The spontaneous polymerization of methyl methacrylate-IV: Formation of cyclic dimers and linear trimers

✍ Scribed by J. Lingnau; M. Stickler; G. Meyerhoff

• Book ID: 103073347
• Publisher: Elsevier Science
• Year: 1980
• Tongue: English
• Weight: 463 KB
• Volume: 16
• Category: Article
• ISSN: 0014-3057
• DOI: 10.1016/0014-3057(80)90050-6

✦ Synopsis

The mechanism of the spontaneous polymerization of methyl methaerylate (MMA) is still unknown. We now present evidence for the formation of I.I.2.2-tetrasubstituted cyciobutanes in a side-reaction confirming, by the kinetics of their formation, the postulated biradical mechanism of initiation. The structures and formation kinetics of linear trimers were determined thus verifying the en-enophil mechanism for the formation of unsaturated oligomers.

As was shown for the spontaneous polymerization of styrene [I ], investigation of the oligomers formed in side-reactions provides an effective tool for establishing the initiation mechanism. The Mayo mechanism for styrene cannot be applied to methyl methacrylate (MMA), since the analogous Diels Alder adducts (d. scheme I) would not have any tendency to homolysis as is the rearomatization in the case of styrene.