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Synthesis of Polymeric Topological Isomers through Electrostatic Self‐Assembly and Covalent Fixation with Star Telechelic Precursors
Author(s) -
Tezuka Yasuyuki,
Tsuchitani Akiko,
Oike Hideaki
Publication year - 2004
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.200400223
Subject(s) - covalent bond , polymer , tetrahydrofuran , polymer chemistry , self assembly , macromolecule , materials science , chemistry , organic chemistry , solvent , biochemistry
Summary: A pair of macromolecular constitutional isomers having topologically distinctive, dicyclic constructions, that is, θ‐shaped and manacle‐shaped polymers, has been synthesized from a polymer self‐assembly, comprised of three‐armed star poly(tetrahydrofuran) [poly(THF)] having N ‐phenylpyrrolidinium salt end groups carrying dicarboxylate counteranions ( 1S / 2d ). The presence of the two constitutional polymeric isomers was confirmed by means of a reversed‐phase liquid chromatography (RPC) technique. Moreover, size exclusion chromatography (SEC) showed that a major component possesses notably larger hydrodynamic volume than the others, and is assignable as a manacle‐shaped isomer while a minor component is assigned as a θ‐shaped isomer. The statistics of the covalent‐linking process of 1S / 2d were consistent with the other experimental results.An “electrostatic self‐assembly and covalent fixation” process of a trifunctional star‐shaped precursor gives rise to θ‐shaped and manacle‐shaped polymers.