Cationic polymerization of styrenes under essentially neutral conditions

Kuznetsov, Dmitry M.; Tumanov, Vasily V.; Smit, W. A.

doi:10.1007/s10965-013-0128-2

Cited by 10 publications

(8 citation statements)

References 23 publications

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“…These initial results indicate that AcAcH is necessary for efficient glucose fuel combustion, with the sugar acting as an assisting/supporting fuel whereas coordinating ligand AcAcH is the primary fuel. This result parallels the lower acidity of glucose hydroxyl groups (−OH, pK a ≈ 14) versus that of AcAcH (pK a ≈ 9), 52,53 thereby preventing efficient metal ion coordination in the competing presence of the base (NH 4 OH) in the IGZO precursor formulation. Furthermore, a nearstoichiometric amount of AcAcH vs total metals (M:AcAcH = 1:4) and wt% Glu = 10 affords the best-performing IGZO transistors.…”

Section: ■ Results and Discussionmentioning

confidence: 98%

Carbohydrate-Assisted Combustion Synthesis To Realize High-Performance Oxide Transistors

et al. 2016

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Owing to high carrier mobilities, good environmental/thermal stability, excellent optical transparency, and compatibility with solution processing, thin-film transistors (TFTs) based on amorphous metal oxide semiconductors (AOSs) are promising alternatives to those based on amorphous silicon (a-Si:H) and low-temperature (<600 °C) poly-silicon (LTPS). However, solution-processed display-relevant indium-gallium-tin-oxide (IGZO) TFTs suffer from low carrier mobilities and/or inferior bias-stress stability versus their sputtered counterparts. Here we report that three types of environmentally benign carbohydrates (sorbitol, sucrose, and glucose) serve as especially efficient fuels for IGZO film combustion synthesis to yield high-performance TFTs. The results indicate that these carbohydrates assist the combustion process by lowering the ignition threshold temperature and, for optimal stoichiometries, enhancing the reaction enthalpy. IGZO TFT mobilities are increased to >8 cm(2) V(-1) s(-1) on SiO2/Si gate dielectrics with significantly improved bias-stress stability. The first correlations between precursor combustion enthalpy and a-MO densification/charge transport are established.

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Section: ■ Results and Discussionmentioning

confidence: 98%

Carbohydrate-Assisted Combustion Synthesis To Realize High-Performance Oxide Transistors

et al. 2016

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“…102 d) Cationic polymerisation promoted by HFIP Cationic polymerisation of styrene and its derivatives, using HFIP as the sole proton source and reaction solvent was also developed by Smit and coworkers. 103 To negate the poor reactivity of styrene, the addition of catalytic amounts of more easily polymerised alkenes, such as -pinene, p-MeO-styrene, or p-Me 2 N-styrene gave reasonable yields of the corresponding mixed polymers (Box 2d). Since HFIP has relatively low Bronsted acidity, the proton transfer step required to initiate polymerisation was postulated to involve a cluster of HFIP molecules.…”

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confidence: 99%

Hexafluoroisopropanol as a highly versatile solvent

et al. 2017

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Hexafluoroisopropanol (HFIP) has recently become a very popular solvent with uses in many different applications; analysis shows that it possesses a wide range of interesting and unique properties. In this Perspective we detail the main uses of HFIP in the natural sciences and disclose the underlying principles that give it such wide appeal. Accordingly, we will show the broad usage and beneficial effects of HFIP in different fields such as organic, inorganic or physical chemistry, chemical biology and polymer science.

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“…However, in the case of even more deactivated substrates such as 1m and 1n, the reaction required 6 d for the styrene to be fully consumed. The reaction could also be expanded to styrenes bearing moderate electron-withdrawing groups (1h and 1i) and even the unsubstituted styrene 1j, which is typically prone to undergo oligomerization in HFIP, 16 confirming the role of the buffer of the amine in the reaction to preclude the side process. These transformations could be conducted under milder reaction conditions (20 °C), which represents a notable improvement when compared to previous reports that required higher temperatures (up to 160 °C).…”

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confidence: 96%

“…15 Importantly, the strategy could be applied irrespective of the nature of the aniline (primary, secondary, or tertiary). Additionally, because the aniline would act as a buffer, even dienes and styrene derivatives, which typically generate oligomers in HFIP, 16 could be tolerated. Herein, we disclose our findings regarding this transformation with a special emphasis on highly deactivated styrenes and their synthetic applications.…”

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confidence: 99%

Lewis Acid/Hexafluoroisopropanol: A Promoter System for Selective ortho-C-Alkylation of Anilines with Deactivated Styrene Derivatives and Unactivated Alkenes

et al. 2020

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Aniline derivatives are frequently encountered in molecules of industrial relevance such as dyes or antioxidants, which make the development of synthetic methods for the functionalization of these privileged structures highly sought-after. A general protocol for the hydroarylation of electronically diverse alkenes with anilines would be ideal to provide densely functionalized compounds. Yet, this transformation has been underexplored compared to more traditional hydroarylation of unactivated alkenes because of the significant challenges associated with the control of the selectivity and its substrate tolerance. Herein, we describe a selective, versatile and user-friendly ortho-C-alkylation of anilines with alkenes that hinges on the beneficial combination of a Lewis acid (Ca(II)) and hexafluoroisopropanol as a solvent. This protocol allows for the extension of this transformation to highly deactivated styrenes and demonstrates a remarkable improved reactivity regarding aliphatic alkenes, styrene derivatives and dienes. In addition, DFT computations were performed which, combined with experimental observations, suggest a nearly concerted mechanism that impart the ortho-selectivity.

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Cationic polymerization of styrenes under essentially neutral conditions

Cited by 10 publications

References 23 publications

Carbohydrate-Assisted Combustion Synthesis To Realize High-Performance Oxide Transistors

Carbohydrate-Assisted Combustion Synthesis To Realize High-Performance Oxide Transistors

Hexafluoroisopropanol as a highly versatile solvent

Lewis Acid/Hexafluoroisopropanol: A Promoter System for Selective ortho-C-Alkylation of Anilines with Deactivated Styrene Derivatives and Unactivated Alkenes

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