One-Pot Synthesis of Strong Anionic/Charge-Neutral Amphiphilic Block Copolymers

Despite the ever more versatile polymerization techniquesthatare becoming available, the synthesis of macromolecules with tailoredfunctionalities can remain a lengthy endeavor. This becomes more conspicuouswhen the implementation of incompatible chemistries (i.e., strongpolyelectrolytes) within sequence-controlled polymers is desired,often requiring (i) polymerization, (ii) chain extension, and (iii)postpolymerization modification. Herein, we explore the productionof strong anionic/charge-neutral block copolymers (BCPs) in a one-potfashion. This straightforward three-step process includes the synthesisof a macroinitiator and chain extension via rapid and efficient photomediatedatom transfer radical polymerization, followed by in situ deprotectionto expose the polyanionic domains. The resulting BCPs, which are strongamphiphiles by nature, are capable of self-assembly in aqueous media,as evidenced by dynamic light scattering, small-angle X-ray scattering,& zeta;-potential measurements, and transmission electron microscopy.We further demonstrate the versatility of our methodology by producingseveral BCPs through sampling of a single reaction mixture, enablingthe straightforward production of strong polymer amphiphiles.