Based on a recently suggested reaction mechanism, which involves the production and propagation of terminal double bonds (TDBs), kinetic models for the polymerization of N‐vinylpyrrolidone in aqueous solution are developed. Two modeling strategies, the classes and the pseudodistribution approach, are applied to handle the multidimensional property distributions that result from this reaction mechanism and to get detailed structural property information, e.g., on the chain length distribution and the distribution of TDBs. The structural property information is then used to develop reduced models with significantly lower computational effort, which can be used for process design, on‐line applications or coupled to computational fluid dynamic simulations. To validate the derivations, the models are first compared against each other and finally to experimental results from a continuous stirred tank reactor. The evolution of monomer conversion and molecular weight average data as well as molecular weight distributions can be represented very well by the models that are derived in this article. These results support the correctness of the reaction mechanism predicted by quantum mechanical simulations.
A first intense investigation in the kinetics of radical polymerization of NVP was done by Senogles et. al. [7] They revealed a variation of the activation energy for the propagation step
Radical PolymerizationAn improved kinetic model for the radical polymerization of N-vinyl-pyrrolidone (NVP) in aqueous medium is developed. Quantum chemical simulations reveal that the transfer to polymer is of minor importance whereas the transfer to monomer by hydrogen abstraction in 3-position of the pyrrolidone ring leads to a radical with a double bond which initiates a new chain bearing a terminal double bond (TDB). The resulting dead chains with one, two, or more TDB are the main source for a strong increase of molar mass in batch reactors at high conversion due to long chain branching and crosslinking. This can be a source for gel formation and fouling in continuous reactors. www.advancedsciencenews.com www.mre-journal.de
To gain insights into the microstructure of polyvinylpyrrolidone (PVP), a detailed reaction mechanism is developed, which characterizes the polymer along the property coordinate chain length, terminal double bonds (TDB), and branching points. For practical purposes, calculations with three property coordinates are unfeasible, and model reduction is needed. Here, a reduced model with only one single property coordinate without significant loss of accuracy is derived. In the first step, the coordinate TDBs are reduced by a linear relationship between TDBs and chain length. As the parameters of this relation are state dependent, they are dynamically adjusted from a parallel calculated 0D model. In a second step, the pseudodistribution approach is used to reduce the 2D distribution to chain length as the only property coordinate and calculate moments of branching points as a function of chain length. A 2D class model is set up for validation. To demonstrate the benefits of the model, the chain length distribution and moments of branching points are calculated for different average residence times and monomer concentrations in a stirred tank reactor. In a future publication, the model will be validated by experimental data in terms of chain length distribution and branching points.
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