Controlled Polymerization of Electron-deficient Naphthalene-diimide Containing Monomer by Negishi-type Catalyst-transfer Polymerization

Abstract

Negishi-type Catalyst-Transfer Polymerization (NCTP) of electron-deficient monomers has been attempted for the first time. Imide or ketone groups in such monomers show an excellent electron-deficient property. However, these functional groups cannot generally tolerate towad highly reactive Grignard reagents. In this work, we applied a zincate complex with lower basicity, ^tBu₄ZnLi₂, for the polymerization of a naphthalene-diimide-containing monomer. Zinc-halogen exchange reaction was quantitatively conducted at 60 °C for 1 h without any protection of the imide group. Then, the polymerization was carried out by adding the Pd catalyst to afford an electron-deficient polymer, PTNDIT (M_n = 8,400 and D = 1.35).