Phosphonium polyelectrolytes: influence of diphosphine spacer on layer‐by‐layer assembly with anionic conjugated polymers

Conrad, Catherine A.; Bedford, Monte S.; Buelt, Ashley A.; Galabura, Yuriy; Luzinov, Igor; Smith, Rhett C.

doi:10.1002/pi.4930

Cited by 10 publications

(18 citation statements)

References 64 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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“…Second, side chains are well‐known to lower the glass transition temperature and decrease crystallinity, and the interplay of these established trends with the influence of intercation spacer had not been examined for PELs. On the basis of prior studies on PELs, the improved solubility was also expected to lead to better film growth linearity for LbL self‐assembly films and smoother/more uniform films. Finally, the LO backbone is identical to that of the LX polymer series, allowing direct comparison of data for the two series in the effort to derive more general structure–property correlations.…”

Section: Resultsmentioning

confidence: 99%

“…The molecular weights and degrees of polymerization are summarized in Table . Because these ionomers are too polar to efficiently pass through a gel permeation chromatography column, the degrees of polymerization were determined from NMR end‐group analysis . A slight excess of phosphine monomer was employed to ensure the identity of the end group.…”

Section: Resultsmentioning

confidence: 99%

“…The layer‐by‐layer (LbL) deposition of PELs allows fabrication of films with precisely controlled thickness and composition . When visible‐absorbing PELs (Chart ) are employed, the LbL films can be used as finely tuned optical or optoelectronic components .…”

Section: Introductionmentioning

confidence: 99%

“…Although significant strides have been made in understanding backbone effects on PEL properties, the role of side chains has not been systematically addressed. Herein, we described polymers LO (Scheme ), which are structural analogues of the LX series (Chart ), but in which the phenylene units in LX have been replaced with 2,5‐dioctyloxyphenylene units.…”

Section: Introductionmentioning

confidence: 99%

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Intercation spacing and side chain effects on phosphonium polymers: Thermal, supramolecular, and bactericidal properties

Yang

Bedford

Wan

et al. 2018

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

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The properties of phosphonium polyelectrolytes (PELs) were evaluated in an effort to assess the influence of both side chain and main chain composition. The influence of side chain was examined by comparing properties of a series of PELs having hydrophobic octyloxy side chains to those of structural analogues lacking the side chains. The influence exerted by backbone flexibility/length of spacer between charges was revealed by comparing properties of two series of polymers with a variable number of methylene units between phosphonium charge‐bearing sites. Side chain composition and spacing between phosphonium units lead to noteworthy influence on thermal stability, glass transition, and crystallinity. The molecular structure of PELs also correlates with trends in film morphology and critical surface energy of PEL dip‐cast films. Sensitivity of morphology to humidity or water in the casting solvent was observed. Supramolecular assembly of films via layer‐by‐layer deposition of PELs alternating with anionic polythiophene derivative layers was also undertaken. The linearity of film growth, amount of material deposited in each bilayer, polycation:polyanion ratio, and film roughness all show noteworthy trends that depend on both the presence/absence of side chains and on spacing between ionic centers. The relationship between side chain and spacer on bactericidal activity against Staphylococcus aureus and Escherichia coli was assessed. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 24–34

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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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Phosphonium polyelectrolytes: influence of diphosphine spacer on layer‐by‐layer assembly with anionic conjugated polymers

Cited by 10 publications

References 64 publications

A new route to phosphonium polymer network solids via cyclotrimerization

A new route to phosphonium polymer network solids via cyclotrimerization

Intercation spacing and side chain effects on phosphonium polymers: Thermal, supramolecular, and bactericidal properties

Organophosphorus Polymers

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