Mathematical Modeling of Free Radical Solution Terpolymerization Reactions in a Batch and Continuous Flow Stirred Tank Reactors

• Published in: Macromolecular theory and simulations Vol. 30; no. 3
• Main Authors: Luciani, Carla V., Choi, Kyu Yong
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 01.05.2021
• Subjects: Chain transfer; Composition; Continuous flow; Continuously stirred tank reactors; Conversion; free radical polymerization; Free radicals; Initiators; kinetics; Maleic anhydride; Mathematical models; modeling; Molecular weight; Monomers; Parameter estimation; Peroxide; Polymethyl methacrylate; Rate constants; Styrene; Terpolymerization; Terpolymers
• DOI: 10.1002/mats.202000094
• ISSN: 1022-1344

A mathematical model that describes a free radical solution terpolymerization is applied to styrene (St), methyl methacrylate (MMA), and maleic anhydride (MAh) polymerization system. This terpolymerization model allows for the use of either monofunctional or bifunctional peroxide initiators, and it is applied to batch and continuous reactions. The key model outputs are global monomer conversion, terpolymer composition, terpolymer average molecular weights, and terpolymer monomer sequence distributions. A few kinetic parameters are estimated such that global conversion is properly predicted by the model including initiator efficiency and two termination rate constants. Molecular weights are shown to be dominated by chain transfer reactions. Experimental trends of conversion, terpolymer molar masses (molecular weights), and composition are reasonably well predicted by the model. A detailed mathematical model for free radical terpolymerization is derived and solved to calculate major process outputs including polymerization rate, copolymer molecular weight averages, and comonomer sequence length distributions in batch and continuous reactors. The model is used for both monofunctional and bifunctional peroxide initiators using the pseudokinetic parameters and rate equations for various polymeric radical species.