Modeling the spontaneous initiation of the polymerization of methyl methacrylate

• Published in: Journal of molecular modeling Vol. 14; no. 11; pp. 1053 - 1064
• Main Authors: Zhang, Cuili, Wang, Xueye, Liu, Liming, Wang, Yanling, Peng, Xinyu
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Springer-Verlag 01.11.2008
• Subjects: Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Computer Appl. in Life Sciences; Computer Applications in Chemistry; Computer Simulation; Methylmethacrylate - chemistry; Models, Molecular; Molecular Medicine; Original Paper; Stereoisomerism; Theoretical and Computational Chemistry; Thermodynamics; Intrinsic reaction coordination (IRC); Methyl methacrylate (MMA); Spontaneous polymerization; Density functional theory (DFT)
• ISSN: 1610-2940; 0948-5023
• DOI: 10.1007/s00894-008-0344-6

The mechanism of the spontaneous initiation of the polymerization of methyl methacrylate (MMA) was investigated theoretically. The six minimum energy paths (MEP) of the possible reactions were calculated using the density functional theory (DFT) in conjunction with the B3LYP functional and 6-31G* basis set. The Diels-Alder initiation mechanism (path (I) and path (II)) with remarkably high energy barriers is not applicable to MMA. Four favorable paths were found (path (III), path (IV), path (V) and path (VI)), which are supporting the Flory mechanism. Path (V) has the lowest active energy. Therefore this path is considered as the main path for the spontaneous polymerization of MMA. Figure The mechanism of the spontaneous initiation of the polymerization of methyl methacrylate (MMA) was investigated theoretically. The six minimum energy paths (MEP) of the possible reactions were calculated using the density functional theory (DFT) in conjunction with the B3LYP functional and 6-31G* basis set.