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Regioregular poly(3-hexylthiophene) has been successfully incorporated into various poly( N, N-dimethylamino-2-ethyl methacrylate)-based block copolymers, i.e., P3HT- b-PDMAEMA, via Grignard metathesis (GRIM) method and atom transfer radical polymerization (ATRP) reactions. The structure of the diblock copolymers was fully confirmed by FT-IR, H NMR spectroscopy, gel permeation chromatography (GPC), and ultraviolet-visible spectroscopy (UV-vis). The recovered copolymers could be treated by protonation of the pending tertiary amine functions and depending on the relative content in PDMAEMA, the copolymers could be solubilized in more polar solvents where P3HT alone proved to be totally insoluble. [ABSTRACT FROM AUTHOR]

Abstract: The synthesis of amphiphilic and adaptative block copolymers has been envisioned following a commutative two-step strategy involving atom transfer radical polymerization (ATRP) and the Huisgen-1,3-dipolar cycloaddition techniques. The reliability of this strategy is based on the use of an azido-containing ATRP initiator, the 2-(2-azidoethoxy)ethylbromoisobutyrate (N3E i BBr), able to be “clicked” to an alkyne-terminated derivative and to promote the ATRP polymerization from the active site. In the context of this work, an alkyne-terminated poly(ε-caprolactone) produced by ring-opening polymerization (ROP) of CL was employed as hydrophobic “clickable” segment. The N3E i BBr initiator was obtained by nucleophilic substitution of the chloride atom from 2-(2-chloroethoxy)ethanol by an azide function and followed by the esterification of the hydroxy function by bromoisobutyryl bromide. This initiator was employed in polymerization of N,N-dimethylamino-2-ethyl methacrylate (DMAEMA) monomer by ATRP in THF at 60°C using CuBr complexed by 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA) as catalytic complex. Low initiation efficiencies were obtained and they were ascribed to intramolecular cyclization during the polymerization as evidenced by ESI-MS and 2D NMR spectroscopy. The “Click” coupling reaction was performed in THF at r.t. and was found to be efficient when using CuBr complexed by 2,2′-bipyridine ligand. To circumvent the low initiation efficiency, the N3E i BBr could be “clicked” in a first step to PCL precursors before initiating the polymerization of DMAEMA monomer by ATRP. In this context, various catalytic complexes in different composition ratio were employed to optimize the “click” coupling step. Moreover, this strategy was found to be suitable to produce well-defined PCL-b-PDMAEMA block copolymers, characterized by narrow polydispersity indices. Since ATRP and the Huisgen-1,3-dipolar cycloaddition both require the use of a copper(I)-based catalyst, the two first strategies were merged in a “one-pot” process in order to obtain in one step a well-defined block copolymer characterized by a narrow polydispersity index and predictable composition and block lengths. [Copyright &y& Elsevier]