Fast-activated anionic polymerization of ε-caprolactam in the bulk under quasi-adiabatic conditions: Comparison of different kinetic models

Abstract

The kinetics of e-caprolactam fast-activated anionic polymerization in the bulk under quasi-adiabatic conditions is analyzed in terms of three semiempirical schemes. Malkin's model, the most frequently quoted approach in the literature, provides an excellent simulation of the polymerization kinetics in our experimental conditions, but the values of the derived parameters do not remain constant, as predicted by the model when different experimental conditions are chosen, and do not allow any correlation with the physical and chemical aspects of the reaction. The same limit exists for Lin's model, with a poorer agreement between simulation and experimental data. Only Kamal-Sourour's model provides almost constant values of the parameters present in the equation and can be considered a valid approach for the description of the whole course of the reaction in our experimental conditions. The relevance of the auto acceleration step is compared for two very fast activators and related to the most accredited interpretation of its occurrence. V C 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4474-4480

Some new perspectives of anionic polyamide 6 (APA 6) synthesis

“…As already described in detail in a previous study of ours, the kinetic data of CL anionic polymerization activated by TESiPIC‐B have been analyzed in terms of the Kamal–Sourour's model, suggested very recently by Teuwen et al . as a model able to describe not only the polymerization kinetics of many thermoset systems, but also the whole course of CL anionic polymerization in the bulk.…”

“…As thoroughly discussed in the aforementioned reference, the values of the six parameters present in Kamal–Sourour's equation provide a useful comparison with those originated by another fast activator, cyclohexylisocyanate blocked with CL (CHIC‐B). Differences between the two activators have been explained by taking in account the role of the uncatalyzed term of the equation, with the corresponding values linked to obvious differences of chemical reactivity between TESiPIC‐B and CHIC‐B.…”

“…A detailed description of the procedure for CL activated anionic polymerization in the bulk as well as a full characterization of the reaction products has been recently published elsewhere . The activator described in the present study is TESiPIC‐B, usually tested at a concentration of 50.7 mmol/l, corresponding to 0.6 mol% referred to 100 mol of CL.…”

Influence of fiber orientation and geometry variation on flow phenomena and reactive polymerization of ϵ-caprolactam

“…Different approaches to describe and model the anionic polymerization of ϵ-caprolactam and to derive kinetic constants have been proposed, which were summarized in Russo et al (2013). Though some models inferred from mechanistic considerations have been proposed (Cimini and Sundberg, 1986), the purely empirical Malkin kinetics can still be regarded as the method of choice (Nagy et al, 2014b;Lee and Kim, 1988;Bolgov et al, 1981;Malkin et al, 1979) which can be explained by the fact that the derived kinetic factors are usually strongly concentration dependent.…”

A Review of Thermoplastic Resin Transfer Molding: Process Modeling and Simulation

“…The experimental data obtained are further adjusted with the modeling. Ruso et al [10,48] and Teuwen [25] wrote a comprehensive review summarizing research in this field. We, in the current study, will describe the most important milestones in the development of kinetic models in order to tell the entire story.…”