Controlled synthesis of amphiphilic block copolymers based on polyester and poly(amino methacrylate): Comprehensive study of reaction mechanisms

Laetitia Mespouille, Magali Vachaudez, Fabian Suriano, Pascal Gerbaux, Wim Van Camp, Olivier Coulembier, Philippe Degée, Robert Flammang, Filip Du Prez, Philippe Dubois

Research output: Contribution to journalArticlepeer-review

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 (N3EiBBr), 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 N3EiBBr 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 N3EiBBr 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.

Original languageEnglish
Pages (from-to)990-1003
Number of pages14
JournalReactive and Functional Polymers
Volume68
Issue number5
DOIs
Publication statusPublished - 1 May 2008
Externally publishedYes

Keywords

  • Adaptative
  • Amphiphilic
  • ATRP
  • Block copolymer
  • Click reaction
  • Huisgen-1,3-dipolar cycloaddition

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