1862-8338/asset/olbannerleft.gif?v=1&s=5ebdb3321e618841fbc0c3a0b23eb6e5ea76b580)
1862-8338/asset/olbannerright.gif?v=1&s=2ba0e309cfc8f6d9f10c5fd5f9a68692244fd449)
Special Article Series - Full Paper
Mathematical Modeling of Acid-Catalyzed 1,3-Propanediol Polymerization
Article first published online: 25 JAN 2012
DOI: 10.1002/mren.201100069
Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Additional Information
How to Cite
Mueller, P. A., Rajagopalan, B., Congalidis, J. P. and Murphy, E. R. (2012), Mathematical Modeling of Acid-Catalyzed 1,3-Propanediol Polymerization. Macromolecular Reaction Engineering, 6: 126–152. doi: 10.1002/mren.201100069
Publication History
- Issue published online: 11 APR 2012
- Article first published online: 25 JAN 2012
- Manuscript Revised: 8 NOV 2011
- Manuscript Received: 6 SEP 2011
Keywords:
- 1,3-propanediol;
- condensation polymerization;
- mathematical modeling;
- moment equations;
- poly(trimethylene ether glycol)
Abstract
A reaction mechanism for the polymerization of 1,3-propanediol is proposed for two acid catalysts. Population and mass balance equations are derived for small molecules and for polymeric species of chain distributions distinguishable in terms of protonation state and end group functionality. Since the sulfuric acid catalyzed process has two types of polymer linkages, the derivation of the moment equations is challenging. The reverse reactions are also accounted thus creating a moment closure problem. A mass transfer model is developed to predict reaction mixture water content. The Sanchez-Lacombe equation of state is used to calculate phase behavior and species partitioning. Optimization of selected parameters is accomplished by comparison to laboratory data resulting in a fully predictive model.