Direct synthesis via RAFT of amphiphilic diblock polyelectrolytes facilitated by the use of a polymerizable ionic liquid as a monomer

Abstract

A new method for obtaining amphiphilic block polyelectrolytes with a strongly hydrophobic block in homogeneous conditions, is described and demonstrated by synthesizing poly(2-acrylamido-2-methanepropanesulfonate-b-styrene) block copolymers using RAFT polymerization. The technique...

Micellar drug delivery vehicles formed from amphiphilic block copolymers bearing photo-cross-linkable cyclopentenone side groups

“…The observation of a decrease in molecular weight of the block copolymers in comparison to the macro-RAFT agent was observed before and is related to changes in block and column interaction, contraction, or collapse of the polymer coil. 37,38 Block copolymerization involving the chain extension of the POEGA macro-RAFT agents was instead confirmed via MALDI-ToF-MS (Fig. S4a-d †).…”

Strong Anionic/Charge-Neutral Block Copolymers from Cu(0)-Mediated Reversible Deactivation Radical Polymerization

“…Several controlled polymerization techniques, including the ring-opening polymerization of aziridines, , the nitroxide-mediated polymerization of sodium styrene sulfonate, , or the reversible addition–fragmentation chain-transfer (RAFT) polymerization of (meth)­acrylates, now permit the synthesis of anionic and even anionic/charge-neutral macromolecules, although monomer neutralization might be required to facilitate the synthesis . However, in spite of the recent developments in copper-catalyzed polymerization methods, the direct synthesis of strong polyanions via these techniques remains highly challenging.…”

“…Several controlled polymerization techniques, including the ring-opening polymerization of aziridines, 34 , 35 the nitroxide-mediated polymerization of sodium styrene sulfonate, 36 , 37 or the reversible addition–fragmentation chain-transfer (RAFT) polymerization of (meth)acrylates, 38 now permit the synthesis of anionic and even anionic/charge-neutral macromolecules, although monomer neutralization might be required to facilitate the synthesis. 39 However, in spite of the recent developments in copper-catalyzed polymerization methods, 40 the direct synthesis of strong polyanions via these techniques remains highly challenging. While surface-initiated atom transfer radical polymerization can be used to grow homopolymer chains from modified gold or silicon in water/methanol mixtures, 41 difficulties persist for the production of macromolecules with more complex compositions, such as block and random copolymers.…”

Protected Poly(3-sulfopropyl methacrylate) Copolymers: Synthesis, Stability, and Orthogonal Deprotection

“…This remains a particular challenge for sulfonate-based strong polyanions. For such sulfonates, work-arounds have been reported where the inorganic counterion was replaced by a bulky quaternary ammonium salt, which renders the polyelectrolyte more soluble in polar organic solvents. , Disadvantages of this approach, however, remain similar to the directly synthesized strong anionic/hydrophobic copolymers, as the choice of the hydrophobic component is still limited, and the molecular weight characterization of charged species remains challenging.…”