ATRP Enhances Structural Correlations In Polymerization‐Induced Phase Separation. (13th March 2023)

• Record Type: Journal Article
• Authors: Sicher, Alba; Whitfield, Richard; Ilavsky, Jan; Saranathan, Vinodkumar; Anastasaki, Athina; Dufresne, Eric R.
• Is Part Of: Angewandte Chemie. Volume 135:Number 16(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2023-03-13
• Subjects: ATRP -- Biomimetic Synthesis -- Nanostructures -- Phase Separation -- Polymerization; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202217683
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Synthetic methods to control the structure of materials at sub‐micron scales are typically based on the self‐assembly of structural building blocks with precise size and morphology. On the other hand, many living systems can generate structure across a broad range of length scales in one step directly from macromolecules, using phase separation. Here, we introduce and control structure at the nano‐ and microscales through polymerization in the solid state, which has the unusual capability of both triggering and arresting phase separation. In particular, we show that atom transfer radical polymerization (ATRP) enables control of nucleation, growth, and stabilization of phase‐separated poly‐methylmethacrylate (PMMA) domains in a solid polystyrene (PS) matrix. ATRP yields durable nanostructures with low size dispersity and high degrees of structural correlations. Furthermore, we demonstrate that the length scale of these materials is controlled by the synthesis parameters. Abstract : Controlled‐radical polymerization in the solid state is used to induce and arrest the phase separation of highly structurally correlated inclusions. The obtained solid structure is durable and has low size dispersity. It is possible to tune the length scale spontaneously emerging in the system by modifying the synthesis parameters.