Shake, shear, and grind! - the evolution of mechanoredox polymerization methodology.

In the last half decade, mechanoredox catalysis has enabled an entirely new genre of polymerization methodology. In this paradigm, mechanical force, such as ultrasonic cavitation bubble collapse or ball mill grinding, polarizes piezoelectric nanoparticles; the resultant piezopotential drives the redox processes necessary for free- and controlled-radical polymerizations. Since being introduced, evolution of these methods facilitates exploration of mechanistic underpinnings behind key electron-transfer events. Mechanical force has not only been identified as a "greener" alternative to more traditional reaction stimuli (e.g., heat, light) for the synthesis of commodity polymers, but also a potential technology to enable the production of novel thermoplastic and thermoset materials that are either challenging, or even impossible, to access using conventional solution-state approaches. In this Feature Article, significant contributions to such methods are highlighted within. Advances and ongoing challenges in both ultrasound and ball milling driven reactions for radical polymerization and crosslinking are identified and discussed.

Mechanoredox Catalysis Enables a Sustainable and Versatile Reversible Addition-Fragmentation Chain Transfer Polymerization Process.

The sustainable synthesis of macromolecules with control over sequence and molar mass remains a challenge in polymer chemistry. By coupling mechanochemistry and electron-transfer processes (i.e., mechanoredox catalysis), an energy-conscious controlled radical polymerization methodology is realized. This work explores an efficient mechanoredox reversible addition-fragmentation chain transfer (RAFT) polymerization process using mechanical stimuli by implementing piezoelectric barium titanate and a diaryliodonium initiator with minimal solvent usage. This mechanoredox RAFT process demonstrates exquisite control over poly(meth)acrylate dispersity and chain length while also showcasing an alternative to the solution-state synthesis of semifluorinated polymers that typically utilize exotic solvents and/or reagents. This chemistry will find utility in the sustainable development of materials across the energy, biomedical, and engineering communities.

Diaryliodonium salts facilitate metal-free mechanoredox free radical polymerizations.

Mechanically-induced redox processes offer a promising alternative to more conventional thermal and photochemical synthetic methods. For macromolecule synthesis, current methods utilize sensitive transition metal additives and suffer from background reactivity. Alternative methodology will offer exquisite control over these stimuli-induced mechanoredox reactions to couple force with redox-driven chemical transformations. Herein, we present the iodonium-initiated free-radical polymerization of (meth)acrylate monomers under ultrasonic irradiation and ball-milling conditions. We explore the kinetic and structural consequences of these complementary mechanical inputs to access high molecular weight polymers. This methodology will undoubtedly find broad utility across stimuli-controlled polymerization reactions and adaptive material design.

Controlled Polymerization of Norbornene Cycloparaphenylenes Expands Carbon Nanomaterials Design Space.

Carbon-based materials-such as graphene nanoribbons, fullerenes, and carbon nanotubes-elicit significant excitement due to their wide-ranging properties and many possible applications. However, the lack of methods for precise synthesis, functionalization, and assembly of complex carbon materials has hindered efforts to define structure-property relationships and develop new carbon materials with unique properties. To overcome this challenge, we employed a combination of bottom-up organic synthesis and controlled polymer synthesis. We designed norbornene-functionalized cycloparaphenylenes (CPPs), a family of macrocycles that map onto armchair carbon nanotubes of varying diameters. Through ring-opening metathesis polymerization, we accessed homopolymers as well as block and statistical copolymers constructed from "carbon nanohoops" with a high degree of structural control. These soluble, sp2-carbon-dense polymers exhibit tunable fluorescence emission and supramolecular responses based on composition and sequence. This work represents an important advance toward bridging the gap between small molecules and functional carbon-based materials.