Blending the Effectiveness of Anionic Polymerization with the Versatility of RAFT by Use of the Atom Transfer Radical Addition–Fragmentation Technique

• Published in: Macromolecular chemistry and physics 2019-05, Vol.220 (10), p.n/a
• Main Authors: Forrester, Michael J., Bradley, William, Lin, Fang‐Yi, Hernández, Nacú B., Williams, R. Chris, Kraus, George, Cochran, Eric W.
• Format: Article
• Language: English
• Subjects: Addition polymerization; Anionic polymerization; ATRAF; Block copolymers; Chain transfer; chain transfer agents; Chains (polymeric); Conversion; Fragmentation; Organic chemistry; Polyelectrolytes; Polymerization; RAFT; Reagents
• ISSN: 1022-1352; 1521-3935
• DOI: 10.1002/macp.201900065

The efficient conversion of a living anionic polymer chain end to a macrochain transfer agent suitable for reversible addition–fragmentation chain transfer (RAFT) polymerization is reported. Conversion to the macrochain transfer agent efficiency reached as high as 97% by capping the polyanion with alcohol, coupling with α‐bromoisobutryl bromide, followed by atom‐transfer radical addition–fragmentation with bis(thiobenzyl)disulfide to add the chain transfer agent functionality. To our knowledge, this is the most efficient marriage of anionic and reversible addition–fragmentation transfer polymerization reported to date, and can be carried out under common industrial processing conditions. The combination of these polymerization methods broadens the scope of commercially accessible block copolymers by exploiting the advantages of both RAFT and anionic polymerization chemistries. A new method is developed to allow for highly efficient and cost‐effective conversion of an anionically grown polymer into a RAFT macro‐chain transfer agent. This allows for the large‐scale production of a wide variety of styrenic/diene copolymers with meth(acrylic) monomer sources, thereby allowing for the introduction of a staggering number of new industrially relevant polymeric materials.