Stereospecific bulk polymerization of methyl methacrylate initiated by its tactic polymers

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Abstract
Methyl methacrylate (MMA) was polymerized by radical initiation at 90°C by its own preformed tactic polymers, i.e., conventional (c‐PMMA), isotactic (i‐PMMA), and syndiotactic (s‐PMMA) PMMA, and also by a preformed 1:1 stereocomplex of i‐PMMA and s‐PMMA. The collected polymers were separated into two fractions by extraction with boiling acetone and characterized by 60 MHz NMR spectra and viscometry. Higher polymerization rates were obtained in the presence of stereo‐regular PMMA than in the presence of c‐PMMA. Moreover, it appeared that i‐PMMA promoted the formation of s‐PMMA, and conversely s‐PMMA the formation of i‐PMMA, especially in the initial stages of the reaction. A higher M̄v of the preformed polymer yielded a higher rate and a higher stereospecificity of the polymerization. No polymerization took place in the absence of performed PMMA. The results support a replica mechanism proposed by Szwarc, in which polymerization is preceded by a specific arrangement of monomeric units along the polymeric chain into a distinctive pattern. Such arrangement coupled with a strong tendency of the isotactic and syndiotactic species to associate may lead to the present stereospecific replica polymerization. This association is demonstrated by rapid gelation during polymerization and by lowering of reduced viscosity in very dilute mixtures of i‐PMMA and s‐PMMA in MMA.