Recent Advances and Challenges in Barbier Polymerization

Abstract

The Barbier reaction, a classical name reaction for carbon‐carbon bond formation, has played important roles in organic chemistry for over 120 years. The introduction of the Barbier reaction into polymer chemistry for the development of a novel Barbier polymerization, expands the methodology, monomer, chemical structure and property libraries of polymerization, aggregation‐induced emission (AIE) and non‐traditional intrinsic luminescence (NTIL). This mini review focuses on Barbier polymerization, including the brief introduction of the history and importance of polymerization methods design and the achievements of Barbier polymerization from molecular design strategies, functionalities and properties. An outlook of Barbier polymerization is also proposed. This mini review on Barbier polymerization therefore may cause inspirations to scientists in different fields.

Barbier polymerization towards synthesizing polar polyolefin analogues for polyolefin modification

“…In previous research, carbonyl groups in the form of ketones, esters, and amides have been successfully polymerized through Barbier polymerization. [29][30][31][32][33][34][35][36] Dimethyl succinate (DMS), dimethyl glutarate (DMG), dimethyl adipate (DMA), and dimethyl pimelate (DMP) are important and commercially available chemicals, which however have not been investigated as monomers of Barbier polymerization yet. It is highly desirable to investigate the Barbier polymerization of these alkyl diesters monomers towards the preparation of PPAs.…”

Clickable Polymerization‐Induced Emission Luminogens Toward Color‐Tunable Modification of Non‐Traditional Intrinsic Luminescent Polymers

“…For example, the introduction of the Barbier reaction into polymer chemistry for the development of Barbier polymerization of different carbonyl, ester, and aldehyde monomers results in a series of NTIL polymers with adjustable emission wavelengths through PIE strategy of a series of phenylmethanol-containing PIEgens. [24,[27][28][29][30][31][32][33][34][35][36][37] A series of poly(1,3dicarbonyl)s is revealed to exhibit NTIL characteristics through PIE strategy via nucleophilic substitution polymerization. [38] Currently, PIE strategy has been widely demonstrated as a versatile strategy for the design of NTIL polymers in different polymerization systems, including Friedel-Crafts reaction and Michael polyaddition.…”

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.…”