Post-polymerization modification based on reactive fluorinated polymers reaction

Du, Yiying; Zeng, Qiugui; Yuan, Ling; He, Lina

doi:10.1080/10601325.2021.1903328

Cited by 9 publications

(8 citation statements)

References 146 publications

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“…For the purpose of investigating degraded components, 31 P NMR and 19 F NMR were collected from the Fenton′s solution. Before and after the Fenton′s test, 1 H NMR, 31 P NMR, and 19 F NMR spectra of the polymer material were measured and compared.…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

“…The resistance to radical attack of the PWN70-C18 membrane is underpinned by investigating the Fenton′s solution and the tested membrane via NMR. No peaks in 31 P and 19 F NMR of the Fenton′s solution could be observed, demonstrating that no smaller fragments are detached from the polymer (Figure S12A). Before and after the test, the 31 P and 19 F NMR spectra of the membrane exhibited no changes (Figure S13).…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

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Modification of Phosphonated Poly(pentafluorostyrene) toward Ductile Membranes for Electrochemical Applications

Stigler,

Wagner,

Thiele

et al. 2023

Macromolecules

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In terms of proton exchange membranes, phosphonated poly(pentafluorostyrene) (PWN) is an auspicious material. It provides a high ion-exchange capacity, good thermal and chemical stabilities, as well as reduced anhydride formation and high proton dissociation degree due to low pK a. One major drawback preventing the utilization in fuel cells as pure material lies in its poor mechanical stability. Therefore, the need for modifying the polymer structure arises. Herein, we have investigated a rapid and scalable postfunctionalization of poly(pentafluorostyrene) to mechanically modified PWN. Alkyl chains of different lengths ranging from a chain of 6 carbons (-C06) to 18 carbons (-C18) were introduced via para-fluoro-thiol reaction, followed by substitution of the residual para-fluor atoms with phosphonic acid groups via Michaelis-Arbuzov reaction. For the first time, we were able to produce free-standing PWN membranes. Via differential scanning calorimetry measurements, molecular dynamics simulation, and tensile testing, we have proven that the plasticization effect ascends with increasing alkyl chain length. Thereby, the alkyl modification also turned out to be thermally stable (>332 °C), demonstrated with TGA-FTIR measurements. The membrane with 68% phosphonic acid groups and 28% C18 alkyl chains showed a proton conductivity of 93.6 ± 6.9 mS cm–1 and outperformed the Nafion membrane (N-212), which exhibited a proton conductivity of 69.2 ± 6.21 mS cm–1 at 105 °C and a relative humidity of approximately 90%.

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Section: ■ Materials and Methodsmentioning

confidence: 99%

Section: ■ Materials and Methodsmentioning

confidence: 99%

Modification of Phosphonated Poly(pentafluorostyrene) toward Ductile Membranes for Electrochemical Applications

Stigler,

Wagner,

Thiele

et al. 2023

Macromolecules

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“…Post‐polymerization modifications through the chemistry of fluorinated polymers have been recently reviewed 123 . They are based on displacement of pentafluorophenol from ester pendent chains, or on p ‐substitution of perfluorobenzyl ester.…”

Section: Click and Other Reactions For Post‐polymerization Assembly And Modificationsmentioning

confidence: 99%

Playing construction with the monomer toy box for the synthesis of multi‐stimuli responsive copolymers by reversible deactivation radical polymerization protocols

D’Acunzo

Masci

2021

Journal of Polymer Science

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In this review article, we survey the 2016–June 2021 scientific literature on the synthesis of multi‐stimuli responsive (MSR) polymers, the main focus being on reversible deactivation radical polymerization techniques (RDRPs, also known as controlled radical polymerizations). In fact, along more than 40 years of extensive research, RDRPs have boosted the synthesis of stimuli‐responsive polymers. RDRPs are now robust, versatile, relatively user‐friendly and even interconvertible, thus allowing control over composition, sequence, and topology of polymers. Such control can afford materials with well‐defined responses to physical, chemical, and biological external stimuli. Furthermore, “click” reactions are used to combine macromolecular precursors or to introduce specific functional groups in the target structure. As a result, MSR polymers are obtained from diverse combinations of commercial or specially synthesized building blocks arranged at will into desired sequences and architectures. Thanks to this versatility, self‐assembling polymeric structures are designed either to respond to triggers and perform specific applicative tasks, or to investigate the influence of structural variables on the responsivity of polymers. The “green” trend emerging in the field of responsive polymers and RDRPs is also briefly discussed.

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Section: Introductionmentioning

confidence: 99%

“…[1,2] Among them, nucleophilic aromatic substitutions on perfluorobenzyl groups have been receiving increased attention due to their high reaction efficiencies and the possibility of monitoring through 19 F NMR spectroscopy. [3][4][5] Photo-trigged reactions on/with polymers have the advantage of temporal and spatial control of the light stimulus [6] and are being investigated for triggered release applications. [7] Apart from initiating polymerizations, the photoactivation of polymer-bound groups can trigger a variety of reaction types, including i) unselective coupling through C-H insertions or radical-radical recombination (as found, for example, for the benzophenone moiety) [8] ; ii) dimerizations (for example, of coumarin side groups) [9] ; iii) the release of photoprotected ("photo-caged") groups (ortho-nitrobenzyl esters are a common example of photo-caged acids) [10,11] ; and iv) selective reactions between two complementary reactive groups following the photo-triggered aisomerization, deprotection, or activation of one of the groups.…”

Section: Introductionmentioning

confidence: 99%

Photochemistry of Azide‐Functional Polymers: Soluble Sulfoximine Polymers through Selective Nitrene–Sulfoxide Addition

Bakar

Roth

2022

Macro Chemistry & Physics

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Organic azides are a common functional group in polymer chemistry. Upon irradiation, they form nitrenes which are usually exploited for crosslinking based on their "universal" reactivity allowing insertion into nearby C-H bonds. Herein, it is demonstrated that polymer-bound perfluorophenyl azide groups selectively form sulfoximines when irradiated in the presence of an excess of sulfoxide, without observable crosslinking. Poly(4-azido-2,3,5,6-tetrafluorobenzyl methacrylate) (carrying an azide group in every repeat unit) is prepared through azide-para-fluoro postpolymerization modification of a 2,3,4,5,6-pentafluorobenzyl-functional precursor. Samples of the azide-functional polymer are irradiated (𝝀 max = 254 nm) in dichloromethane in the presence of varying amounts of five different sulfoxides. Products are characterized by 1 H and 19 F NMR spectroscopy, Fourier transform infrared spectroscopy, size exclusion chromatography, and differential scanning calorimetry. Irradiations for 7 h with a 40-70-fold molar excess of sulfoxides gave soluble products with azide-to-sulfoximine conversions of 89-96%. This first example of a selective nitrene-based reaction in the polymer arena shows that sulfoxide solvents must be avoided if crosslinking is desired and provides access to novel sulfoximine-functional materials.

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Post-polymerization modification based on reactive fluorinated polymers reaction

Cited by 9 publications

References 146 publications

Modification of Phosphonated Poly(pentafluorostyrene) toward Ductile Membranes for Electrochemical Applications

Modification of Phosphonated Poly(pentafluorostyrene) toward Ductile Membranes for Electrochemical Applications

Playing construction with the monomer toy box for the synthesis of multi‐stimuli responsive copolymers by reversible deactivation radical polymerization protocols

Photochemistry of Azide‐Functional Polymers: Soluble Sulfoximine Polymers through Selective Nitrene–Sulfoxide Addition

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