Molecular weight distribution of polyethylene terephthalate in homogeneous, continuous-flow-stirred tank reactors

Abstract

Poly(ethylene terephthalate) (PET) formation in homogeneous, continuous-flow-stirred tank reactors (HCSTRs) operating at steady state has been simulated. The feed to the reactor is assumed to consist of the monomer bis-(hydroxyethyl) terephthalate and monofunctional compound (MF1) cetyl alcohol. The overall polymerization is assumed to consist of the polycondensation, reaction with monofunctional compounds, redistribution, and cyclization reactions. At a given time, the reaction mass consists of polyester molecules (Pn), polyester molecules with an ending of molecules of monofunctional compound (MFn), and cyclic polymers (Cn). A mass balance for each of these species in the reactor gives rise to a set of algebraic equations to be solved simultaneously. The MWD calculations show that the redistribution reaction plays a major role and cannot be ignored, This result is in contrast lo the observation for semi-batch reactors, for which redistribution becomes important when the cyclization reaction is included. For the same residence times of semi-batch and HCSTRs, the latter gives considerably lower-number average molecular weight, Nav, and polydispersity index, ρ. However, for the same conversions, the ρ for CSTR is higher. The concentration of the monofurctional compound, [MF1]0, in the feed and the reactor temperature both influence ρ, but the effect is small within the range studied