The addition reaction of alcohols and aromatic carbodiimides and its application to produce thermo-reversible polymer networks

• Published in: Polymer (Guilford) Vol. 305; p. 127176
• Main Authors: Mu, Linyu, Eling, Berend, Luinstra, Gerrit A.
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 12.06.2024
• Subjects: Carbodiimide; Crosslinking; Guanidine; Hydroxy; iso-Urea; Polyol; Self-healing; Thermo-reversible; Hydroxy; iso-Urea; Thermo-reversible; Carbodiimide; Guanidine; Crosslinking; Self-healing; Polyol
• ISSN: 0032-3861; 1873-2291
• DOI: 10.1016/j.polymer.2024.127176

The addition reaction of primary alcohols onto aromatic carbodiimides giving iso-ureas was studied in bulk at various temperatures. A side reaction at 60 °C was found to occur between carbodiimide and iso-urea yielding N,N′-substituted polyguanidine oligomers. The occurrence of this side reaction coincides with a reduced conversion of the alcohol; the carbodiimide was always fully converted to either iso-urea or polyguanidine. The formation of the polyguanidine was reversible at higher temperatures to reform iso-urea and carbodiimide. The latter reaction was complete at about 130 °C. The thermo-reversibility of the guanidine bond was utilized to produce thermo-reversible self-healing polymer networks by reaction of polyether diol and a 1.5 to 2-fold molar excess of aromatic biscarbodiimide. The materials were soft and elastic and showed a glass transition at −60 °C. The guanidine linkages in the polymers started to unzip above 60 °C as was indicated by a drop in the E-modulus, at about 130 °C sufficient guanidine crosslinks had unzipped to provide the polymer liquid-like properties. The guanidine crosslinks were reformed after cooling to ambient temperature giving back the polymer network. [Display omitted] •The reaction of carbodiimide and hydroxyl gave stable isourea bonds.•Using excess carbodiimide yielded thermo-reversible guanidine linkages.•Reacting polyol with excess bis-carbodiimide provided crosslinked polymer.•The crosslinks were stable below 60 °C and unzipped above 130 °C.•The thermosetting polymers showed thermally self-healable properties.