Blue solutions of potassium in ethers as initiators of anionic polymerization

Dainton, F. S.; Wiles, D. M.; Wright, A. N.

doi:10.1002/pol.1960.1204514510

Cited by 40 publications

(9 citation statements)

References 10 publications

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“…Solvated electrons initiate living polymerization of acrylates. 27,28 As expected, MA readily polymerized to give polymers of moderate size with a polydispersity index of >2.5. For C4, solvated electrons led to decomposition but not to polymerization.…”

Section: ■ Synthesis and Characterizationsupporting

confidence: 65%

Electron-Beam Irradiation of Cinnamate Films Affords Nanoscale Patterned Substrates for Use in Devices and as Scaffolds in Tissue Engineering

Strunk

Bojanowski

Huck

et al. 2020

ACS Appl. Nano Mater.

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The fabrication of electronic, photonic, and metamaterial-based devices, or tissue engineering requires the controlled deposition and patterning of materials. Electron-beam lithography (EBL) offers unprecedented miniaturization of those devices because of its high resolution. We present a concept to induce a classic photochemical reaction in condensed matter via EBL. We investigate the response of a tetrameric cinnamate monomer in thin films toward photon and electron radiation. In the solid state, photoexcitation and electron bombardment similarly induce [2 + 2] cycloadditions, forming insoluble truxilic acid esters, as shown via IR spectroscopy measurements. Subsequently, we employed the investigated material as an electron-beam resist, showing resistance against wet-chemical etchants. Structures with resolution down to 60 nm were obtained, not achievable with conventional photolithography, proving that [2 + 2] cycloaddition of cinnamic acid containing compounds is suitable for applications in the field of EBL.

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Section: ■ Synthesis and Characterizationsupporting

confidence: 65%

Electron-Beam Irradiation of Cinnamate Films Affords Nanoscale Patterned Substrates for Use in Devices and as Scaffolds in Tissue Engineering

Strunk

Bojanowski

Huck

et al. 2020

ACS Appl. Nano Mater.

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“…In the environment of excess K À /e s À , reductive polymerization and nucleophilic elimination can continuously occur to form the final black polymeric carbon. [15] These hypotheses can be…”

Section: Methodsmentioning

confidence: 99%

Phase Transfer‐Mediated Degradation of Ether‐Based Localized High‐Concentration Electrolytes in Alkali Metal Batteries

et al. 2022

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Localized high-concentration electrolytes (LHCEs) have attracted interest in alkali metal batteries due to the advantages of forming stable solid-electrolyte interphases (SEIs) on anodes and good chemical/ electrochemical stability. Herein, a new degradation mechanism is revealed for ether-based LHCEs that questions their compatibility with alkali metal anodes (Li, Na, and K). Specifically, the ether solvent reacts with alkali metals to generate solvated electrons (e s À ) that attack hydrofluoroether co-solvents to form a series of byproducts. The ether solvent essentially acts as a phase-transfer reagent that continuously transfers electrons from solid-phase metals into the solution phase, thus inhibiting the formation of stable SEI and leading to continuous alkali metal corrosion. Switching to an ester-based solvating solvent or intercalation anodes such as graphite or molybdenum disulfide has been shown to avoid such a degradation mechanism due to the absence of e s À .

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“…Solvated electrons ( e sol − ) can generate radical anions upon reaction with olefins . The e sol − are, however, under‐utilized in polymerizations largely due to a prevailing dogma that the radical component dimerizes ( Figure a), leading to misguided subsequent work . We, however, established the importance of monomer solubility/polarity on the resulting mechanism, whereby nonpolar monomers promote radical anion propagation, hence, the activated monomer concentration, [M]*, is kept low (Figure a) .…”

Section: Introductionmentioning

confidence: 95%

Rapid One‐Step Synthesis of Complex‐Architecture Block Polymers Using Inductively “Armed–Disarmed” Monomer Pairs

Chang

Oyola‐Reynoso

Cutinho

et al. 2018

Macromol. Rapid Commun.

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A facile method is reported for rapid, room-temperature synthesis of block copolymers (BCP) of complex morphology and hence nontraditional spherical assembly. The use of solvated electrons generates radical anions on olefinic monomers, and with a felicitous choice of monomer pairs, this species will propagate bimechanistically (via radical and the anion) to form BCPs. Molecular weight of the obtained BCP range from M = 97 000-404 000 g mol (polydispersity index, PDI = 1.4-3.0) depending on monomer pairs. The composition of the blocks can be controlled by changing monomer ratio, with the caveat that yield is affected. Detailed characterization by 2D nuclear magnetic resonance spectroscopy, differential scanning calorimetry (DSC), and analysis of the mechanisms involved indicate the structure of obtained block copolymers to be at least a triblock with a complex central unit. Evaluating trends in the Hammett parameter segregates monomer pairs into "armed and disarmed" groups with respect to radical or anionic polymerization akin to oligosaccharides synthesis.

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Blue solutions of potassium in ethers as initiators of anionic polymerization

Cited by 40 publications

References 10 publications

Electron-Beam Irradiation of Cinnamate Films Affords Nanoscale Patterned Substrates for Use in Devices and as Scaffolds in Tissue Engineering

Electron-Beam Irradiation of Cinnamate Films Affords Nanoscale Patterned Substrates for Use in Devices and as Scaffolds in Tissue Engineering

Phase Transfer‐Mediated Degradation of Ether‐Based Localized High‐Concentration Electrolytes in Alkali Metal Batteries

Rapid One‐Step Synthesis of Complex‐Architecture Block Polymers Using Inductively “Armed–Disarmed” Monomer Pairs

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