Convenient route to tetraarylphosphonium polyelectrolytes via metal-catalysed P–C coupling polymerisation of aryl dihalides and diphenylphosphine

Wan, Wang; Yang, Xiaoyan; Smith, Rhett C.

doi:10.1039/c6cc08938k

Cited by 19 publications

(25 citation statements)

References 23 publications

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“…The proposed synthetic route for M1 was inspired by the Ni‐catalyzed P–C coupling route described by Cristau's group (Scheme ) . This method involved using an excess (∼5 equiv) of tolylbromide as solvent/reactant and heating at 200 °C for at least 24 h with ∼70% yield.…”

Section: Resultsmentioning

confidence: 99%

“…This method involved using an excess (∼5 equiv) of tolylbromide as solvent/reactant and heating at 200 °C for at least 24 h with ∼70% yield. To decrease the amount of wasted aryl halide, shorten the reaction time, and improve the yield, we modified the procedure to include diisopropylamine as a base to facilitate the requisite deprotonation steps . Under these conditions, we found that the reaction was quantitative in ethylene glycol solvent after 15 h at 180 °C under N 2 .…”

Section: Resultsmentioning

confidence: 99%

“…On the basis of our prior work with linear tetraarylphosphonium polymers, we expected P1 to have good thermal stability. TGA was thus applied to probe the thermal stability of P1 .…”

Section: Resultsmentioning

confidence: 99%

“…Tetraarylphosphonium salts of the form [PAr 4 ] + [NTf 2 ] − are also thermally stable to heating for several days at 425 °C in air, making them promising candidates for ionic units in high‐stability polymers . Our group recently reported a new route to tetraarylphosphonium polyelectrolytes having decomposition temperatures of up to 460 °C, with one that is stable at 65 °C in 6 M NaOH( aq ) for at least 24 h ( R3 in Scheme ) . Such robust properties are necessary for their use in antibacterial coatings and as membranes in alkaline fuel cells and related electrochemical energy conversion technologies …”

Section: Introductionmentioning

confidence: 99%

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A new route to phosphonium polymer network solids via cyclotrimerization

Yang

Wen

Chumanov

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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An organo‐main group network solid having tetrahedral phosphonium vertices was prepared from a diacetyl monomer via a straightforward cyclotrimerization reaction. The network solid composition was examined by FT‐IR spectroscopy and elemental microanalysis, revealing quantitative reaction of carbonyl moieties and a 67% degree of cross‐linking. The reaction yielded a material having a layered structure that is comprised of an amorphous polymer and which is thermally stable up to 370 °C in air with a char yield of 40% upon heating as high as 800 °C under N2. The polymer is stable to 6 M NaOH(aq) at 60 °C for 24 h and takes up only 10.63% of water by mass at room temperature. The surface morphology, as examined by AFM, revealed a very smooth as‐prepared film (RMS roughness of 3 nm). The specific surface area measured by BET analysis with N2 gas is 9 m2 g−1, indicating a type II, nonporous material. Physisorption with CO2 revealed that the phosphonium network solid has additional affinity for CO2, suggesting that such materials may have use for applications such as CO2 capture. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1620–1625

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

“…On the basis of our prior work with linear tetraarylphosphonium polymers, we expected P1 to have good thermal stability. TGA was thus applied to probe the thermal stability of P1 .…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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A new route to phosphonium polymer network solids via cyclotrimerization

Yang

Wen

Chumanov

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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“…A metal‐catalyzed phosphorus–carbon coupling strategy involving aryl halides or aryl triflates with diphenylphosphine was recently utilized by Smith and co‐workers to prepare tetraarylphosphonium polyelectrolytes. The resulting PILs exhibited thermal stability up to 460 °C and reasonable alkaline stability …”

Section: Introductionmentioning

confidence: 99%

Correlating structure with ionic conductivity in bis(phosphonium)‐containing [NTf₂] thiol–ene networks

Sims

Bontrager

Whittaker

et al. 2019

Polymer International

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Thiol–ene photopolymerization was employed in order to prepare a series of covalently crosslinked bis(phosphonium)‐containing poly(ionic liquid) (PIL) networks. While the counteranion was held constant (NTf2), the structure of the bis(phosphonium)‐containing ‘ene’ monomer was varied in order to explore the breadth of thermal, mechanical and conductive properties available for this system. Towards this end, it was determined that more flexible spacers within the cationic monomer led to PIL networks with lower Tg values and higher conductivities. Most notable was a two‐ to three‐orders‐of‐magnitude increase in ionic conductivity (from 10−9 to 10−6 S cm−1 at 30 °C, 30% relative humidity) when the R group on phosphonium was changed from phenyl to isopropyl. Changing the functional group ratio to off‐stoichiometry also led to a slight increase in conductivity. Although the thermal stability (Td5%) of the phosphonium ionic liquid monomers was found to be significantly higher (>400 °C) than that of analogous imidazolium monomers, this improvement was not observed to directly transfer over to the polymer where a two‐step decomposition pathway was observed. The first step is attributed to the thiol monomer backbone while the second step correlates well with decomposition of the phosphonium portion of the PIL. © 2019 Society of Chemical Industry

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Organophosphorus Polymers

Green

Orthaber

2019

Encyclopedia of Inorganic and Bioinorganic Chemistry

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This article discusses polymers containing phosphorus centers that impart essential properties, functions, and responses to the discussed materials. By incorporating this heteroelement, the toolbox for tailoring optical, electronic, and structural properties as well as chemical reactivity is greatly expanded over “carbon” analogs. We discuss unsaturated (e.g., phosphaalkenes), saturated (e.g., phosphine oxides), and cyclic (e.g., phospholes) phosphorus motifs incorporated into conjugated polymers. Such organophosphorus systems are believed to have a bright future in optoelectronic devices, with this being demonstrated in organic light‐emitting diodes as acceptor and emitter materials, and in fundamental studies as responsive sensor systems. Saturated organophosphorus polymers allow for chemical transformations at the phosphorus centers by means of oxidation, metal (Lewis acid) coordination, quaternization, and so on. These modifications and transformations are used in sensing, scavenging, and catalytic systems. Moreover, in this article, we cover selected inorganic polymers, that is, polymers having exclusively inorganic skeletal atoms. These mainly include the polyphosphine and phosphinoborane classes of materials, for which recent fundamental studies have illustrated their potential as ceramic precursors. Polymerization methods are often similar to those applied in organic polymers, but a large variety of polymerizations have also been specifically developed for phosphorus and other pnictogens, and these have also been employed to synthesize these fascinating materials.

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Convenient route to tetraarylphosphonium polyelectrolytes via metal-catalysed P–C coupling polymerisation of aryl dihalides and diphenylphosphine

Cited by 19 publications

References 23 publications

A new route to phosphonium polymer network solids via cyclotrimerization

A new route to phosphonium polymer network solids via cyclotrimerization

Correlating structure with ionic conductivity in bis(phosphonium)‐containing [NTf₂] thiol–ene networks

Organophosphorus Polymers

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Convenient route to tetraarylphosphonium polyelectrolytes via metal-catalysed P–C coupling polymerisation of aryl dihalides and diphenylphosphine

Cited by 19 publications

References 23 publications

A new route to phosphonium polymer network solids via cyclotrimerization

A new route to phosphonium polymer network solids via cyclotrimerization

Correlating structure with ionic conductivity in bis(phosphonium)‐containing [NTf2] thiol–ene networks

Organophosphorus Polymers

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Product

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Correlating structure with ionic conductivity in bis(phosphonium)‐containing [NTf₂] thiol–ene networks