Chemical Engineering Science, Vol.175, 139-147, 2018
Continuous enzymatic synthesis of polycaprolactone in packed bed reactor using pressurized fluids
Continuous processing of reagents allows high reaction yields and better operational process control, allied with cost reduction compared to batch mode. In this work, a packed-bed reactor (PBR) system using Novozym 435 for enzymatic ring-opening polymerization (epsilon-ROP) of epsilon-caprolactone (epsilon-CL) with dichloromethane as a cosolvent in supercritical CO2 (scCO(2)) or in n-butane media, was investigated. The reactions carried out in scCO(2) reached yields above 93 wt%, average molecular weight (Mn) of up to 31.2 kDa and polydispersity (D) from 1.4 to 1.6 for only 15 min processing. The apparent monomer conversion rate constant (kapp) ranged from 0.094 to 0.180 min(-1). Otherwise, reactions performed with n-butane provided yields above 80 wt%, Mn values of 25.4 kDa and D in the range of 1.4-1.6, also obtained for 15 min of reaction. The maintenance of high yields and molecular weights for up to 6 enzymatic reuses were obtained for both systems studied. (C) 2017 Elsevier Ltd. All rights reserved.