Nonisocyanate Polyurethane Segmented Copolymers from Bis-Carbonylimidazolides

Bis-carbonylimidazolide (BCI) functionalization enables an efficient synthetic strategy to generate high molecular weight segmented nonisocyanate polyurethanes (NIPUs). Melt phase polymerization of ED-2003 Jeffamine, 4,4 '-methylenebis(cyclohexylamine), and a BCI monomer that mimics a 1,4-butanediol chain extender enables polyether NIPUs that contain varying concentrations of hard segments ranging from 40 to 80 wt. %. Dynamic mechanical analysis and differential scanning calorimetry reveal thermal transitions for soft, hard, and mixed phases. Hard segment incorporations between 40 and 60 wt. % display up to three distinct phases pertaining to the poly(ethylene glycol) (PEG) soft segment Tg, melting transition, and hard segment Tg, while higher hard segment concentrations prohibit soft segment crystallization, presumably due to restricted molecular mobility from the hard segment. Atomic force microscopy allows for visualization and size determination of nanophase-separated regimes, revealing a nanoscale rod-like assembly of HS. Small-angle X-ray scattering confirms nanophase separation within the NIPU, characterizing both nanoscale amorphous domains and varying degrees of crystallinity. These NIPUs, which are synthesized with BCI monomers, display expected phase separation that is comparable to isocyanate-derived analogues. This work demonstrates nanophase separation in BCI-derived NIPUs and the feasibility of this nonisocyanate synthetic pathway for the preparation of segmented PU copolymers. Bis-carbonylimidazolide chemistry enables a series of poly(ethylene glycol)-containing non-isocyanate polyurethanes (NIPUs) through a facile, melt-phase polycondensation reaction. These NIPUs display predictable nanoscale phase separation behavior that correlate with hard segment concentration. Thermomechanical and spectroscopic analysis characterizes distinct nanoscale domains with poly(ethylene glycol) soft segments, which is previously unachievable with NIPUs synthesized through an alternative cyclic carbonate approach. image