Introduction of a Luminophore into Generic Polymers via Mechanoradical Coupling with a Prefluorescent Reagent

Abstract

Herein, we report a novel strategy for introducing a luminophore into generic polymers facilitated by mechanical stimulation. In this study, polymeric mechanoradicals were formed in situ under ball‐milling conditions to undergo radical–radical coupling with a prefluorescent nitroxide‐based reagent in order to incorporate a luminophore into the polymer main chains via a covalent bond. This method allowed the direct and conceptually simple preparation of luminescent polymeric materials from a wide range of generic polymers such as polystyrene, polymethyl methacrylate, and polyethylene. These results indicate that the present mechanoradical coupling strategy may help to transform existing commodity polymers into more valuable functional materials.

The mechanochemical synthesis of polymers

“…Ito's group realised this concept through ball milling. 177 Polymeric macroradicals formed in situ under ball milling conditions underwent radical coupling reaction with a prefluorescent nitroxide based reagent. A series of luminescent polymeric materials were obtained from polystyrene, polyethylene, poly(methyl methacrylate), poly(phenylene sulfide), and polysulfone, showing off its synthetic versatility.…”

Mechanochemistry: New Tools to Navigate the Uncharted Territory of “Impossible” Reactions

“…However, despite the simplicity of this methodology, the number of papers produced on this topic is low; some questions remain and need to be better understood. [157] During the preparation of the present manuscript, a noteworthy contribution by Cao and co-workers [158] contributed significantly to shedding light on this subject by broadening its scope. They devised a mechanochemical-induced strategy to synthesize a library of 1,2-diketoindolizine derivatives from indolizines and epoxides by using BaTiO 3 as the piezoelectric material (Table 11).…”

“…These unusual features make mechano‐redox methodologies a cost‐effective and environmentally benign alternative to photocatalytic chemistry for the oxidation of organic substrates. However, despite the simplicity of this methodology, the number of papers produced on this topic is low; some questions remain and need to be better understood [157] …”

Generation of aryl radicals fromin situactivated homolytic scission: driving radical reactions by ball milling

“…Recently, mechanical stress has been witnessed with great potential to support radical generation through chemical bond breaking in polymer chemistry. 15 Representative works are contributions from Sijbesma 16 a and Otsuka 16 b – h to radical-type mechanochromic polymers. However, direct covalent-bond cleavage of stable small molecules by mechanical force to generate radicals is quite a tough issue.…”