The modification of polysulfone by metalation

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

doi:10.1002/pol.1988.140260211

Cited by 79 publications

(44 citation statements)

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“…Benzyl protons H [15][16][17] are all within 0.2 ppm of one another, the furthest downfield being H 15 , which is affected by the electronic effect of the imine group. The H 17 1 H triplet is coupled with H 16 . A trace amount of disubstituted repeat units was observed for H 9 at 7.89 ppm and for H 15 at 7.50 ppm.…”

Section: Nmr Of Psf-benziminesmentioning

confidence: 97%

“…Samples for differential scanning calorimetry analysis were initially heated at a rate of 10°C/min under a nitrogen atmosphere to well below the polymer T d point, quenched in liquid nitrogen, and then reheated at the same rate. 12, 16 The slightly viscous, orange solution of PSf-Li was stirred for an additional 15 min, and then precooled benzonitrile (9.30 mL, 90.4 mmol) was poured quickly into the reaction flask under vigorous stirring; this resulted in a viscous and orange heterogeneous mixture. The viscosity decreased while the reaction was gradually warmed to Ϫ10°C over a period of 1.5 h. The modified PSf was recovered by precipitation from 95% ethanol and then washed, filtered, and dried in a vacuum oven at 60°C for several hours.…”

Section: Materials and Characterizationmentioning

confidence: 99%

“…11,12,16 In this study, two modified polymers with different amounts of pendant benzimine groups (PSf-benzimine) were prepared by the addition of benzonitrile to PSf-Li. Although the reaction of PSf-Li (DS ϭ 0.5) with benzonitrile was quantitative, PSf-Li (DS ϭ 2.0) resulted in a less than fully substituted addition product with a DS of 1.68.…”

Section: Synthesesmentioning

confidence: 99%

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Modified polysulfones. VI. Preparation of polymer membrane materials containing benzimine and benzylamine groups as precursors for molecularly imprinted sensor devices

Robertson

Guiver

Bilodeau

et al. 2003

J. Polym. Sci. A Polym. Chem.

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A modified polysulfone containing benzylamine groups was synthesized as a reactive membrane material. Polysulfone was activated at the ortho-sulfone site by direct lithiation with n-butyllithium, and the resulting lithiated polysulfone was then reacted with benzonitrile; this yielded a polymer with pendant benzimine groups. The structure was confirmed by NMR and IR spectroscopy and by the transformation of imine to ketone by acid hydrolysis. The polymeric benzimine was also reduced to benzylamine with sodium cyanoborohydride in an acidic medium. The structure and degree of substitution of both benzylamine derivatives were determined by NMR and IR spectroscopy. The modified polysulfone containing benzylamine groups initiated the polymerization of N-carboxyanhydride of ␥-benzyl-L-glutamate [Glu(OBzl)-NCA]. The side-chain oligopeptide of Glu(OBzl)-NCA attached to polysulfone was converted into molecular recognition sites.

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Section: Nmr Of Psf-benziminesmentioning

confidence: 97%

Section: Materials and Characterizationmentioning

confidence: 99%

Section: Synthesesmentioning

confidence: 99%

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Modified polysulfones. VI. Preparation of polymer membrane materials containing benzimine and benzylamine groups as precursors for molecularly imprinted sensor devices

Robertson

Guiver

Bilodeau

et al. 2003

J. Polym. Sci. A Polym. Chem.

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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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“…20,22,23 Following addition, the lithiated polysulfone solution was stirred for 15 min and then warmed gradually to -30°C over about 1 h. TMSBA (16.3 g, 91.8 mmol) was injected promptly into the reaction solution, which immediately became cloudy white, and then the solution was stirred with gradual warming to -15°C. The polymer was recovered by precipitation from ice water, washed with iceethanol, and dried in an oven at 110°C.…”

Section: Synthesis Of Psf-s-hbtmsmentioning

confidence: 99%

Enhancement in the Gas Permeabilities of Novel Polysulfones with Pendant 4-Trimethylsilyl-α-hydroxylbenzyl Substituents

et al. 2003

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A series of modified polymers with 4-trimethylsilyl-R-hydroxylbenzyl (HBTMS) substituents were made as new materials for membrane gas separation. HBTMS was introduced onto polysulfone (PSf), tetramethylpolysulfone (TMPSf), and hexafluoropolysulfone (6FPSf) by forming lithiated polymer intermediates followed by treatment with an electrophile, p-trimethylsilylbenzaldehyde. The resulting side substituent contains the bulky trimethylsilyl (TMS) groups separated from the polymer chain by an aromatic ring. The polymer structures were characterized by NMR spectroscopy, and thermal properties were investigated by differential scanning calorimetry and thermogravimetry. The permeability coefficients of the resulting polymers PSf-HBTMS, TMPSf-HBTMS, and 6FPSf-HBTMS showed considerable increases over the unmodified polymers. TMPSf-HBTMS showed the greatest improvements in gas transport properties with large increases in both CO 2 and O2 permeabilities of ∼3-fold (72 and 18 Barrers, respectively) compared with TMPSf. In the case of the CO2/N2 gas pair, there was an absence of the typical accompanying tradeoff shown by decreases in permselectivity with increasing permeability. Comparisons of this series of polymers containing the new HBTMS substituent were made with those having other TMS pendant groups.

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The modification of polysulfone by metalation

Cited by 79 publications

References 0 publications

Modified polysulfones. VI. Preparation of polymer membrane materials containing benzimine and benzylamine groups as precursors for molecularly imprinted sensor devices

Modified polysulfones. VI. Preparation of polymer membrane materials containing benzimine and benzylamine groups as precursors for molecularly imprinted sensor devices

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

Enhancement in the Gas Permeabilities of Novel Polysulfones with Pendant 4-Trimethylsilyl-α-hydroxylbenzyl Substituents

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