Synthesis of a Poly(3-dodecylthiophene) Bearing Aniline Groups for the Covalent Functionalization of Carbon Nanotubes

The functionalization of carbon nanotubes by polymers necessitates two steps, first their modification by oxidizing them or by covalently attaching small compounds to them, then the growth of the polymer chains from these anchors or their grafting onto them. In order to better control the process and the rate of functionalization, we develop polymers able to covalently react with the carbon nanotubes by their side chains in one step. We describe the synthesis of a copolymer of dodecylthiophene and its analogue bearing an aniline group at the end of the dodecyl side chain. This copolymer can functionalize single-walled carbon nanotubes (SWNTs) non-covalently and disperse more SWNTs than its hexyl analogues. UV-Vis and fluorescence spectroscopies show that in these non-covalent hybrids, the polymer forms p-stacked aggregates on the SWNTs. The non-covalent hybrids can be transformed into covalent ones by diazonium coupling. In these covalent hybrids the polymer is no longer p-stacked. According to Raman spectroscopy, the conformation of the poly(3-hexylthiophene) backbone is more ordered in the non-covalent hybrids than in the covalent ones.