Fast and Scalable Synthetic Route to Densely Grafted, Branched Polystyrenes and Polydienes via Anionic Polymerization Utilizing P2VP as Branching Point

• Published in: Macromolecular rapid communications. 2024-04, Vol.45 (8), p.e2300674-n/a
• Main Authors: Schußmann, Max G., Kreutzer, Lukas, Hirschberg, Valerian
• Format: Article
• Language: English
• Subjects: Anionic polymerization; Anions; Anions - chemistry; branched topologies; Dienes; Graft copolymers; high grafting density; mechanical properties, pom‐pom; Molecular Structure; Molecular weight; Polymerization; Polymers; Polymers - chemical synthesis; Polymers - chemistry; Polystyrene; Polystyrene resins; Polystyrenes - chemistry; Polyvinyls - chemical synthesis; Polyvinyls - chemistry; Purification; Pyridines; scalable; Styrene; Synthesis; Topology
• ISSN: 1022-1336; 1521-3927
• DOI: 10.1002/marc.202300674

Defined, branched polymer architectures with low dispersity and architectural purity are of great interest to polymer science but are challenging to synthesize. Besides star and comb, especially the pom‐pom topology is of interest as it is the simplest topology with exactly two branching points. Most synthetic approaches to a pom‐pom topology reported a lack of full control and variability over one of the three topological parameters, the backbone or arm molecular weight and arm number. A new, elegant, fast, and scalable synthetic route without the need for post‐polymerization modification (PPM) or purification steps during the synthesis to a pom‐pom and a broad variety of topologies made from styrene and dienes is reported, with potential application to barbwire, bottlebrush, miktoarm star, Janus type polymers, or multi‐graft copolymers. The key is to inset short poly(2‐vinyl‐pyridine) blocks (