Enzyme- and metal-catalyzed synthesis of a new biobased polyester

• Published in: Organic Process Research & Development
• Main Authors: Gebhard, Jakob, Neuer, Björn, Luinstra, Gerrit A., Liese, Andreas
• Format: Article in Journal/Newspaper
• Language: English
• Published: American Chemical Society 2017
• Subjects: 540: Chemie; 620: Ingenieurwissenschaften; 620; 540; Merz; Antarc*; Antarctica
• Online Access: http://hdl.handle.net/11420/3165

Linear aliphatic polyesters were prepared from Pripol 1012, a diacidic C18 fatty acid dimer, and 1,3-propanediol employing a lipase or a titanium tetrabutanoate. Metal-based catalysis (route M) was carried out with a precondensation at 180 °C and 600 mbar followed by a final condensation at 220 °C and 0.3-0.6 mbar. Enzyme catalysis was carried out with an immobilized Candida antarctica lipase B after either a precondensation step at 180 °C and 600 mbar (route E1) or 80 °C and 100 mbar (route E2) and a final condensation at 80 °C and 0.3-0.6 mbar. Polyesters were obtained along routes M, E1, and E2 with weight-average molecular weights, Mw, at final conversion of 84.6, 26.7, and 15.6 kg mol-1, respectively. The final molecular weight via route E2 was most probably constrained by depletion of 1,3-propanediol during precondensation. Rheological measurements of the polyesters in melt revealed a Newtonian-like behavior at 80 °C. The dynamic viscosities fulfill the Cox-Merz rule. The power law for the viscosity as a function of Mw possesses an exponent of 3.7 ± 0.2. A polyesterdiol of Mn ≈ 6 kDa prepared along route M was used in the synthesis of a polyurethane elastomer with a Young modulus of 2.5 MPa, an elongation at break of 554%, an ultimate tensile strength of 3.5 MPa, and a Shore A hardness of 38.