Anionic Synthesis of Primary and Secondary Amine-Functionalized Polymers Using Imine Chemistry

A review of methods for the anionic synthesis of well-defined, amine-functionalized polymers using imines as functionalizing agents is provided. The disparate results in the literature regarding functionalizations with N -(benzylidene)trimethylsilylamine to form primary amine functionalized polymers are discussed; the efficiency of functionalization depends on the molecular weight of the polymeric organolithium(PLi). Efficient functionalizations are observed for PLi with n>10 000 g/mol. The poor functionalization yields using ketimines with enolizable hydrogens is explained. The use of N -trimethylsilyldiphenylcarbimide as a quantitative primary amine functionalizing reagent is described. Recent results on the anionic synthesis of secondary amine-functionalized polymers using N -(benzylidene)methylamine as the functionalization agent are presented.