Synthesis and characterization of α,ω-and α-functionalized hydrogenated polybutadienes: Telechelic and semi-telechelic amine and phosphite terminated polymers

Polymers with terminal amine or phosphite groups (X) were synthesized from tosylated derivatives of hydrogenated a-hydroxy- and a-dihydroxy-poly-1,3-butadienes, produced by anionic techniques. Products are semi-telechelic and telechelic polymers with X = NH₂ (5), NHPh (6), NHPrⁿ (7), NH(CH₂)₃NMe₂ (8), O(CH₂)₂NH₂ (9), O(CH₂)₂NH(CH₂)₂NH₂ (10), NMe₂ (13), OPO₂C₆H₄ (14) of varying ethyl side-group content, controlled molar mass (M_n = 600-3000) and low polydispersity. Characterization of polymers by n.m.r. and i.r. spectroscopy is reported, with comparative studies on short chain model systems. Thermal properties and viscosities have been investigated in relation to molar mass, backbone structure and terminal functionality; comparisons are made with related saturated and unsaturated systems, and with polymers containing terminal ionic functionalities, formed by alkylation. protonation, or coordination with Cu(II), Ni(II) and Fe(III) chlorides. Effects of end-groups on variations in T_g, higher thermal transitions and on melt viscosities are discussed. Oxidation of phosphite end-groups is also observed. © 1997 Elsevier Science Ltd.