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Controlled variation of monomer sequence-distribution in the synthesis of aromatic poly(ether ketone)s

Lim, K. J. C., Cross, P., Mills, P. and Colquhoun, H. M. (2016) Controlled variation of monomer sequence-distribution in the synthesis of aromatic poly(ether ketone)s. High Performance Polymers, 28 (8). pp. 984-992. ISSN 1361-6412

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To link to this item DOI: 10.1177/0954008315612140

Abstract/Summary

The effects of varying the alkali metal cation in the high-temperature nucleophilic synthesis of a semi-crystalline, aromatic poly(ether ketone) have been systematically investigated, and striking variations in the sequence-distributions and thermal characteristics of the resulting polymers were found. Polycondensation of 4,4'-dihydroxybenzophenone with 1,3-bis(4-fluorobenzoyl)benzene in diphenylsulfone as solvent, in the presence of an alkali metal carbonate M2CO3 (M= Li, Na, K, or Rb) as base, affords a range of different polymers that vary in the distribution pattern of 2-ring and 3-ring monomer units along the chain. Lithium carbonate gives an essentially alternating and highly crystalline polymer, but the degree of sequence-randomisation increases progressively as the alkali metal series is descended, with rubidium carbonate giving a fully random and non-thermally-crystallisable polymer. Randomisation during polycondensation is shown to result from reversible cleavage of the ether linkages in the polymer by fluoride ions, and an isolated sample of alternating-sequence polymer is thus converted to a fully randomised material on heating with rubidium fluoride.

Item Type:Article
Refereed:Yes
Divisions:Interdisciplinary centres and themes > Chemical Analysis Facility (CAF)
Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
Interdisciplinary centres and themes > Chemical Analysis Facility (CAF) > NMR (CAF)
Interdisciplinary centres and themes > Chemical Analysis Facility (CAF) > Thermal (CAF)
Interdisciplinary centres and themes > Chemical Analysis Facility (CAF) > Xray (CAF)
ID Code:43742
Publisher:Sage

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