Synthesis, Morphology, and Properties of Segmented Poly(ether amide)s with Uniform Oxalamide-Based Hard Segments

Abstract

The synthesis, morphology, and properties of segmented poly(ether amide)s based on flexible PTHF segments (Mn = 1.1 × 103 g mol–1) and uniform rigid oxalamide segments were investigated. The amount of oxalamide groups in the hard segment and the spacer length of bisoxalamide-based hydrogen bonded arrays were varied systematically. The segmented poly(ether amide) with single oxalamide groups connecting the polyether blocks was a sticky solid with a melting temperature of ∼25 °C. Incorporation of uniform hard segments consisting of two interconnected oxalamide units provided highly phase-separated thermoplastic elastomers with a broad temperature-independent rubber plateau. By decreasing the aliphatic spacer length separating two oxalamide units from 10 to 2 methylene groups, the melting transitions increased from 140 to 200 °C. FT-IR evidenced strongly hydrogen bonded and highly ordered bisoxalamide hard segments with degrees of ordering between 66 and 90%. AFM revealed the presence of fiber-like nanocrystals with lengths up to several hundreds of nanometers randomly dispersed in the soft PTHF matrix. The long dimension of the crystals was found parallel to the direction of the hydrogen bonds. One of the other small dimensions of the crystal approximately equals the length of the oxalamide segment, whereas the other one may correspond to the height of a stack containing ca. 10–20 hydrogen-bonded sheets. Upon heating, the crystalline phase melts over a broad temperature range to give a homogeneous melt according to temperature-dependent FT-IR, SAXS, and rheology data. Increasing the number of oxalamide groups in the hard segment to three afforded a highly phase-separated material with a melting transition above 200 °C. The segmented copolymers with two or three oxalamide groups in the hard segment show a distinct yield point and have an elastic modulus between 121 and 210 MPa, a stress at break ranging from 15 to 27 MPa, and strain at break of 150 up to 900%. The results demonstrate that alternating block copolymers with soft PTHF segments and uniform hard segments containing two or three oxalamide groups are TPEs with good thermal and mechanical properties.