Modified polysulfones. IV. Synthesis and characterization of polymers with silicon substituents for a comparative study of gas‐transport properties

Guiver, Michael D.; Robertson, Gilles P.; Rowe, Sheri; Foley, Stephen Ronan; Kang, Yong Soo; Park, Hyun Chae; Won, Jongok; Thi, Hoai Nam Le

doi:10.1002/pola.1187

Cited by 20 publications

(20 citation statements)

References 24 publications

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“…This shows a trend similar to our previous observations, 11,17,26 which is that substitution at the ortho ether site is more effective in increasing permeability than at the ortho sulfone sites. This is due to the fact that the ether linkage is more flexible and is hindered more readily by bulky substituents than the already hindered sulfone linkage.…”

Section: Resultssupporting

confidence: 78%

“…11,17 All PSf polymer derivatives had lower T g values than PSf. PSf-s-HBTMS had a T g ∼13°C higher than that of PSf-o-HBTMS.…”

Section: Resultsmentioning

confidence: 99%

“…PSf's were activated by direct lithiation 20 or by brominationlithiation 21 to produce reactive lithiated intermediates that were then converted by various electrophiles to yield derivatives of PSf. 11,12,[22][23][24][25][26] In comparison with previous work in which TMS, dimethylphenylsilyl (DMPS), and methyldiphenylsilyl (MDPS) groups were introduced on PSf and TMPSf, 11,12,26 this work reports the improvements in gas permeability for polymers PSf, TMPSf, and 6FPSf modified to contain the new bulky side substituent 4-trimethylsilyl-R-hydroxylbenzyl (HBT-MS). HBTMS contains TMS, phenyl, and OH groups and is distinct from TMS and DMPS since the TMS group is spaced further from the polymer chain.…”

Section: Introductionmentioning

confidence: 99%

“…In addition, they hinder chain motions and disrupt chain packing thereby improving gas permeability with minimal loss in permselectivity. [11][12][13][14][15][16][17] The chemical structure and physical properties of the membrane material influence the permeability and permselectivity. 18 Transport properties depend on the free volume within the polymer and on the segmental mobility of the polymer chains.…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Resultssupporting

confidence: 78%

“…11,17 All PSf polymer derivatives had lower T g values than PSf. PSf-s-HBTMS had a T g ∼13°C higher than that of PSf-o-HBTMS.…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

et al. 2003

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“…Gas permeabilities have been shown to be significantly improved by introducing organosilanes onto the polymer main chain 3,4 and postsilylation of polymers. Trialkylsilyl groups introduced onto phenyl rings of polystyrene, 5 on the polypropyne chain, [6][7][8][9][10][11] and on the phenyl rings of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) [12][13][14] and polysulfones [15][16][17][18] result in high gas permeability. Many efforts have been made to improve the permeation properties of polysulfones by modifying the chemical structure because aromatic polysulfones such as bisphenol A polysulfone (PSf) and poly(phenyl sulfone) have been widely used for gas separation membranes.…”

Section: Introductionmentioning

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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Synthese von Materialien mit erweitertem π‐System durch C‐H‐Aktivierung

2014

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Die Aktivierung von aromatischen C‐H‐Bindungen durch einen Übergangsmetallkatalysator ist ein wichtiges Thema in der Synthesechemie. In den letzten Jahren hat sich die schnelle und regiospezifische Erweiterung von π‐Systemen durch C‐H‐Aktivierung zu einer idealen Methode zur Herstellung von organischen Materialien mit ausgedehntem π‐System entwickelt. Dieser Aufsatz fasst neuere Reaktionen zur C‐H‐Aktivierung für die Erweiterung von π‐Systemen im Hinblick auf neue optoelektronische konjugierte Materialien zusammen.

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Modified polysulfones. IV. Synthesis and characterization of polymers with silicon substituents for a comparative study of gas‐transport properties

Cited by 20 publications

References 24 publications

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

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

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

Synthese von Materialien mit erweitertem π‐System durch C‐H‐Aktivierung

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