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Enthalpy-driven ring-opening polymerization of highly strained macrocyclic biaryl-ether-ketones

Colquhoun, H.M., Zhu, Z.X. and Dudman, C.C. (2005) Enthalpy-driven ring-opening polymerization of highly strained macrocyclic biaryl-ether-ketones. Macromolecules, 38 (25). pp. 10421-10428. ISSN 0024-9297

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To link to this item DOI: 10.1021/ma051781x


Highly strained macrocyclic ether-ketones obtained by nickel-catalyzed cyclization of linear precursor oligomers undergo ring-opening polyinerization via ether exchange in the presence of nucleophilic initiators such as fluoride or phenoxide anions. Strain enthapies of these macrocycles, from DSC analyses of their exothermic ring-opening polymerization are in the range 50-90 kJ mol(-1). Melt-phase polymerization generally affords slightly cross-linked materials, but solution-phase polymerization at high macrocycle concentrations gives fully soluble, high molar mass polymers with inherent viscosities of up to 1.78 dL g(-1). Sequence-analysis of the resulting polymers by C-13 NMR shows that alternating or random monomer sequences may be obtained, depending on whether one or both aromatic rings adjacent to the ether linkages are activated toward nucleophilic attack.

Item Type:Article
Divisions:Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:11156

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