Functional group polysulphones by bromination-metalation

Guiver, Michael D.; Kutowy, O.; ApSimon, John W.

doi:10.1016/0032-3861(89)90094-3

Cited by 78 publications

(93 citation statements)

References 11 publications

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“…[29][30][31] Following addition, the lithiated 6FPSf solution was stirred for 15 min at -25°C. ClTMS (16.0 g, 18.7 mL, 147 mmol) was injected promptly into the reaction solution, which immediately became less viscous and dark-red, and then the solution was stirred with gradual warming to 0°C for about 1 h. The polymer was recovered, and the resulting white product (19.1 g; yield 93% calculated from the formula 6FPSf-TMS 2) had a degree of substitution (DS) of 2.0.…”

Section: Preparation Of 6fpsf-s-tms (Ortho Sulfone)mentioning

confidence: 99%

Preparation and Characterization of Polysulfones Containing Both Hexafluoroisopropylidene and Trimethylsilyl Groups as Gas Separation Membrane Materials

Dai¹,

Guiver²,

Robertson³

et al. 2004

Macromolecules

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/npsi/ctrl?action=rtdoc&an=8906267&lang=en http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/ctrl?action=rtdoc&an=8906267&lang=frAccess and use of this website and the material on it are subject to the Terms and Conditions set forth at http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/jsp/nparc_cp.jsp?lang=en NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. For the publisher's version, please access the DOI link below./ Pour consulter la version de l'éditeur, utilisez le lien DOI ci-dessous.http://dx.doi.org/10.1021/ma035739i Macromolecules, 37, 4, pp. 1403Macromolecules, 37, 4, pp. -1410Macromolecules, 37, 4, pp. , 2004 Preparation and characterization of polysulfones containing both hexafluoroisopropylidene and trimethylsilyl groups as gas separation membrane materials Dai, Y.; Guiver, Michael; Robertson, Gilles; Kang, Y.; Lee, Kunchan; Jho, J. Science and Technology, P.O. Box 131, Cheongryang, Seoul 130-650, Korea; and Hyperstructured Organic Materials Research Center and School of Chemical Engineering, Seoul National University, Seoul 151-744, Korea Received November 19, 2003; Revised Manuscript Received December 16, 2003 ABSTRACT: Trimethylsilylated derivatives of hexafluoropolysulfone (6FPSf) and tetramethylhexafluoropolysulfone (TM6FPSf) were prepared by reaction of lithiated polymer intermediates with halotrimethylsilane electrophiles for a membrane gas separation study to compare improvements in gas permeabilities with those of unmodified polymers. Ortho sulfone substituted 6FPSf and TM6FPSf having pendant trimethylsilyl (TMS) groups were obtained by a two-step process involving first direct lithiation of 6FPSf and TM6FPSf solutions with n-butyllithium to afford ortho sulfone dilithiated intermediates, followed by reaction with a TMS electrophile. The corresponding ortho ether 6FPSf derivative was obtained by lithiation of dibrominated 6FPSf at the bromine sites, followed by reaction with a TMS electrophile. The degree of substitution (DS) of the TMS groups was g2.0 and was dependent on the molar ratio of n-butyllithium and electrophile quantity, electrophile reactivity, and reaction conditions. Detailed structural characterization and DS of the modified polymers were obtained by nuclear magnetic resonance spectroscopy. The glass transition temperatures and thermal stabilities were determined by differential scanning calorimetry and thermogravimetric analysis, respectively. Polymer chain d-spacing was investigated using wide-angle X-ray diffraction. Polymer free volume was calculated from the polymer density and specific van der Waals volume. The polymer gas permeability coefficients (P) were measured for He, CO 2,O 2, and N2. Both CO2 and O2 permeabilities of modified 6FPSf increased by 8-9-fold (P(CO2) ) 110 barre...

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Section: Preparation Of 6fpsf-s-tms (Ortho Sulfone)mentioning

confidence: 99%

Preparation and Characterization of Polysulfones Containing Both Hexafluoroisopropylidene and Trimethylsilyl Groups as Gas Separation Membrane Materials

Dai¹,

Guiver²,

Robertson³

et al. 2004

Macromolecules

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“…The introduction of functionality into PSf has been accomplished by copolymerization with functionalized comonomers or by postfunctionalization of commercially available polymers. Examples of the functionalization chemistry include sulfonation, 3 bromination, 4 chloromethylation, 5 amidoalkylation, 6 and lithiation. 7−9 Functionalized PSfs have been actively investigated as membrane materials for gas 1,2,10,11 and liquid separation 12 and for fuel cells (FCs).…”

Section: ■ Introductionmentioning

confidence: 99%

Phenyltrimethylammonium Functionalized Polysulfone Anion Exchange Membranes

et al. 2012

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Anion exchange membrane (AEM) materials were prepared from commercial polysulfone (PSf) by functionalization with tertiary amines via lithiation chemistry. By optimizing the reaction conditions, a degree of substitution (DS) of 0.81 could be achieved without evident polymer decomposition or cross-linking. The PSf containing pendent bis(phenyldimethylamine) substituents were then quaternized with CH3I and ion exchange reaction to provide bis(phenyltrimethylammonium) (PTMA) polymer with hydroxide-conductive properties. Flexible and tough membranes with various ion exchange capacities (IEC)s could be prepared by casting the polymers from DMAc solutions. The ionomeric membranes showed considerably lower water uptake (less than 20%), and thus dimensional swelling in water, compared with many reported AEMs. The hydroxide conductivities of the membranes were above 10 mS/cm at room temperature. The unusually low water uptake and good hydroxide conductivity may be attributed to the “side-chain-type” structures of pendent functional groups, which facilitate ion transport. Although the PTMA substituents on the AEM were found to have insufficient long-term stability for alkaline fuel cell application, the investigation gives some insight and directions for polymeric designs by postfunctionalization.

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“…[6,7] Bromine-containing polymers are often prepared either by post-bromination or by the polymerization of brominated monomers. [8] Compared with sulfonic acid units, phosphonic acid units are known for their higher chemical and thermal stability and greater ability to retain water. [9] Phosphonated polymers are anticipated as potential proton exchange membranes (PEMs) for possible high-temperature fuel cell applications, which will enhance the kinetics of the electrode reactions and reduce the risk of catalyst poisoning.…”

Section: Introductionmentioning

confidence: 99%

Fluorinated Poly(aryl ether) Containing a 4‐Bromophenyl Pendant Group and its Phosphonated Derivative

Liu¹,

Robertson²,

Guiver³

et al. 2006

Macromol. Rapid Commun.

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Summary: A high‐molecular‐weight fluorinated poly(aryl ether) with a 4‐bromophenyl pendant group has been synthesized based on a bromo‐bisphenol. A phosphonic acid derivative is readily prepared from this in high conversion yield. The phosphonated polymer possesses excellent thermal, oxidative, and dimensional stability, low methanol permeability, and reasonable proton conductivity, and may be a candidate polymeric electrolyte membrane for fuel cell applications.

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Functional group polysulphones by bromination-metalation

Cited by 78 publications

References 11 publications

Preparation and Characterization of Polysulfones Containing Both Hexafluoroisopropylidene and Trimethylsilyl Groups as Gas Separation Membrane Materials

Preparation and Characterization of Polysulfones Containing Both Hexafluoroisopropylidene and Trimethylsilyl Groups as Gas Separation Membrane Materials

Phenyltrimethylammonium Functionalized Polysulfone Anion Exchange Membranes

Fluorinated Poly(aryl ether) Containing a 4‐Bromophenyl Pendant Group and its Phosphonated Derivative

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