Date of Award
Master of Applied Science (MASc)
Free radical (co-)polymerization of low-density polyethylene (LDPE) is carried out commonly in high pressure autoclaves or tubular reactors. The severe thermodynamic conditions of the process hinder ethylene from going to full conversion. One remedy to improve the monomer conversion is to investigate the effectiveness of initiators, such as difunctional organic peroxides. In the present work, a kinetic model based on a postulated reaction mechanism for free radical ethylene (co-) polymerization initiated by difunctional initiators is applied to analyze the dynamic behavior of a continuous LDPE isothermal autoclave reactor and a non-isothermal tubular reactor. The model describes the rates of initiation, propagation and the population balance equations. It predicts variations of the initiator and monomer concentrations and reaction temperature as well as molecular weight distribution of reactive macromolecular species. Variations of the pressure, velocity and transport/physical properties of the reacting mixture were accounted for in the tubular reactor. Model predictions are compared to experimental data collected from literatures for one monofunctional (dioctanoyl) and two difunctional initiators namely, (2,2-bis(tert-butylperoxy)-butane and 2.5-dimetyl hexane-2t-butylperoxy-5perpivalate).
In comparison with dioctanoyl peroxide, polymerization with difunctional initiators requires a lesser amount of initiators and gives higher ethylene conversion in a shorter time. The modeling of LSPE with difunctional initiators was then extended to ethylene copolymerization with vinyl acetate and butyl acrylate. The model helps to determine the influence of reactivity ratio on the end-use product properties. Details of modeling a multiple feed LSPE tubular reactor are included for both homo- and co-polymerization reactions. The effect of monomer and initiator injections on the productivity and (co)polymer rheology and composition are investigated as well.
Finally, an optimization method was applied to determine the optimal values of control variables via maximization of an objective function expressed in terms of monomer conversion, number average molecular weight, polydispersity and final desired composition of copolymer product. The results show that we can obtain a polymer with desired characteristics by proper manipulation of the control variables.
Fard, Pegah Khazraei Karimi, "Modeling and optimization of ethylene copoplymerization in high pressure reactor using difunctional initiators" (2007). Theses and dissertations. Paper 242.