Abstract
The anionic polymerization of methyl methacrylate (MMA) was investigated using dilithium tetra-tert-butylzincate (TBZL), which is a bulky zincate, as an initiator. Poly(methyl methacrylate) (PMMA) with a narrow molecular weight distribution was obtained by conducting the polymerization in toluene at −80 °C. Chain-end analysis revealed the formation of PMMA with a tert-butyl group at the α-end and a hydrogen atom at the ω-end. These results suggest the living nature of the present polymerization. However, a prolonged polymerization time or elevated temperature caused backbiting reactions. Postpolymerization modification of the formed PMMA was also investigated using TBZL as a transesterification catalyst. Chain-end analysis revealed that terminal-selective transesterification occurred only at the monomeric unit at the terminating chain end. Therefore, TBZL appears to play dual roles in the production of chain-end-modified PMMA: an initiator for anionic polymerization and a catalyst for terminal-selective transesterification.
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