Synthesis of stimuli-responsive double hydrophilic block copolymers by ATRP and RAFT and their use as nanostructure-directing agents of mesoporous silica materials

Anthony Phimphachanh (1, 2) , Emilie Molina (2) , Mélody Mathonnat (2) , Mael Bathfield (2) , Julien Reboul (2) , Jason Richard (2) , Nathalie Marcotte (2) , Julien Pinaud (2) , Joseph Chamieh (3) , Laurent Leclercq (3) , Herve Cottet (3) , Simon Harrisson (4, 5) , Mathias Destarac (4, 5) , Philippe Dieudonne-George (1) , Martin In (1) , Patrick Lacroix-Desmazes (2) , Corine Gerardin (2)

1 L2C - Laboratoire Charles Coulomb
2 ICGM - Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier
3 IBMM - Institut des Biomolécules Max Mousseron [Pôle Chimie Balard]
4 IMRCP - Interactions moléculaires et réactivité chimique et photochimique
5 IMRCP - P3R - IMRCP - Polymères de Précision par Procédés Radicalaires

A series of double hydrophilic block copolymers DHBCs has been synthesized by controlled radical polymerization (Figure 1). Poly(ethylene oxide)-b-poly(acrylic acid) PEO-b-PAA was prepared by ATRP in acetone. PEO-b-PAA and PEO-b-Poly(N-isopropyl acrylamide) PEO-b-PNIPAM were prepared by RAFT using a PEO-based dithiobenzoate macro-RAFT agent, in water and dioxane respectively. Poly(poly(ethylene glycol) methyl ether acrylate)-b-PAA PmPEGA-b-PAA was prepared by RAFT in water using a trithiocarbonate RAFT agent. Poly(acrylamide)-b-PAA PAM-b-PAA and PAM-b-poly(3-acrylamidopropyl)trimethylammonium chloride) PAM-b-PAPTAC were prepared by RAFT/MADIX using xanthate as control agent, in water/ethanol for the PAM block and directly in water for the second block. The block copolymers have been characterized by SEC, pH titration, conductimetry, and capillary electrophoresis (CE).The reversible formation of micelles by variation of temperature in the case of PEO-b-PNIPAM, or by the mixing of polyelectrolyte DHBCs with a polyelectrolyte of opposite charge in the right range of pH (e.g. anionic PEO-b-PAA associated with cationic oligochitosan) has been studied. The micelles have been characterized by various scattering techniques and CE.Such stimuli-responsive (T, pH, ionic strength) micellar systems have been involved as structuring agents in the synthesis of nanostructured mesoporous silica by sol-gel process. A relationship between the composition of the DHBCs, the composition of the micelles, the experimental conditions of micelle formation and the final mesostructure of the silica materials is foreseen. This strategy has been applied to the preparation of drug-loaded silica for biomedical applications.

Domaines: Matériaux

Anthony Phimphachanh, Emilie Molina, Mélody Mathonnat, Mael Bathfield, Julien Reboul, et al.. Synthesis of stimuli-responsive double hydrophilic block copolymers by ATRP and RAFT and their use as nanostructure-directing agents of mesoporous silica materials. 254th ACS National Meeting, Aug 2017, Washington, United States. pp.2719554. ⟨hal-01804723⟩