Anionic Polymerization

Quirk, Roderic P.

doi:10.1002/9781118480793.ch7

Cited by 4 publications

(2 citation statements)

References 237 publications

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“…Then, we analyzed the commercially available low MW PS sample by NMR spectroscopies and high-resolution APCI (atmospheric pressure chemical ionization) mass spectrometry (see the details in the final chapter of the SI). In conclusion, we have reasonably determined the terminal structures as a sec -butyl group and a hydrogen atom, which are probably attached in the process of anion polymerization . On the basis of the analyses, tacticity of the oligostyrene was found to be atactic, and the oligomer sample is mainly composed of the 6–8 mers.…”

Section: Methodsmentioning

confidence: 70%

Dynamic Polymer Free Volume Monitored by Single-Molecule Spectroscopy of a Dual Fluorescent Flapping Dopant

et al. 2021

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Single-molecule spectroscopy (SMS) of a dual fluorescent flapping molecular probe (N-FLAP) enabled realtime nanoscale monitoring of local free volume dynamics in polystyrenes. The SMS study was realized by structural improvement of a previously reported flapping molecule by nitrogen substitution, leading to increased brightness (22 times) of the probe. In a polystyrene thin film at the temperature of 5 K above the glass transition, the spectra of a single N-FLAP molecule undergo frequent jumps between short-and long-wavelength forms, the latter one indicating planarization of the molecule in the excited state. The observed spectral jumps were statistically analyzed to reveal the dynamics of the molecular environment. The analysis together with MD and QM/MM calculations show that the excited-state planarization of the flapping probe occurs only when sufficiently large polymer free volume of more than, at least, 280 Å 3 is available close to the molecule, and that such free volume lasts for an average of 1.2 s.

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Section: Methodsmentioning

confidence: 70%

Dynamic Polymer Free Volume Monitored by Single-Molecule Spectroscopy of a Dual Fluorescent Flapping Dopant

et al. 2021

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“…Although this “grafting onto” approach suffers from limited grafting density due to steric repulsion between side chains, the mechanical response of most biological soft tissues can be well-mimicked by bottlebrush networks in the lower range of grafting densities. Separate formation of precursors with a very low dispersity, Đ , employing anionic polymerization 28 allows for their characterization individually to enable high level of precision on the molecular structure. Additionally, we use anionic polymerization, an industrial method producing yearly kilograms of polymers possibly enabling scale-up as the necessary industrial equipment and expertise exist.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of well-defined linear–bottlebrush–linear triblock copolymer towards architecturally-tunable soft materials

Asadi

Ruggeri

et al. 2022

Polym. Chem.

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Tuning Reactivities of tert‐Butyllithium by the Addition of Stoichiometric Amounts of Tetrahydrofuran

Kleinheider,

Schrimpf,

Scheel

et al. 2024

Chemistry A European J

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In alkyllithium chemistry the highest reactivity has historically been linked to the smallest degree of aggregation possible. Since tert‐butyllithium is known to form a monomer in tetrahydrofuran solution, using just stoichiometric amounts of the lewis base to selectively form a dimeric species seemed irrational. In this study, we showed a considerable increase of the reactivity of t‐BuLi when using stoichiometric amounts of THF in the non‐polar solvent n‐pentane in order to enable the deprotonation of simple methyl silanes and other low C–H‐acidic substrates. In this context, we were able to obtain the corresponding aggregates of t‐BuLi with the ligand THF in suspension and as crystalline solids and investigate them by single crystal X‐ray structural analysis, in situ FTIR spectroscopy and quantum chemical calculations. Furthermore, we were able to explain the enhanced reactivity of t‐BuLi with stoichiometric amounts of THF on the basis of structural features of the bridged dimer obtained under these conditions. With these findings, we present a new target in the aggregation of alkyllithium reagents: the selectively formed “frustrated” aggregates!

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Anionic Polymerization

Cited by 4 publications

References 237 publications

Dynamic Polymer Free Volume Monitored by Single-Molecule Spectroscopy of a Dual Fluorescent Flapping Dopant

Dynamic Polymer Free Volume Monitored by Single-Molecule Spectroscopy of a Dual Fluorescent Flapping Dopant

Synthesis of well-defined linear–bottlebrush–linear triblock copolymer towards architecturally-tunable soft materials

Tuning Reactivities of tert‐Butyllithium by the Addition of Stoichiometric Amounts of Tetrahydrofuran

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