Thermal decomposition of 2,2'-azobis(2-methyl-4-hydroxybutyl) propionate in the N,N-dimethylformamide/methyl methacrylate system

J. Szafko; K. Onderko; B. Pabin-Szafko

Published : 2022-09-17

Vol. 48 No. 5 (2003)

Thermal decomposition of 2,2'-azobis(2-methyl-4-hydroxybutyl) propionate in the N,N-dimethylformamide/methyl methacrylate system

J. Szafko K. Onderko B. Pabin-Szafko

Abstract

The thermal decomposition of the initiator 2,2'-azobis(2-methyl-4-hydroxybutyl)propionate (AIB-BD) at 333 K in N,N-dimethylformamide (DMF), methyl methacrylate (MMA) and various DMF/MMA mixtures was studied by volumetric method. The values of the stationary rate AIB-BD of decomposition for various initial 3 concentrations of the initiator [I](0) (within the range of 0.067-0.132 mol . dm(-3)) were determined according to differential eq. (7). These values, according to eq. (8), allowed to determinate the order W of initiator decomposition reaction [defined in eqs. (2) and (4)]. The order x can be regarded as equal to 1 for the whole system, i.e., from a pure solvent (DMF) to pure monomer (MMA). The presented method of determination of the order x cannot be replaced by the estimation of linearity of eq. (10) what is frequently used in the publications, since the other kinetic dependences are also linear for x = 1 and x = 2. The thermal decomposition rate constant (k(d)) of AIB-ID is equal 5.19 . 10(-4) min(-1) and 4.12 . 10(-4) min(-1) in pure DMF and MMA, respectively. The kd values concerning DMF/MMA mixtures were found to be dependent on the mixture composition. This dependence is represented by a monotonically decreasing function of the monomer mole fraction (x(M)). The relation k(d) = f(x(M)) has been interpreted on the basis of a model of initiator solvation by monomer MMA and solvent DMF [eqs. (11) and (12)] The results obtained for the DMF/MMA/AIB-BD system were compared with (previously studied) DMF/MMA/AIBN system.

Keywords

polimeryzacja rodnikowa ; metakrylan metylu ; rozpad termiczny inicjatorów azowych ; rzędowość reakcji rozpadu ; solwatacja inicjatora ; stała szybkości rozpadu termicznego methyl methacrylate radical polymerization ; azoinitiators thermal decomposition ; order of decomposition reaction ; thermal decomposition rate constant ; initiator solvation ; stała szybkości rozpadu termicznego

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Szafko, J., Onderko, K., & Pabin-Szafko, B. (2022). Thermal decomposition of 2,2’-azobis(2-methyl-4-hydroxybutyl) propionate in the N,N-dimethylformamide/methyl methacrylate system. Polimery, 48(5), 329–336. Retrieved from https://polimery.ichp.vot.pl/index.php/p/article/view/1868

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J. Szafko polimery@ichp.pl

Affiliation
Technical University of Szczecin, Polymer Institute, Department of Physical Chemistry of Polymers, ul. Pułaskiego 10, 70-322 Szczecin, Poland

K. Onderko

B. Pabin-Szafko