Telechelic ionomeric elastomers with quaternary ammonium groups (Me2RN+) attached terminally to polybutadiene (M¯n ˜ 2.7 × 103; M¯w/M¯n = 1.27; containing 62% 1,4-linkages) have been synthesised by an anionic technique using a functionalised initiator and terminator, followed by quaternisation of the resulting a,?-bis(dimethylamino)polybutadiene. By using differing alkyl halides for quaternisation and by ion exchange chromatography, a series of dialkylated telechelic cationomers has been produced containing alkyl groups, R = Me, Et, n-Pr, n-Bu or n-C5H11 with counter anions X = I-, Br-, PF6- or SO42-. The glass transition temperatures, Tg, of these cationomers are c.6°C higher than for the precursor, non-quaternised polymer but are essentially unchanged with variations in groups R or anions X. Dynamic mechanical thermal analyses of the cationomers have been carried out and a secondary transition, Ti, associated with relaxation of ionic cross-linking interactions, observed. Values of Ti decrease as the size of R increases from C1 to C5, and as the anion X is changed from Br- to I- to PF6- or SO42- to PF6MIN. Activation energies can be derived from the frequency dependence of Ti values or from the temperature dependence of shift parameters, obtained from the master curves of the dependence on frequency of the shear storage (G') and loss (G?) moduli; these activation energies are dependent on the nature of the counter anion, being greatest for the polymer containing the dinegative SO42-, but are essentially unchanged by the variations in alkyl group, R, implemented in this study. Other results of the dynamic mechanical analyses on the cationomeric elastomers are discussed in relation to their ionic cross-linking.
|Number of pages
|British Polymer Journal
|Published - 1990
|International Macromolecules '89 on Functional Polymers and Biopolymers - Oxford, Engl
Duration: 4 Sept 1989 → 8 Sept 1989