| 초록 |
Anionic polymerization of carbonyl-containing polar vinyl monomers (acrylates and methacryltaes) has often been challenged by side reactions involving the carbonyl group, which deteriorate the control of the polymerization. However, proper selection of initiators as well as additives has been proved effective to suppress such difficulties. Some of the additives are also effective in monomer-selective living copolymerization of acrylate and methacrylate. Based on these advancements, we could control a variety of features of polymerization reactions: (1) By transforming the stereoregularity of it-specific polymerization of MMA to syndiotactic(st-)-specific one through the addition of Lewis-acid additives, stereoblock PMMA and stereoblock copolymers with narrow MMD were obtained without deteriorating the living nature of the original polymerization system. (2) When the isotactic (it-)PMMA living anion was used as a macroinitiator for the monomer-selective copolymerization of nBuA and MMA, a triblock copolymer, it-PMMA-block-poly(nBuA)-block-st-PMMA was successfully prepared, which underwent stereocomplex formation reversibly in bulk. (3) Polymerization of a divinyl monomer, 2-(methacryloyloxy)ethyl acrylate (MAEA), with EtAl(ODBP)2 gave a soluble linear polymer with narrow MMD up to 90 % conversion, which consisted of an acrylate main-chain and meth-acrylate side groups through acrylate-selective living polymerization process. |
