Comparing Ammonium and Phosphonium Polymerized Ionic Liquids: Thermal Analysis, Conductivity, and Morphology

Hemp, Sean T.; Zhang, Mingqiang; Allen, Michael; Cheng, Shijing; Moore, Robert B.; Long, Timothy Edward

doi:10.1002/macp.201300322

Cited by 93 publications

(102 citation statements)

References 48 publications

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“…Compared with traditional organic frameworks, ionic hypercrosslinked polymers, specifically those involving ionic liquids as monomers, have attracted growing attention. These materials can possess good thermal and chemical stability, properties that can be tuned upon simple counterion exchange, and which can readily form layer‐by‐layer self‐assembled films with other ionic polymers . For example, Yang et al reported an alkaline anion exchange membrane R1 (Scheme ) comprised of copolymerized imidazolium‐functionalized ionic liquids with styrene and acrylonitrile.…”

Section: Introductionmentioning

confidence: 99%

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: Introductionmentioning

confidence: 99%

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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“…Long and co‐workers have recently reviewed several synthetic approaches towards phosphonium PILs, the majority of which involved the polymerization of vinylbenzylphosphonium monomers . In a prototypical example, Hemp et al reported a series of PILs where an increase in T d5% (temperature at which 5% of the PIL had decomposed) of 100–200 °C occurred when the cation was changed from ammonium to phosphonium across a wide range of counteranions (Cl, BF 4 , OTf, NTf 2 ) . An increase in ionic conductivity (log σ ) of up to an order of magnitude was also observed for the phosphonium PILs.…”

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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“…There are only a few examples of phosphonium aprotic poly(ionic liquids) which are showing excellent properties. For example, Hemp et al synthesized poly(ionic liquids) composed of aprotic phosphonium cations . The polymers were used as nonviral gene delivery agents and compared with ammonium analogs showing enhanced DNA binding with better transfection efficiencies.…”

Section: Introductionmentioning

confidence: 99%

Proton Conducting Membranes Based on Poly(Ionic Liquids) Having Phosphonium Counter‐Cations

Işık

Porcarelli

Lago

et al. 2017

Macromol. Rapid Commun.

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Proton conducting polymeric membranes are highly searched in many different technologies ranging from energy to biosensing. Protic ionic liquids and their polymeric version represent a new family of proton conducting molecules with relatively facile synthesis and excellent properties. In this work, protic poly(ionic liquids) having the most popular phosphonium counter-cations are presented for the first time. The synthesis is carried out through proton transfer reactions or through ion exchange reactions by using commercially available tertiary phosphines. Tributyl-, trioctyl-, and tricyclohexyl-phosphine are selected to form the desired cations. Polystyrene sulfonic acid, poly(2-acrylamido-2-methyl-1-propanesulfonic acid), and lithium poly[(4-styrenesulfonyl) (trifluoromethanesulfonyl)imide] polymers are used to form the polymeric anions. The chemical structure of the protic poly(ionic liquids) is confirmed by spectroscopic characterizations such as Fourier transform infrared and nuclear magnetic resonance spectroscopies. Thermal properties of the polymer are characterized by means of differential scanning calorimetry and thermogravimetric analysis. Polymers exhibit good membrane forming ability as well as high ionic conductivities in the range of 10 to 10 S cm from 30 to 90 °C.

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Comparing Ammonium and Phosphonium Polymerized Ionic Liquids: Thermal Analysis, Conductivity, and Morphology

Cited by 93 publications

References 48 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

Proton Conducting Membranes Based on Poly(Ionic Liquids) Having Phosphonium Counter‐Cations

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Comparing Ammonium and Phosphonium Polymerized Ionic Liquids: Thermal Analysis, Conductivity, and Morphology

Cited by 93 publications

References 48 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

Proton Conducting Membranes Based on Poly(Ionic Liquids) Having Phosphonium Counter‐Cations

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Product

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