscopy, Electron, Transmission; D015394:Molecular Structure; D058105:Polymerization; D011145:Polyvinyls / Q000138:chemical synthesis* / Q000737:chemistry; D016062:Porosity; D033362:Powder Diffraction; D013237:Stereoisomerism; D013499:Surface Properties; D014961:X-Ray Diffraction
chemical_list: D003432:Cross-Linking Reagents; D011145:Polyvinyls