Well phase separated segmented copolymers via acyclic diene metathesis (ADMET) polymerization

Abstract

Segmented oligomers consisting of polyoctenylene hard segments and unsaturated polytetrahydrofuran soft segments were prepared using acyclic diene metathesis (ADMET) copolymerization techniques. These are the first such segmented materials prepared via metathesis chemistry. Two different molecular weight α,ω-poly(tetrahydrofuran)diene soft segment monomers of the structure [CH2CH(CH2)4[O(CH2)4]-nO(CH2)4CHCH2] (1) were synthesized by the cationic living polymerization of tetrahydrofuran (THF). Trifluoromethanesulfonic anhydride, (CF3SO2)2O (triflic anhydride) (2), was employed as the initiator, followed by in situ bis-functionalization with 5-hexen-1-ol, [CH2=CH(CH2)4OH] (3), to yield soft segment dienes with vinyl end groups. The functionality of these soft segment monomers was approximately 1.9. These telechelic monomers possessed sufficient functionality to be homopolymerized or copolymerized with 1,9-decadiene (4) to generate well phase separated, segmented oligomers exhibiting hard segment/soft segment thermal behavior. The segmented copolymers were characterized by 1H-NMR, 13C-NMR, and IR spectroscopy, elemental analysis, and TGA and DSC analysis. Average molecular weights were determined by gel permeation chromatography (GPC) and end-group analysis. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3441–3449, 1997