Linear High Molecular Weight Ladder Polymers by Optimized Polycondensation of Tetrahydroxytetramethylspirobisindane and 1,4-Dicyanotetrafluorobenzene

Abstract

/npsi/ctrl?action=rtdoc&an=8934286&lang=en http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/ctrl?action=rtdoc&an=8934286&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/ma801000uMacromolecules, 41, 20, pp. 7411-7417, 2008 Linear high molecular weight ladder polymers by optimized polycondensation of tetrahydroxytetramethylspirobisindane and 1,4-dicyanotetrafluorobenzene Song, Jingshe; Du, Naiying; Dai, Ying; Robertson, Gilles; Guiver, Michael; Thomas, Sylvie; Pinnau, Ingo ABSTRACT: A study on the optimization of conditions for polycondensation of 3,3,3′,3′-tetramethyl-1,1′-spirobisindane-5,5′,6,6′-tetrol, TTSBI, with 1,4-dicyanotetrafluorobenzene (DCTB) in dimethylformamide (DMF) at 50-70°C is reported. A linear PIM-1 polymer (PIM ) polymer with intrinsic microporosity) with high molecular weight was obtained by optimized reaction conditions. Of the solvents tested, DMF was the preferred solvent for this reaction. The optimized molar ratio TTSBI/DCTB/K 2 CO 3 was 1/1/2.04. The mechanism of PIM-1 crosslinking during polymerization was studied, and gel-free, high molecular weight PIM-1 polymer was prepared. The physical properties of anhydrous K 2 CO 3 significantly affected the reaction rate. Flexible tough polymer films were cast from PIM-1 solution in chloroform, and pure permeability data are reported for several gases.

Photo-oxidative enhancement of polymeric molecular sieve membranes

“…The PIM-1 polymer was synthesized following the method described by Budd and McKeown 22 , and an optimized recipe by Guiver and co-workers 49 . A one-step polycondensation via a double aromatic nucleophilic substitution from purified monomers, 5,5 0 ,6,6 0 -tetrahydroxy-3,3,3 0 ,3 0 -tetramethyl-1,1 0 -spirobisindane (TTSBI, 10.213 g, 30 mmol, Alfa Aesar) and 2,3,5,6-tetrafluoroterephthalonitrile (TFTPN, 6.003 g, 30 mmol, Matrix Scientific), was performed in the presence of K 2 CO 3 (8.292 g, 60 mmol, Aldrich) in anhydrous DMF (200 ml, Alfa Aesar).…”

Gas transport behavior of mixed-matrix membranes composed of silica nanoparticles in a polymer of intrinsic microporosity (PIM-1)

“…PIM-1 polymer was synthesized by polycondensation reaction of 5,5 ′ ,6,6 ′ -tetrahydroxy-3,3,3 ′ ,3 ′ -tetramethyl-1,1 ′ -spirobisindane (TTSBI) with 2,3,5,6-tetrafluoro-terephthalonitrile (TFTPN) in dimethylacetamide (DMAc) [23,24]. The molecular weight (M w ) and molecular dispersity (M w /M n ), determined by gel permeation chromatography (GPC) in THF against polystyrene standards, were approximately 100,000 Da and 2.9, respectively.…”

“…Among these novel materials, PIM-1, containing the contorted spirobisindane unit, has attracted the most attention due to its relative ease of synthesizing high molecular weight polymer and the combination of outstanding permeability with moderate selectivity, especially for O 2 /N 2 and CO 2 /CH 4 pairs, which overcome the upper bound trade-off proposed by Robeson [18,19]. Since the initial reports of Budd et al and McKeown et al, structurally new PIMs and additional data on PIM-1 have appeared [20][21][22][23][24][25].…”

Polymers of Intrinsic Microporosity

“…Both methods provide PIM-1 with sufficiently high average molecular mass to provide mechanically robust solvent cast films but generally the low temperature method is favoured as it is easier to control and more suitable to scale up [64]. A modified "high temperature" method of continuous production of PIM-1 using flow reactors has been patented, although the average molecular mass of the resulting polymer was modest [65].…”

“…An alternative preparation method involves the initial formation of the silyl ether of the biscatechol monomer A1; although successful, this appears to be an unnecessary additional synthetic step [66]. The concentration of the monomers in the standard "low-temperature" polymerisation is important as at very high concentrations insoluble crosslinked material is produced [64] whereas at low concentrations a large amount of cyclic oligomers of modest molecular mass is formed [66,67]. The optimal concentration appears to be around 3 mmol of each monomer per 10-15 mL DMF.…”