The preparation and characterization of phosphorus-terminated poly-1,3-butadiene: new telechelic ionomers

W. E. Lindsell, K. Radha, I. Soutar, M. J. Stewart

Research output: Contribution to journalArticle

Abstract

Polybutadienyllithium systems, with high 1,4-microstructure, low polydispersity and M ¯n in the range (2-10) × 103, have been produced in hydrocarbon solvents by using n-butyllithium or 3-dimethylamino-propyllithium as initiator. Termination of these 'living' polymers with chlorophosphine, ClPR2 (R = Ph, Et or Cy), occurs to give oxidatively unstable phosphine derivatives Y-(C4H6)n-PR2, in up to 93% efficiency. Oxidation products include the related phosphine oxides. Quaternization of the phosphinated polymers in situ with iodomethane gives a quantitative conversion into the cationomeric polymers Y'-(C4H6)n-PR2Me+I-, including the novel dicationic telechelic systems with Y' = I+NMe3(CH2)3, which show thermoplastic elastomeric properties. The products have been characterized by gel permeation chromatography, end-group analysis and 1H, 13C and 31P nuclear magnetic resonance spectroscopy. Model quaternary phosphonium derivatives, trans- and cis-t-BuCH2CHCHCH2PR2Me+I- and t-BuCH2CH(CHCH2)PR2Me+I-, are reported and help establish the terminal geometry of the quaternary phosphonium-capped polybutadienes: the addition of phosphorus to the terminal butadienyl follows the order cis-1,4>trans-1,4>1,2 with the amount of 1,2-termination being smallest when R is the bulky cyclohexyl group. © 1990.

Original languageEnglish
Pages (from-to)1374-1378
Number of pages5
JournalPolymer
Volume31
Issue number7
Publication statusPublished - Jul 1990

Keywords

  • anionic polymerization
  • cationomer
  • n.m.r.
  • phosphonium group
  • telechelic poly-1,3-butadiene

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    Lindsell, W. E., Radha, K., Soutar, I., & Stewart, M. J. (1990). The preparation and characterization of phosphorus-terminated poly-1,3-butadiene: new telechelic ionomers. Polymer, 31(7), 1374-1378.