Microstructure and Properties of Poly(amide urethane)s: Comparison of the Reactivity of α‐Hydroxy‐ω‐O‐phenyl Urethanes and α‐Hydroxy‐ω‐O‐hydroxyethyl Urethanes

Abstract

Summary: Poly(amide urethane)s were prepared from ε‐caprolactam, amino alcohols, and diphenyl carbonate or ethylene carbonate in three steps. Polycondensation was performed either with α‐hydroxy‐ω‐O‐phenyl urethanes or with α‐hydroxy‐ω‐O‐hydroxyethyl urethanes; it was found that the reactivity at 90 °C of the first is much higher than that of the latter. For nearly equal reactivity, the temperature for the polycondensation of α‐hydroxy‐ω‐O‐hydroxyethyl urethanes had to be increased from 90 °C to 150 °C. The microstructure of the resulting poly(amide urethane)s differs by the content of urea groups in the polymer chains, which is 5% for poly(amide urethane)s prepared from α‐hydroxy‐ω‐O‐phenyl urethanes and 15% for poly(amide urethane)s prepared from α‐hydroxy‐ω‐O‐hydroxyethyl urethanes. As a consequence, the thermal properties of the poly(amide urethane)s differ slightly.Synthesis of poly(amide urethane)s.magnified imageSynthesis of poly(amide urethane)s.

Synthesis and characterization of alternating poly(amide urethane)s from ε-caprolactone, diamines and diphenyl carbonate

“…A formate end group is the result of the work up, because the purified product was obtained by precipitation of a solution in formic acid into diethyl ether. In formic acid, the CH 2 OH end group converts into a CH 2 A resonance signal with small intensity was observed at dZ5.75 ppm attributed to protons of a urea linkages as was observed in the series of poly(amide urethane)s obtained from 3-caprolactam, amino alcohols, and diphenyl carbonate [8] or ethylene carbonate [9]. These defects in the microstructure, however, are below 5 mol%.…”

“…In previous papers [8][9][10], the successful synthesis of alternating poly(amide urethane)s, poly(amide urea)s, and poly(amide urethane urethane)s from 3-caprolactam, amino alcohols or diamines, and diphenyl carbonate or ethylene carbonate was reported including their thermal properties. In this paper, we focus on a different route to synthesize poly(amide urethane)s comprising alternating amide and urethane linkages.…”

“…Polymers and copolymers that contain 3-caprolactone moieties are widely used for medical application, biodegradable sutures, tissue engineering, and artificial skin [5][6][7]. From the point of view of materials which might be of interest for the manufacture of powder coatings, we have already described the synthesis of alternating poly(amide urethane)s employing 3-caprolactam, amino alcohols, and diphenyl carbonate or ethylene carbonate as carbonic acid esters in previous papers [8,9]. Furthermore, we prepared poly(amide urea)s and poly(amide urethane urethane)s from 3-caprolactam, diamines, and diphenyl carbonate or ethylene carbonate [10].…”

Synthesis and thermal and mechanical properties of nonisocyanate poly(ether urethane) thermoplastic elastomers containing dibutylene terephthalate and poly(tetramethylene ether) segments

“…(2) Transurethane polycondensation of diurethanes or urethane containing compounds: This method is suitable to prepare NI-TPUs or NI-TPUEs. Researchers reported aliphatic NI-TPUs synthesized through transurethane polycondensation, including amorphous 14,15 and crystallizable 16,17 polyurethanes, poly(amide urethane)s, [18][19][20] poly(ether amide urethane)s, 21 poly(ether urethane)s, 22,23 and polyureas. [24][25][26] These NI-TPUs are thermoplastics other than NI-TPUEs because they lack resilience.…”

Influence of crystallizable units on the properties of aliphatic thermoplastic poly(ether urethane)s synthesized through a non-isocyanate route

“…21 Meanwhile, Sharma et al synthesized a series of α -hydroxy- ω -amino-amides and transformed them into α -hydroxy- ω -O-phenyl urethanes or α -hydroxy- ω -O-hydroxyethyl urethanes, from which several alternating poly(amide urethane)s were synthesized. 22 –24 Zhao et al synthesized a series of aliphatic segmented poly(amide urethane)s containing short nylon-6 segments 25 , poly(ether amide urethane)s containing poly(ethylene glycol) (PEG) sequences and short nylon-6 segments, 26 poly(ether urethane)s (PEIUs) with short or long PEG segments, 27,28 and aliphatic polyureas. 29,30 They are all crystallizable thermoplastics with good thermal and mechanical properties.…”