Lignin valorization by forming toughened lignin-co-polymers: Development of hyperbranched prepolymers for cross-linking

The preparation of hyperbranched polymers from a unique combination of commercially available A2, B3 and CB13-type monomers is presented. Direct melt condensation of aliphatic dicarboxylic acid (A2) to compounds having trihydroxy groups ((B3), triethanolamine) and trihydroxy-monoamino groups ((CB13), tris(hydroxymethyl)aminomethane) led to a series of hyperbranched polyesters with amine cores and amide linkages. Because of the monomers availability and simplicity of the synthetic process, hyperbranched poly(ester-amine-amide) (HBPEAA) materials can be readily scaled up. This approach was used to synthesize series of prepolymers with varying degree of branching (DB) and distance between branching points. Taking the advantage of reactivity differences of COOH with the NH2 and OH groups, the hyperbranched polymer with different arrangement of amide linkage along the network was synthesized. The influence of reaction conditions such as monomer compositions, temperature and mode of mixing on the polymerization was examined. The DB of the HBPEAA (0.46–0.63) was dependant on the synthetic route. The HBPEAA exhibited moderate molecular weights as determined by NMR and ESI-MS. Thermogravimetric analysis revealed that the prepolymers exhibit reasonable thermal stability. The synthesized prepolymer was successfully utilized to copolymerize with 40% lignin to form toughened elastomeric materials with tensile strength of 12 MPa, Young's modulus of 33 MPa and 149% elongation.

► A monomer combination of a B3 + A2 + CB31 led to a series of hyperbranched polyester prepolymers.
► Polymerization was achieved by melt condensation.
► The hyperbranched polyesters had amine cores and amide linkages.
► The hyperbranched prepolymers were copolymerized with lignin to form toughened elastomers.