02538nas a2200229   4500008004100000022001400041245014600055210006900201260000900270300001200279490000700291520170500298653002102003653002802024653001502052653001902067100002102086700001902107700002202126700002802148856013202176       2018                        eng d  a0887-624X00aIntrinsically microporous polyimides containing spirobisindane and phenazine units: synthesis, characterization and gas permeation properties0 aIntrinsically microporous polyimides containing spirobisindane a  cAPR   a766-7750 v563 aA new diamine containing spirobisindane and phenazine units, namely, 3,3,3,3-tetramethyl-2,2,3,3-tetrahydro-1,1-spirobi[cyclopenta[b]phen azine]-7,7-diamine (TTSBIDA) was synthesized starting from commercially available 5,5,6,6-tetrahydroxy-3,3,3,3-tetramethyl-1,1-spirobisindane (TTSBI). TTSBI was oxidized to 3,3,3,3-tetramethyl-2,2,3,3-tetrahydro-1,1-spirobi[indene]-5,5,6,6-tet raone (TTSBIQ) which was subsequently condensed with 4-nitro-1,2-phenylenediamine to obtain 3,3,3,3-tetramethyl-7,7-dinitro-2,2,3,3-tetrahydro-1,1-spirobi[cyclope nta[b]phenazine] (TTSBIDN). TTSBIDN was converted into TTSBIDA by reduction of the nitro groups using hydrazine hydrate in the presence of Pd/C as the catalyst. A series of new polyimides of intrinsic microporosity (PIM-PIs) were synthesized by polycondensation of TTSBIDA with commercially available aromatic dianhydrides. PIM-PIs exhibited amorphous nature, high thermal stability (T-10&gt;480 degrees C) and intrinsic microporosity (BET surface area=59-289 m(2)/g). The gas permeation characteristics of films of selected PIM-PIs were evaluated and they exhibited appreciable gas permeability as well as high selectivity. The CO2 and O-2 permeability of PIM-PIs were in the range 185.4-39.2 and 30.6-6.2 Barrer, respectively. Notably, polyimide derived from TTSBIDA and 4,4-(hexafluoroisopropylidene)diphthalic anhydride (PIM-PI-6FDA) exhibited high CO2 and O-2 permeability of 185.4 and 30.6 Barrer with CO2/CH4 and O-2/N-2 selectivity of 43.1 and 5.1, respectively. The data of PIM-PI-6FDA for CO2/CH4 and O-2/N-2 gas pairs were located near Robeson upper bound. (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 766-77510aGas permeability10aintrinsic microporosity10apolyimides10aspirobisindane1 aShrimant, Bharat1 aDangat, Yuvraj1 aKharul, Ulhas, K.1 aWadgaonkar, Prakash, P.  uhttps://library.ncl.res.in/content/intrinsically-microporous-polyimides-containing-spirobisindane-and-phenazine-units-synthesis02571nas a2200241   4500008004100000022001400041245012400055210006900179260000900248300001000257490000700267520172200274653001501996653001902011653002802030653001402058653003302072100002102105700002602126700002202152700002802174856012702202       2018                        eng d  a0887-624X00aSynthesis, characterization, and gas permeation properties of adamantane-containing polymers of intrinsic microporosity0 aSynthesis characterization and gas permeation properties of adam  cJAN   a16-240 v563 a<p>A new bis(catechol) monomer, namely, 4,4-((1r,3r)-adamantane-2,2-diyl)bis(benzene-1,2diol) (THADM) was synthesized by condensation of 2-adamantanone with veratrole followed by demethylation of the formed (1r,3r)-2,2-bis(3,4 dimethoxyphenyl)adamantane. Polycondensation of THADM and various compositions of THADM and 5,5,6,6-tetrahydroxy-3,3,3,3-tetramethylspirobisindane was performed with 2,3,5,6-tetrafluoroterephthalonitrile (TFTPN) to obtain the homopolymer and copolymers. These polymers demonstrated good solubility in common organic solvents such as dichloromethane, chloroform, and tetrahydrofuran and could be cast into tough films from their chloroform solutions. GPC analysis revealed that number average molecular weights of polymers were in the range 48,100-61,700 gmol(-1), suggesting the formation of reasonably high molecular weight polymers. They possessed intrinsic microporosity with Brunauer-Emmett-Teller (BET) surface area in the range 703-741 m(2)g(-1). Thermogravimetric analysis of polymers indicated that 10% weight loss temperature was in the range 513-518 degrees C demonstrating their excellent thermal stability. THADM-based polymer of intrinsic microporosity (PIM) showed P(CO2)=1080, P(O-2)=232 and appreciable selectivity [(CO2/CH4)=22.6, (CO2/N-2)=26.7, and (O-2/N-2)= 5.7]. The gas permeability measurements revealed that with increase in the content of adamantane units in PIMs, selectivity increased and permeability decreased, following the trade-off relationship. The gas separation properties of PIMs containing adamantane units were located close to 2008 Robeson upper bound for gas pairs such as CO2/CH4, CO2/N-2, H-2/N-2, and O-2/N-2. (c) 2017 Wiley Periodicals, Inc.</p>10aadamantane10aGas permeation10aintrinsic microporosity10amembranes10astructure-property relations1 aShrimant, Bharat1 aShaligram, Sayali, V.1 aKharul, Ulhas, K.1 aWadgaonkar, Prakash, P.  uhttps://library.ncl.res.in/content/synthesis-characterization-and-gas-permeation-properties-adamantane-containing-polymers