Polymerization of methacrylates containing furan nuclei with different electron‐donor capacity

Abstract

S U M M A R Y :The polymerization of furfuryl methacrylate (FMA) and carbomethoxyfurfuryl methacrylate (CMFMA) has been studied. It has been established that under equal conditions the rate of CMFMA polymerization is greater than the rate of polymerization of FMA. The temperature dependence of the rate constants showed that the polymerization of FMA is associated with a greater energy of activation. These results are explained by z-complex formation between the furan nuclei on the one hand and the methacrylic double bonds or the growing methacrylic radicals on the other. Complex stability depends on the electron-donor capacity of the furan nuclei. ZUSAMMENFASSUNG:Die Polymerisation von Furfurylmethacrylat (FMA) und Carbomethoxyfurfurylmethacrylat (CMFMA) wurde untersucht. Unter gleichen Bedingungen ist die Polymerisationsgeschwindigkeit von CMFMA grol3er als diejenige von FMA. Die Temperaturabhangigkeit der Geschwindigkeitskonstanten zeigte aunerdem, da13 die FMA-Polymerisation mit einer grol3eren Aktivierungsenergie verbunden ist.Diese Ergebnisse wurden mit einer x-Komplexbildung zwischen den Furanringen einerseits und den Methacrylatdoppelbindungen oder den wachsenden Methacrylatradikalen anderseits erklart. Die Stabilitat der Komplexe hangt von der Elektronenabgabekapazitat der Furanringe ab.

Kinetic Study of the Thermopolymerization of Furfuryl Methacrylate in Bulk by Mathematical Modeling. Part A: Simulation of Experimental Data and Sensitivity Analysis of Kinetic Parameters

“…The depression of the degradative transfer reaction in the CMFMA system could, in turn, explain the observed increase in the global polymerization rate for this monomer in comparison to FM (Figure 4). Mijajlov and Boudevska [13] accounted for this effect by the possible differences in stability of the p complex which could be formed between furan nuclei and methacrylic double bonds in both monomers (HenriciOlivé's theory). They presumed that this kind of p complex should be more stable for FM (as this possesses more donors of p electrons in its nucleus than CMFMA) which explains the slower polymerization rate of FM in comparison to CMFMA.…”

“…It has been stated previously that in this work, for the simulation of the thermopolymerization of FM initiated by AIBN at different temperatures (333, 343, and 353 K), the experimental data obtained by Mijailov and Boudevska [13] was used. The values of the kinetic constants (k in , k 0 trd , k p , k trd1 , k is , k tc ) at these temperatures were calculated using Arrhenius' equations shown in Table 2.…”

“…Experimental data of thermopolymerization of FM in bulk initiated by AIBN. [13] Monomer conversion (x) with polymerization time (t) at different initial initiator concentration and temperature. Initial monomer concentration in the polymerizing sample is primary microradical (R) to the acrylic double bond.…”

“…[13] and are assembled in Table 1. For simulation of the experiments, a numerical multi-step integration subroutine ODE15S [18] of ordinary differential equations system (ODES) was used.…”

“…[1,3,7,9] The aim of this work was to extend the application of the proposed model to the thermopolymerization of two acrylfuranic monomers, namely, FM and carbomethoxyfurfuryl methacrylate (CMFMA, see Figure 1) in order to estimate the versatility and utility of the developed tool for the theoretical in-depth study of the kinetics of formation of three-dimensional networks for different furanic structures under different experimental conditions. With this idea in mind, for the current work the cross-linked model was applied to the polymerization, yielding up to 90% conversion of the monomer over a temperature range of 333-353 K. [13] It is logical to expect that such drastic variations both in the experimental conditions (compared to the preceding photocured system) and in the monomer structure (notably the presence of the carbomethoxy group in the C-5 position of the furan ring) would require appropriate modification to the previously developed model to be made. Such modifications were introduced in this work.…”