Modeling Heterogeneous copolymerization of fluorinated monomers in scCO2

In recent years the use of supercritical carbon dioxide (scCO2) in polymer processing and reaction has emerged as a “green” alternative to replace both environmentally hazardous organic solvents and water, whose utilization involves the production of large amount of waste streams. Moreover, scCO2 is non-toxic, inexpensive, and often exhibits intense plasticizing effect on polymers. In this work, the copolymerization of fluorinated monomers in scCO2 is explored. Batch free-radical copolymerization reactions of vinylidene fluoride (VDF) and hexafluoropropylene (HFP) have been carried out at temperature of 50 C and pressure of 400 bar using DEPDC as initiator and different amounts of stabilize…

The rate of polymerization in two loci reaction systems: VDF-HFP precipitation copolymerization in supercritical carbon dioxide

When the copolymerization of vinylidene fluoride (VDF) and hexafluoropropylene (HFP) is carried out in supercritical carbon dioxide (scCO 2) under heterogeneous conditions, the reaction occurs both in the continuous CO 2-rich phase and in the dispersed polymer-rich phase. The two phases being characterized by different values of reactant concentrations and kinetic parameters, one would expect that the reaction kinetics is affected by the polymer phase holdup in the reactor. However, the reaction rate is almost insensitive to the amount of produced polymer, at least at specific reaction conditions. This apparent contradiction is discussed and clarified in this paper by a series of comparativ…

Self-Diffusion of Small Molecules into Rubbery Polymers: A Lattice Free-Volume Theory

In the framework of the Free Volume Theory, a new equation was derived for the evaluation of self-diffusion coefficients of small molecules in polymers above the mixture glass transition temperature. The derivation of the equation turned out to be straightforward once the equivalence between the free-volume and the unoccupied volume given by Thermodynamic Lattice Theories is assumed. A parameter evaluation scheme is proposed, which is substantially simpler compared to the conventional Vrentas-Duda approach, even without losing generality. The key assumption is discussed and its consistency is verified from a numerical viewpoint. A comparison with experimental solvent self-diffusion coeffici…

Modeling Heterogeneous copolymerization in scCO2

ScCO2 as polymerization medium for high value polymers: two recent cases

In recent years the use of supercritical carbon dioxide (scCO2) in polymer processing and polymerization reactions has merged as a “green” alternative to replace both organic solvents, environmentally hazardous (VOCs), and water, which use involves the production of large amount of waste streams. ScCO2 is non-toxic, inexpensive, and often exhibits high solubility in polymer matrixes. Moreover, it causes polymer plasticization, thus favoring the diffusion of low MW species (monomers, initiators or additives) in the polymer phase. In this work, the use of scCO2 as polymerization medium for two different special polymers is discussed. Fluorinated copolymers mainly find application in environme…

Copolymerization of VDF and HFP in Supercritical Carbon Dioxide: A Robust Approach for Modeling Precipitation and Dispersion Kinetics

A kinetic model is developed for the heterogeneous free-radical copolymerization of vinylidene fluoride and hexafluoropropylene in supercritical CO2. The model accounts for polymerization in both the dispersed (polymer-rich) phase and in the continuous (polymer-free) supercritical phase, for radical interphase transport, diffusion limitations, and chain-length-dependent termination in the polymer-rich phase. A parameter evaluation strategy is developed and detailed to estimate most of the kinetic parameters a priori while minimizing their evaluation by direct fitting. The resulting model predictions compare favorably with the experimental results of conversion and MWD at varying monomer fee…

Copolymerization of VDF and HFP in Supercritical Carbon Dioxide: A Robust Approach for Modeling Precipitation and Dispersion Kinetics

A kinetic model is developed for the heterogeneous free-radical copolymerization of vinylidene fluoride and hexafluoropropylene in supercritical CO 2. The model accounts for polymerization in both the dispersed (polymer-rich) phase and in the continuous (polymer-free) supercritical phase, for radical interphase transport, diffusion limitations, and chain-length-dependent termination in the polymer-rich phase. A parameter evaluation strategy is developed and detailed to estimate most of the kinetic parameters a priori while minimizing their evaluation by direct fitting. The resulting model predictions compare favorably with the experimental results of conversion and MWD at varying monomer fe…

Model predictive control for continuous lactide ring‐opening polymerization processes

International audience; Polylactic acid (PLA) is an attractive environment-friendly thermoplastic that is bio-sourced and biodegradable. PLA is industrially produced by the ring-opening polymerization of Lactide. This reaction is sensitive to drifts in the operating conditions and impurities in the raw materials that may affect the reaction rate as well as the polymer properties, which can be very costly in continuous processes. It is therefore crucial to employ a control strategy that allows recovering the nominal conditions and maintaining the desired properties and conversion level in case of drift. Three control strategies are discussed in this paper: Proportional-Integral controller (P…

Dynamic optimization of a continuous Lactide ring-opening polymerization process

An increasing attention has been paid to the production of the polylactic acid (PLA) in recent years, owing to its properties as a biodegradable thermoplastic besides the fact that it is derived from renewable resources. PLA is industrially produced by ring opening polymerization of lactide. This reaction is sensitive to deviations in the operating conditions that highly affect the reaction rate and the polymer properties. Therefore, a process monitoring and control policy is crucial in order to restore the nominal conditions in case of drift. In this paper, a continuous PLA process is considered with three cascade reactors, two tubular and one loop reactor, that is described by partial dif…