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

Abstract

Despite recent developments in controlled polymerization techniques, the straightforward synthesis of block copolymers that feature both strong anionic and charge-neutral segments remains a difficult endeavor. In particular, solubility issues may arise during the direct synthesis of strong amphiphiles and typical postpolymerization deprotection often requires harsh conditions. To overcome these challenges, we employed Cu(0)mediated reversible deactivation radical polymerization (Cu(0)-RDRP) on a hydrophobic isobutoxy-protected 3-sulfopropyl acrylate. Cu(0)-RDRP enables the rapid synthesis of the polymer, reaching high conversions and low dispersities while using a single solvent system and low amounts of copper species. These macromolecules are straightforward to characterize and can subsequently be deprotected in a mild yet highly efficient fashion to expose their strongly charged nature. Furthermore, a protected sulfonate segment could be grown from a variety of charge-neutral macroinitiators to produce, after the use of the same deprotection chemistry, a library of amphiphilic, double-hydrophilic as well as thermoresponsive block copolymers (BCPs). The ability of these various BCPs to self-assemble in aqueous media was further studied by dynamic light scattering, ζ-potential measurements as well as atomic force and electron microscopy.

Effect of Polyelectrolyte Charge Density on the Linear Viscoelastic Behavior and Processing of Complex Coacervate Adhesives

“…The PBSPMA homopolymer and P­(BSPMA x - co -OEGMA y ) copolymers were synthesized using a two-step procedure (i.e., RAFT polymerization followed by nucleophilic deprotection). While the production of the strong anionic homopolymer is straightforward, the feasibility of a proper statistical copolymerization had to be investigated. , The homopolymerization kinetics of either BSPMA or OEGMA (∼100 equiv to the RAFT agent) were followed using a combination of 1 H NMR spectroscopy and SEC (Figure ). The ln­([M] 0 /[M]) vs time plots, constructed from 1 H NMR conversion data, indicate very similar kinetic profiles between the two methacrylates with comparable apparent rate constants of k BSPMA = 0.168 h –1 and k OEGMA = 0.177 h –1 .…”

Scalable Fabrication of Reversible Antifouling Block Copolymer Coatings via Adsorption Strategies

“…The 2-cyanopropan-2-yl propyl trithiocarbonate (CPP-TTC) chain transfer agent and PEG 90 -Br macroinitiator were synthesized as reported elsewhere. , …”

“…The 2-cyanopropan-2-yl propyl trithiocarbonate (CPP-TTC) chain transfer agent and PEG 90 -Br macroinitiator were synthesized as reported elsewhere. 50,51 AIBN was recrystallized twice from methanol. Commercially available monomers were passed over a short aluminum oxide (basic) column to remove inhibitors prior to their direct use in the polymerizations.…”

Vegetable Oil as a Continuous Phase in Inverse Emulsions: ARGET ATRP for Synthesis of Water-Soluble Polymers

“…Over the years, various ATRP techniques have been developed to improve various environmental aspects, such as dramatically diminished copper catalyst loading from thousands to single digits of ppm loading by continuous regeneration of transition metal catalyst complex. This is accomplished by the reduction of deactivators (Cu­(II)/L) to activators (Cu­(I)/L) by chemical reducing agents, e.g., ascorbic acid, − glucose, zerovalent metal, − and also external factors including electric current, ultrasonic waves, , and light. − One of the research directions in ATRP is polymerization in aqueous and dispersed media ,, or using nontoxic biobased solvents derived from biomass . The polymerization of hydrophilic monomers is attractive because they dissolve in water and do not require organic solvents.…”