Abstract
This study reports on tailoring biobased aliphatic poly(amide‐urea) (PAU) thermoplastics by means of reactive extrusion requiring neither the use of diisocyanate monomers nor time‐consuming PAU polycondensation in a separate step prior to melt processing. Key intermediate is N,N′‐carbonyl‐biscaprolactam (CBC), which enables rapid and temperature‐programmable polycondensation of biobased diamines and difunctional aminoamides (AA) derived from diamines and dicarboxylic acids. Within a few minutes during melt processing using a twin‐screw extruder, CBC‐mediated advancement of biobased diaminoamides affords high molecular weight PAU. Whereas PAUs derived from short‐chain AAs are stiff and brittle materials with high melting temperatures close to thermal decomposition; the incorporation of AAs derived from sebacic acid and dimer fatty acid renders urea‐functional thermoplastics flexible and processable. Hence, the variation of oligomethylene segment lengths by incorporating short‐ and long‐chain AA building blocks in CBC‐mediated melt‐phase polycondensation governs PAU melting temperature (124–249 °C), Young's modulus (100–1900 MPa), tensile strength (6–51 MPa), and elongation at break (0.3–230%). image
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