Synthesis and characterization of amphiphilic triblock polymers by copper mediated living radical polymerization

Abstract 2-Dimethylaminoethyl methacrylate (DMAEMA) and 2-diethylaminoethyl methacrylate (DEAEMA) block copolymers have been synthesized by using poly(ethylene glycol), poly(tetrahydrofuran) (PTHF) and poly(ethylene butylenes) macroinitiators with copper mediated living radical polymerization. The use of difunctional macroinitiator gave ABA block copolymers with narrow polydispersities (PDI) and controlled number average molecular weights (Mn’s). By using DMAEMA, polymerizations proceed with excellent first order kinetics indicative of well-controlled living polymerization. Online 1H NMR monitoring has been used to investigate the polymerization of DEAEMA. The first order kinetic plots for the polymerization of DEAMA showed two different rate regimes ascribed to an induction period which is not observed for DMAEMA. ABA triblock copolymers with DMAEMA as the A blocks and PTHF or PBD as B blocks leads to amphiphilic block copolymers with Mn’s between 22 and 24 K (PDI 1.24–1.32) which form aggregates/micelles in solution. The critical aggregation concentrations, as determined by pyrene fluorimetry, are 0.07 and 0.03 g dm−1 for PTHF- and PBD-containing triblocks respectively.

[1]  Sébastien Perrier,et al.  Copper(I)-Mediated Living Radical Polymerization in the Presence of Oxyethylene Groups: Online 1H NMR Spectroscopy To Investigate Solvent Effects , 2000 .

[2]  P. Dubois,et al.  Alternative Atom Transfer Radical Polymerization for MMA Using FeCl3 and AIBN in the Presence of Triphenylphosphine: An Easy Way to Well-Controlled PMMA† , 1998 .

[3]  M. Sawamoto,et al.  Metal-catalyzed living radical polymerization. , 2001, Chemical reviews.

[4]  P. Dubois,et al.  Controlled Radical Polymerization of Methyl Methacrylate in the Presence of Palladium Acetate, Triphenylphosphine, and Carbon Tetrachloride , 1997 .

[5]  S. Armes,et al.  Polymeric Surfactants for the New Millennium: A pH‐Responsive, Zwitterionic, Schizophrenic Diblock Copolymer , 2002 .

[6]  P. Dubois,et al.  Controlled Radical Polymerization of Methacrylic Monomers in the Presence of a Bis(ortho-chelated) Arylnickel(II) Complex and Different Activated Alkyl Halides , 1996 .

[7]  V. Percec,et al.  Living radical polymerization of styrene initiated by arenesulfonyl chlorides and CuI(bpy)nCl , 1995 .

[8]  S. Armes,et al.  Synthesis of shell cross-linked micelles with pH-responsive cores using ABC triblock copolymers , 2002 .

[9]  S. Armes,et al.  Influence of polymer architecture on the structure of complexes formed by PEG-tertiary amine methacrylate copolymers and phosphorothioate oligonucleotide. , 2002, Journal of controlled release : official journal of the Controlled Release Society.

[10]  M. Sawamoto,et al.  Nickel-Mediated Living Radical Polymerization of Methyl Methacrylate1 , 1997 .

[11]  P. Dubois,et al.  Controlled radical polymerization of methyl methacrylate initiated by an alkyl halide in the presence of the Wilkinson catalyst , 1998 .

[12]  D. Haddleton,et al.  Atom Transfer Polymerization of Methyl Methacrylate Mediated by Alkylpyridylmethanimine Type Ligands, Copper(I) Bromide, and Alkyl Halides in Hydrocarbon Solution , 1999 .

[13]  M. Sawamoto,et al.  Living Radical Polymerization of Methyl Methacrylate with Ruthenium Complex: Formation of Polymers with Controlled Molecular Weights and Very Narrow Distributions1 , 1996 .

[14]  D. Haddleton,et al.  Atom Transfer Radical Polymerization of Methyl Methacrylate Initiated by Alkyl Bromide and 2-Pyridinecarbaldehyde Imine Copper(I) Complexes , 1997 .

[15]  S. Armes,et al.  Synthesis of controlled-structure sulfate-based copolymers via atom transfer radical polymerisation and their use as crystal habit modifiers for BaSO4 , 2002 .

[16]  Krzysztof Matyjaszewski,et al.  Controlled/"living" radical polymerization. atom transfer radical polymerization in the presence of transition-metal complexes , 1995 .

[17]  K. Jankova,et al.  Synthesis of Amphiphilic PS-b-PEG-b-PS by Atom Transfer Radical Polymerization , 1998 .

[18]  K. Matyjaszewski,et al.  Step-Growth Polymers as Macroinitators for ``Living'' Radical Polymerization: Synthesis of ABA Block Copolymers , 1997 .