Polycondensation reaction kinetic modeling

Modeling the Polycondensation Reaction Kinetics for the Synthesis of Aiiphatic Polyesters... 

Kinetic experiments and rigorous modelling of the mass-transfer controlled polycondensation reaction have shown that even at low melt viscosities the diffusion of EG in the polymer melt and the mass transfer of EG into the gas phase are the rate-determining steps. Therefore, the generation of a large surface area is essential even in the prepolycondensation step. 

In this section, the kinetics of the second step, that is, the polycondensation reaction of aliphatic polyesters, is investigated and a simple theoretical model is proposed to simulate both esterification and transesterification reactions taking place during polycondensation. 

Esterification and polycondensation kinetics of PPSu synthesis can be well described on the basis of rather simple simulation models, taking into account the reaction kinetics and the functional group modeling approach. The latter is a very beneficial technique which includes aspects of the reaction mechanism although with the minimum computational effort. 

Many publications have appeared on the kinetics of transesterification, dealing with either PET or model compounds. A selection of these papers is summarized in Table 2.5. The overall reaction order of polycondensation is 3, being 1 each for ester, alcohol, and catalyst [43], The reaction rate of poly condensation is generally limited by the rate of removal of EG from the reaction mixture. A... 

Many studies on the modelling of esterification, melt polycondensation, or solid-state polycondensation refer to the reaction scheme and kinetic data published by Ravindranath and co-workers. Therefore, we will examine the data sources they have used over the years. The first paper concerned with reactor modelling of PET production was published by Ravindranath el al. in 1981 [88], The reaction scheme was taken from Ank and Mellichamps [89] and from Dijkman and Duvekot [90], The kinetics for DEG formation are based on data published by Hovenkamp and Munting [60], while the kinetics for esterification were deduced... 

The kinetics of polycondensation hy nucleophilic aromatic substitution in highly polar solvents and solvent mixtures to yield linear, high molecular weight aromatic polyethers were measured. The basic reaction studied was between a di-phenoxide salt and a dihaloaromatic compound. The role of steric and inductive effects was elucidated on the basis of the kinetics determined for model compounds. The polymerization rate of the dipotassium salt of various bis-phenols with 4,4 -dichlorodiphenylsulfone in methyl sulfoxide solvent follows second-order kinetics. The rate constant at the monomer stage was found to be greater than the rate constant at the dimer and subsequent polymerization stages. 

Laubriet et al. [Ill] modelled the final stage of polycondensation by using the set of reactions and kinetic parameters published by Ravindranath and Mashelkar [112]. They used a mass-transfer term in tire material balances for EG, water and DEG adapted from film tlieoiy J = (kia), (c,- — c ), with c being the interfacial equilibrium concenttation of the volatile species i. 

Hence, the performed above analysis has shown that different solvents using in low-temperature nonequilibriiun polycondensation process can result not only in symthesized polymer quantitative characteristics change, but also in reaction mechanism and polymer chain structure change. This effect is comparable with the observed one at the same polymer receiving by methods of equilibrium and nonequilibrium polycondensation. Let us note, that the fractal analysis and irreversible aggregation models allow in principle to predict symthesized polymer properties as a function of a solvent, used in synthesis process. The stated above results confirm Al-exandrowicz s conclusion [134] about the fact that kinetics of branched polymers formation effects on their topological structures distribution and macromolecules mean shape. 

In modeling the polycondensation kinetics, there is also a question of how we define the reaction rate constants. In the above reaction represented by a functional-group modeling framework, the forward rate constant k is the reaction rate constant for reaction of a methyl ester group with a hydroxyl group, not the reaction rate constant for DMT and ethylene glycol molecules. For example, the above reaction can be represented as follows ... 

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