Anionic synthesis of primary amine functionalized polystyrenes via hydrosilation of allylamines with silyl hydride functionalized polystyrenes

A general anionic omega-chain-end functionalization methodology is described and illustrated by the synthesis of omega-primary amine functionalized polystyrenes. First, the quantitative omega-silyl hydride functionalization of well-defined poly(styryl)lithium (M-n = 2200 and 14 100 g/mol) was effected with dimethylchlorosilane in hydrocarbon solution at room temperature. In the second step, involving amination by hydrosilation, the silyl hydride functionalized polystyrene was added quantitatively to 3-[N,N- bis(trimethylsilylamino]-l-propene, a protected amine, using Karstedt's Pt(0) hydrosilation catalyst in benzene. One of the principal advantages of this method is the fact that it is not necessary to use protecting groups for many functional groups, as illustrated by the quantitative primary amine functionalization of omega-silyl hydride functionalized poly(styryl)lithium with allylamine using the Karstedt's hydrosilation catalyst. The silyl hydride and amine functionalized polystyrenes were characterized by SEC, FTIR, H-1 and C-13 NMR, MALDI-TOF mass spectrometry, and end-group titration.