Turbo-Grignard Reagent Mediated Polymerization of Styrene under Mild Conditions Capable of Low Đ and Reactive Hydrogen Compatibility

Abstract

To develop novel polymerizations capable of manipulating low molecular weight distribution (Đ) through novel polymerization species rather than radical, anionic, or cationic species is highly desirable and challenging, which will enable polymer chemistry with a new polymerization mode and synthetic route. Grignard reagent mediated alkene polymerization is generally regarded as anionic polymerization that is not applicable for nonpolar monomers like styrene (St). Here, the turbo-Grignard reagent mediated polymerization of St is demonstrated to exhibit intriguing all-in-one characteristics of covalent–anionic–radical polymerization. Under mild conditions, polystyrenes with narrow molecular weight distribution can be obtained with over 99% monomer conversion by using a series of turbo-Grignard reagents (RMgX·LiCl) as initiators, including alkylMgCl·LiCl, BnMgCl·LiCl, and allylMgCl·LiCl. In comparison with traditional Grignard reagent mediated reactions and polymerizations exhibiting zero tolerance with reactive hydrogen, this turbo-Grignard reagent mediated polymerization exhibits compatibility with reactive hydrogen under mild conditions and expands the library of polymerization with an intriguing turbo-Grignard reagent mediated all-in-one covalent, anionic, and radical polymerization mode.

Nucleophilic Substitution Polymerization‐Induced Emission of 1,3‐Dicarbonyl Compounds as a Versatile Approach for Aggregation‐Induced Emission Type Non‐Traditional Intrinsic Luminescence†

“…For example, polyesterification, polyamidation, coupling polymerizations, ring‐ opening metathesis polymerization, click polymerization, Michael polymerization, multicomponent polymerization, living polymerizations and Barbier polymerization, are based on corresponding esterification, amidation, coupling reactions, olefin metathesis reaction, click reaction, Michael reaction, multicomponent reaction, reversible‐deactivation reactions and Barbier reaction, respectively. [ 12,17‐18,25‐46 ] Further exploration of polymerization methods will expand the monomer, polymer and functionality libraries of polymer chemistry, which will eventually result in the prosperous polymer science with abundant synthetic polymers for a better human life.…”

Compatibility of Barbier Covalent-Anionic-Radical Polymerization with Air and Divinylbenzene

“…The Barbier reaction, developed by Phillippe Barbier in 1899, is a successful C–C bond formation reaction through nucleophilic addition reaction between organohalides and carbonyls in the presence of metals (e.g., Mg). − Compared with the analogous Grignard reaction, developed by Victor Grignard (Phillippe Barbier’s PhD student) in 1900, the Barbier reaction exhibits reactive hydrogen tolerance, attributed to its unique 3-in-1 covalent-anion-radical mechanism, which can be achieved under mild conditions in one pot. Since 2017, the Barbier reaction has been introduced into polymer chemistry successfully, where a series of hydroxyl- and amine-containing polymers have been prepared with intriguing properties through step-growth Barbier polymerization. − Attributed to the unique 3-in-1 covalent-anion-radical characteristics of polymerization species, chain-growth covalent-anionic-radical polymerization (CARP) was developed, where polymers with full monomer conversion and Đ low to 1.05 were prepared under an inert atmosphere. − Meanwhile, divinylbenzene (DVB) typically gives highly cross-linked polymers insoluble in solvents by both radical and anionic polymerization, which are commonly used as ion-exchange resins and chromatography columns . The preparation of soluble DVB-containing polymers is still challenging, especially for the preparation of DVB-containing polymers with close to 100% vinyl side chains at high DVB conversion.…”