In this study, a series of bio-based thermoplastic polyurethane (TPU) was synthesized via the solvent-free one-shot method using 100% bio-based polyether polyol, prepared from fermented corn, and 1,4-butanediol (BDO) as a chain extender. The average molecular weight, degree of phase separation, thermal and mechanical properties of the TPU-based aromatic (4,4-methylene diphenyl diisocyanate: MDI), and aliphatic (bis(4-isocyanatocyclohexyl) methane: H12MDI) isocyanates were investigated by gel permeation chromatography, Fourier transform infrared spectroscopy, atomic force microscopy, X-ray Diffraction, differential scanning calorimetry, dynamic mechanical thermal analysis, and thermogravimetric analysis. Four types of micro-phase separation forms of a hard segment (HS) and soft segment (SS) were suggested according to the [NCO]/[OH] molar ratio and isocyanate type. The results showed (a) phase-mixed disassociated structure between HS and SS, (b) hydrogen-bonded structure of phase-separated between HS and SS forming one-sided hard domains, (c) hydrogen-bonded structure of phase-mixed between HS, and SS and (d) hydrogen-bonded structure of phase-separated between HS and SS forming dispersed hard domains. These phase micro-structure models could be matched with each bio-based TPU sample. Accordingly, H-BDO-2.0, M-BDO-2.0, H-BDO-2.5, and M-BDO-3.0 could be related to the (a)-form, (b)-form, (c)-form, and (d)-form, respectively.
Keywords: bio-based polyurethane; biomaterials; micro-phase separation; polymerization; thermoplastic polymer.