Ligated Living Anionic Polymerization

Teyssie and Jerome [63] have solved the temperature problem to some extent by conducting anionic polymerization of acrylates and methacrylates in the presence of LiCl, LiOR, or Li0(CH2CH20)nMe. These agents complex with lithium enolate chain ends. 

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The statistical anionic copolymerization of acrylates and methacrylates is also controlled in the presence of LiOEEM (30), as testified by the copolymerization of MMA and tBuA in THF at —78°C. Block copolymers were also prepared by the sequential polymerization of at least two methacrylates and acrylates. For instance, PMMA- >/c cA -PbBuA and PMMA-fcZocA -PnNonA were synthesized . The addition order of the comonomers is important. Indeed, when living PnBuA is the macroinitiator of the MMA polymerization, the expected block copolymer is contaminated by homo-PnBuA, which is not the case when the polymerization sequence is reversed. A fuUy acrylic-based thermoplastic elastomer, PMMA-fcZocA -P(2EtHA)-fcZocA -PMMA, was prepared by the sequential LiOEEM-ligated polymerization of MMA, 2-EtHA and MMA. ... 

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