Thermal Decomposition of Diethyl Ketone Triperoxide (DEKTP) in Methyl Methacrylate: Theoretical and Experimental Study of the Initial Solvation State and its Influence on the Polymerization Process.

KARLA DELGADO RODRIGUEZ; FRANCISCO J. ENRÍQUEZ-MEDRANO; ADRIANA ESPINOZA MARTÍNEZ; GASTÓN BARRETO; NORA EYLER; ADRIANA CAÑIZO; GRACIELA MORALES

JOURNAL OF APPLIED POLYMER SCIENCE

JOHN WILEY & SONS INC

Lugar: New York; Año: 2015

0021-8995

The decomposition rate constant (kd) of 3,3,6,6,9,9-hexaethyl-1,2,4,5,7,8-hexaoxacyclononane (DEKTP, diethyl ketone triperoxide) in methyl methacrylate (MMA) was determined by the kinetic study of its thermal decomposition at temperatures from 110 until 140°C. The calculated kd for DEKTP in MMA was 2.4 times lower than in Styrene (St). Semi-empirical quantum chemical calculations demonstrated that the DEKTP molecule in MMA requires a higher interaction energy than in St, which explains its low kd value. Bulk polymerization kinetics of DEKTP in MMA revealed the presence of an induction period, in contrast with polymerizations with St, providing clear evidence of the influence of the state of solvation at the early stages of bulk polymerization. This work provides mechanistic insight on the interactions between multi-functional cyclic peroxides and vinyl monomers, and their influence on polymerization kinetic.