Hybrid Block Copolymer Synthesis by Merging Photoiniferter and Organocatalytic Ring‐Opening Polymerizations

Abstract

Access to block copolymers from monomers that do not polymerize via a common mechanism requires initiation from a multifunctional species that allows orthogonal polymerization chemistries. We disclose a strategy to provide well‐defined polyacrylamido‐b‐polyether block copolymers by a one‐pot combination of photoiniferter polymerization and organocatalytic ring‐opening polymerization (ROP) using a hydroxy‐functionalized trithiocarbonate photoiniferter as the dual initiator at ambient temperature. Our results reveal good compatibility between the two polymerization systems and highlight that they can be performed in arbitrary order or simultaneously with good retention of the thiocarbonylthio functionality. We also demonstrate selective temporal control over the photoiniferter polymerization during concurrent ROP. We harnessed the efficiency of combining these polymerization systems to provide tailor‐made block copolymers from chemically distinct monomers.

Polyphosphonate-Based Macromolecular RAFT-CTA Enables the Synthesis of Well-Defined Block Copolymers Using Vinyl Monomers

“…This strategy involved the use of 2-bromo-isobutyryl groups as functional initiators or as part of the cyclic monomer (CH 2 O) 2 P­(O)­OR to form macroinitiators for ATRP via ROP of cyclic phosphates followed by the preparation of block or graft copolymers (Scheme A,B). − In contrast, no PPE-containing block copolymers have been reported previously using a RAFT protocol. Besides the well-known PEGylated macro-CTAs, , other CTAs used mostly hydrophobic polyesters, polyethers, and polycarbonates from ROP to prepare block copolymers. − A water-soluble PPE macro-CTA opens up the possibilities of replacing commercial PEGylated CTAs in a broad range of applications, such as drug encapsulation or polymerization-induced self-assembly, for example. , …”

One-Pot Synthesis of Polyester-Based Linear and Graft Copolymers for Solid Polymer Electrolytes

“…In the one-pot synthesis of BCPs, we try the combination of RAFT polymerizations of methacrylate monomers (MMA, BMA, and PEGMA) or styrene and ROP of ε-CL. 69,70 our one-pot synthesis method uses ACVA bifunctional free radical initiator instead of traditional free radical initiators combined with ROP catalysts. (Figure 4).…”

A Simple and Green Oxygen‐Tolerant RAFT Polymerization without Additional Catalyst and Initiator

“…Stimuli-responsive (smart and dynamic) reversible deactivation radical polymerizations (RDRPs) have recently attracted increasing attention from researchers due to their simple operation and spatiotemporalcontrol. [1][2][3][4] External stimuli, such as microwave, [5] ultrasound, [6] light, [7][8] and electricity, [9] are able to mediate the activation-deactivation process of RDRP, including nitroxide-mediated polymerization (NMP), [10][11] atom transfer radical polymerization (ATRP), [12][13] reversible addition-fragmentation chain transfer (RAFT), [14][15][16] resulting in switchable polymerization. Among them, light-driven RAFT polymerization has emerged as an attractive technique due to easy operation and functional group tolerance.…”