Silylium dual catalysis in living polymerization of methacrylates via <i>In situ</i> hydrosilylation of monomer

Xu, Tao; Chen, Eugene Y.‐X.

doi:10.1002/pola.27641

Cited by 19 publications

(21 citation statements)

References 84 publications

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“…The activity of these reactions can be tuned by the degree of interaction with the charge compensating anion. For example, silylium [SiR 3 ] + [B(C 6 F 5 ) 4 ] − can be generated by hydride abstraction − of an SKA or a hydrosilane. The formal cation will render a highly reactive system.…”

Section: Mechanismmentioning

confidence: 99%

“…GT-LPP also works well with employment of discrete silylium (SiR 3 + ) LAs generated by hydride abstraction − or ligand dissociation. ,,, This strategy has found great success in the polymerization of several monomers, most notably MC and methyl cinnamate (MCin). MCin, which contains a β-substituted phenyl group that both stabilizes the alkene electronically and protects the β-carbon sterically, and is thus not polymerizable by any other known methods, would require the strong and sterically unhindered LA SiMe 3 + for polymerization by GT-LPP .…”

Section: Selectivity and Controlmentioning

confidence: 99%

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Lewis Pair Polymerization: Perspective on a Ten-Year Journey

McGraw

Chen

2020

Macromolecules

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Ten years have passed since the conception of what was termed Lewis pair polymerization (LPP) that employs Lewis acid and base in pairs to not only activate monomers but also effect chain initiation, propagation, and transfer events. Compared to other polymerization methodologies, LPP's cooperative and synergistic two-component catalytic mechanism empowers several unique or advantageous features, including extraordinary tunability of catalyst/ initiator systems, compounded thermodynamic and kinetic control over comonomer sequences in one-pot LPP of monomer mixtures for highly resolved block copolymers, complete chemoselectivity in LPP of multifunctional vinyl monomers, independent tuning of polymerization activity and target polymer molecular weight, controlled heat dissipation in bulk polymerization with unactivated monomers functioning as solvent molecules, and coupled selectivity and livingness with immortality of the active species to produce ultrahigh molecular weight polymers and block copolymers with record-number (53) blocks. Focusing on four fundamental attributes of any polymerization methodologymechanism, kinetics, control, and selectivitythis Perspective narrates the growth and development of LPP, tracing each innovation back to fundamental principles so that each concept can be strategically applied, and describes new frontiers fertile for future research.

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Section: Mechanismmentioning

confidence: 99%

Section: Selectivity and Controlmentioning

confidence: 99%

Lewis Pair Polymerization: Perspective on a Ten-Year Journey

McGraw

Chen

2020

Macromolecules

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“…[ 334 ] Further work by the Kakuchi and Chen groups has allowed the study of various monomers, tertiary silanes and Al(C 6 F 5 ) 3 as a strong Lewis acid. [ 335–338 ]…”

Section: Polymerization Of (Meth)acrylic Monomers and Analogsmentioning

confidence: 99%

Production and Polymerization of Biobased Acrylates and Analogs

Fouilloux

Thomas

2021

Macromol. Rapid Commun.

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To prepare biobased polymers, particular attention must be paid to the obtention of the monomers from which they are derived. (Meth)acrylates and their analogs constitute such a class of monomers that have been extensively studied due to the wide range of polymers accessible from them. This review therefore aims to highlight the progresses made in the production and polymerization of (meth)acrylates and their analogs. Acrylic acid production from biomass is close to commercialization, as three different high‐potential intermediates are identified: glycerol, lactic acid, and 3‐hydroxypropionic acid. Biobased methacrylic acid is less common, but several promising options are available, such as the decarboxylation of itaconic acid or the dehydration of 2‐hydroxyisobutyric acid. Itaconic acid is also a vinylic monomer of great interest, and polymers derived from it have already found commercial applications. Methylene butyrolactones are promising monomers, obtained from bioresources via three different intermediates: levulinic, succinic, or itaconic acid. Although expensive, methylene butyrolactones have a strong potential for the production of high‐performance polymers. Finally, β‐substituted acrylic monomers, such as cinnamic, fumaric, muconic, or crotonic acid, are also examined, as they provide an original access to biobased materials from various renewable raw materials, such as protein waste, lignin, or wastewater.

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“…One of the published reports that has been highlighted is the ring-opening polymerization of ωpentadecatlone catalyzed by DMAP Brønsted base and magnesium halides (Figure 3) [56]. Another achievement in the field has been the polymerization of methacrylate catalyzed by [Et 3 SiH]/[Et 3 Si(L)] + [B(C 6 F 5 ) 4 ] − couple, which was described as a good methodology to produce linear polymethacrylates [57]. Some fields in chemistry have been positively impacted by the dual-assisted processes, such as asymmetric synthesis.…”

Section: Dual Catalysis: An Efficient and Versatile Synthetic Toolmentioning

confidence: 99%

Towards Dual-Metal Catalyzed Hydroalkoxylation of Alkynes

et al. 2021

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Poly (vinyl ethers) are compounds with great value in the coating industry due to exhibiting properties such as high viscosity, soft adhesiveness, resistance to saponification and solubility in water and organic solvents. However, the main challenge in this field is the synthesis of vinyl ether monomers that can be synthetized by methodologies such as vinyl transfer, reduction of vinyl phosphate ether, isomerization, hydrogenation of acetylenic ethers, elimination, addition of alcohols to alkyne species etc. Nevertheless, the most successful strategy to access to vinyl ether derivatives is the addition of alcohols to alkynes catalyzed by transition metals such as molybdenum, tungsten, ruthenium, palladium, platinum, gold, silver, iridium and rhodium, where gold-NHC catalysts have shown the best results in vinyl ether synthesis. Recently, the hydrophenoxylation reaction was found to proceed through a digold-assisted process where the species that determine the rate of the reaction are PhO-[Au(IPr)] and alkyne-[Au(IPr)]. Later, the improvement of the hydrophenoxylation reaction by using a mixed combination of Cu-NHC and Au-NHC catalysts was also reported. DFT studies confirmed a cost-effective method for the hydrophenoxylation reaction and located the rate-determining step, which turned out to be quite sensitive to the sterical hindrance due to the NHC ligands.

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Silylium dual catalysis in living polymerization of methacrylates via In situ hydrosilylation of monomer

Abstract: Silylium ions ("R 3 Si 1 ") are found to catalyze both

Cited by 19 publications

References 84 publications

Lewis Pair Polymerization: Perspective on a Ten-Year Journey

Lewis Pair Polymerization: Perspective on a Ten-Year Journey

Production and Polymerization of Biobased Acrylates and Analogs

Towards Dual-Metal Catalyzed Hydroalkoxylation of Alkynes

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