- Molecular engineering of high-performance nanofiltration membranes from intrinsically microporous poly(ether-ether-ketone)
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Poly(ether-ether-ketone) has received increased attention due to its high thermal and chemical stability, and high performance in various applications. However, it suffers from a semi-crystalline morphology, low fractional free volume, and poor processability, requiring the use of harsh acidic solvents, which leads to undesired sulfonation. In this work, three intrinsically microporous poly(ether-ether-ketones) (iPEEKs), incorporating spirobisindane, Tr?ger's base, and triptycene contorted structures, were developed for organic solvent nanofiltration. Molecular dynamics simulations have assisted the molecular engineering of the polymers and the understanding of the improved membrane performance through the binding energies between solvents and polymers. Application of the design principles of polymers of intrinsic microporosity has led to a paradigm shift with a notable enhancement in both the polymer properties and the subsequently fabricated nanofiltration membranes' performance. The iPEEKs showed excellent solution processability, a high surface area of 205-250 m2 g-1, and excellent thermal stability. Mechanically flexible nanofiltration membranes were prepared from N-methyl-2-pyrrolidone dope solution at iPEEK concentrations of 19-35 wt%. The molecular weight cutoff of the membranes was fine-tuned in the range of 450-845 g mol-1 displaying 2-6 fold higher permeance (3.57-11.09 L m-2 h-1 bar-1) than previous reports. The long-term stabilities were demonstrated by a 7 day continuous cross-flow filtration. This journal is
- Abdulhamid, Mahmoud A.,Akhtar, Faheem Hassan,Ng, Kim Choon,Park, Sang-Hee,Schwingenschl?gl, Udo,Szekely, Gyorgy,Vovusha, Hakkim
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- Synthesis and characterization of triptycene type cross-linker and its use in photoinduced curing applications
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A novel triptycene type diacrylate cross-linker, triptycene hydroquinone diacrylate (THDA) was synthesized from the reaction of triptycene hydroquinone with acryloyl chloride and characterized. The photocuring behaviour and the reaction kinetics of the synthesized cross-linker were investigated by means of photo-differential scanning calorimetry (photo-DSC) experiments. Formulations containing monofunctional (meth)acrylate monomers, namely glycidyl methacrylate (GMA), 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), and 2-ethylhexyl methacrylate (EHMA), cross-linker, THDA and 2,2-dimethoxy-2-phenylacetophenone (DMPA) as a photoinitiator were irradiated. A?conventional cross-linker without triptycene unit such as hydroquinone diacrylate (HDA) was used under the same conditions for comparison. The effects of the structure of the monofunctional monomer and triptycene moiety on the photopolymerization kinetics were evaluated and discussed.
- Ates, Sahin,Aydogan, Binnur,Torun, Lokman,Yagci, Yusuf
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- POLYMERS FOR USE IN ELECTRONIC DEVICES
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In Formula I: Qa is CRX, SiRx, GeRx, PRX, or N; Qb is CRy, SiRy, GeRy, PRy, or N; R1, R2, and R3 are the same or
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- NOVEL COMPOUND HAVING TRIPTYCENE SKELETON AND METHOD FOR PRODUCING THE SAME
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PROBLEM TO BE SOLVED: To provide a novel compound that can be used as a polymerization component of resin. SOLUTION: The present invention provides a compound represented by formula (1) (R1 and R2 independently represent a substituent, R3 each independently represent a hydroxyl group, a group [-OR4] or a halogen atom; R4 is a hydrocarbon group; m1 each independently represent an integer of 0-4; m2 is an integer of 0-2; n is an integer of 1 or greater). SELECTED DRAWING: None COPYRIGHT: (C)2019,JPOandINPIT
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Paragraph 0159
(2019/03/17)
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- A triptycene ionic liquid functional material, its preparation and its use (by machine translation)
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The invention relates to a triptycene ionic liquid functional material, its preparation and its application, which belongs to the technical field of gas chromatography. The triptycene ionic liquid functional material with triptycene parent, cationic functional unit and anion structure unit of the individual performance advantages, as the gas phase chromatography stationary relative nature similar component exhibits high selectivity, high-efficient separation of different polarity can be various component mixture, especially difficult separation of the various isomer mixture, compared with the commercial chromatographic column shows the obvious advantage of separation; and synthetic the triptycene ionic liquid functional material of low cost raw materials, the experimental device is simple and easy to obtain, the synthetic method is simple, high product yield. (by machine translation)
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- Blurring the Lines between Host and Guest: A Chimeric Receptor Derived from Cucurbituril and Triptycene
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We report the synthesis and X-ray crystal structure of a cucurbituril–triptycene chimeric receptor (1). Host 1 binds to guests typical of CB[6]–CB[8], but also binds to larger guests such as blue box (20) and the Fujita square (22). Intriguingly, the geom
- Lu, Xiaoyong,Samanta, Soumen K.,Zavalij, Peter Y.,Isaacs, Lyle
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supporting information
p. 8073 - 8078
(2018/06/04)
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- Hybrid Molecular Container Based on Glycoluril and Triptycene: Synthesis, Binding Properties, and Triggered Release
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We designed and synthesized a “hybrid” molecular container 1, which is structurally related to both cucurbit[n]uril (CB[n]) and pillar[n]arene type receptors. Receptor 1 was fully characterized by 1H NMR, 13C NMR, IR, MS and X-ray single crystal diffraction. The self-association behavior, host–guest recognition properties of 1, and the [salt] dependence of Ka were investigated in detail by 1H NMR and isothermal titration calorimetry (ITC). Optical transmittance and TEM measurements provide strong evidence that receptor 1 undergoes co-assemble with amphiphilic guest C10 in water to form supramolecular bilayer vesicles (diameter 25.6±2.7 nm, wall thickness ≈3.5 nm) that can encapsulate the hydrophilic anticancer drug doxorubicin (DOX) and the hydrophobic dye Nile red (NR). The release of encapsulated DOX or NR from the vesicles can be triggered by hexamethonium (8 c) or spermine (10) which leads to the disruption of the supramolecular vesicles.
- Liu, Wenjin,Lu, Xiaoyong,Xue, Weijian,Samanta, Soumen K.,Zavalij, Peter Y.,Meng, Zihui,Isaacs, Lyle
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supporting information
p. 14101 - 14110
(2018/09/11)
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- Preparation and gas transport properties of triptycene-containing polybenzoxazole (PBO)-based polymers derived from thermal rearrangement (TR) and thermal cyclodehydration (TC) processes
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Polybenzoxazoles (PBOs), such as thermally rearranged (TR) polymers, have been shown to have excellent gas separation performance. Herein we report the preparation and transport properties of two new series of PBO-based polymers that were thermally derived from triptycene-containing o-hydroxy polyimide and polyamide precursors via a thermal rearrangement (TR) process and a thermal cyclodehydration (TC) process, respectively. Incorporation of triptycene units into poly(hydroxyimide) precursor structures led to a significant increase of fractional free volume and created ultrafine microporosity in the converted PBO-based TR polymers, which enabled both high gas permeabilities and high selectivities. Although the TC process of the poly(hydroxyamide) precursor led to moderate improvement in the separation performance of the resulting triptycene-containing PBO polymers as compared to the TR process, the PBO films converted via the TC process exhibited excellent mechanical properties superior to many other TR polymers previously reported in the literature as well as the triptycene-containing TR polymers in this study. In particular, the PBO film thermally rearranged at 450 °C showed a H2 pure gas permeability of 810 barrer, a CO2 permeability of 270 barrer, and CO2/CH4 and H2/CH4 selectivities of 67 and 200, respectively, at 35 °C and 11 atm, which are far beyond the upper bound limits.
- Luo, Shuangjiang,Liu, Junyi,Lin, Haiqing,Kazanowska, Barbara A.,Hunckler, Michael D.,Roeder, Ryan K.,Guo, Ruilan
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p. 17050 - 17062
(2016/11/11)
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- Triptycene-Based Chiral and meso-N-Heterocyclic Carbene Ligands and Metal Complexes
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Based on 1-amino-4-hydroxy-triptycene, new saturated and unsaturated triptycene-NHC (N-heterocyclic carbene) ligands were synthesized from glyoxal-derived diimines. The respective carbenes were converted into metal complexes [(NHC)MX] (M=Cu, Ag, Au; X=Cl, Br) and [(NHC)MCl(cod)] (M=Rh, Ir; cod=1,5-cyclooctadiene) in good yields. The new azolium salts and metal complexes suffer from limited solubility in common organic solvents. Consequently, the introduction of solubilizing groups (such as 2-ethylhexyl or 1-hexyl by O-alkylation) is essential to render the complexes soluble. The triptycene unit infers special steric properties onto the metal complexes that enable the steric shielding of selected areas close to the metal center. Next, chiral and meso-triptycene based N-heterocyclic carbene ligands were prepared. The key step in the synthesis of the chiral ligand is the Buchwald–Hartwig amination of 1-bromo-4-butoxy-triptycene with (1S,2S)-1,2-diphenyl-1,2-diaminoethane, followed by cyclization to the azolinium salt with HC(OEt)3. The analogous reaction with meso-1,2-diphenyl-1,2-diaminoethane provides the respective meso-azolinium salt. Both the chiral and meso-azolinium salts were converted into metal complexes including [(NHC)AuCl], [(NHC)RhCl(cod)], [(NHC)IrCl(cod)], and [(NHC)PdCl(allyl)]. An in situ prepared chiral copper complex was tested in the enantioselective borylation of α,β-unsaturated esters and found to give an excellent enantiomeric ratio (er close to 90:10).
- Savka, Roman,Bergmann, Marvin,Kanai, Yuki,Foro, Sabine,Plenio, Herbert
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p. 9667 - 9675
(2016/07/14)
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- Finely Tuning the Free Volume Architecture in Iptycene-Containing Polyimides for Highly Selective and Fast Hydrogen Transport
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Iptycene-based polyimides have attracted extensive attention recently in the membrane gas separation field due to their unique structural hierarchy and chemical characteristics that enable construction of well-defined yet tailorable free volume architecture for fast and selective molecular transport. We report here a new series of iptycene-based polyimides that are exquisitely tuned in the monomer structure to afford preferred microcavity architecture for hydrogen transport. In particular, a triptycene-containing dianhydride (TPDAn) was prepared to react with two iptycene-containing diamines (i.e., TPDAm and PPDAm) or 2,2′-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) to produce entirely or partially iptycene-based polyimides. The incorporation of iptycene units effectively disrupted chain packing, which resulted in ultrafine microporosity in the membranes with a desired bimodal size distribution with maxima at ~3 and ~7 ?, respectively. Depending on the combination of diamine and dianhydride, the microporosity was feasibly tuned and optimized to meet the needs of challenging H2 separations, especially for H2/N2 and H2/CH4 gas pairs. Particularly, a H2 permeability of 27 barrers and H2/N2 and H2/CH4 selectivities of 142 and 300, respectively, were obtained for TPDAn-6FAP.
- Luo, Shuangjiang,Wiegand, Jennifer R.,Kazanowska, Barbara,Doherty, Cara M.,Konstas, Kristina,Hill, Anita J.,Guo, Ruilan
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p. 3395 - 3405
(2016/06/01)
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- TRIPTYCENE MONOMER AND TRIPTYCENE CONTAINING POLYESTERS AND POLYURETHANES
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The primary diol triptycene derivative triptycene-1,4-hydroquinone-bis(2-hydroxyethyl) ether (TD) is provided, as are methods of using the same to synthesize polyesters and polyurethanes, and polyesters and polyurethanes synthesized therewith.
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Paragraph 0043; 0044
(2015/07/15)
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- Synthesis and characterization of triptycene-based polyimides with tunable high fractional free volume for gas separation membranes
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Robust polymer membranes that are highly permeable and selective are desired for energy efficient gas separation processes. In this study, a series of rigid, bulky triptycene-based diamine monomers were designed, synthesized, and subsequently incorporated into the backbone of polyimides via polycondensation with 2,2′-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) to obtain a series of polyimide membranes with high fractional free volume. These triptycene-containing polyimides with systematic variations in their chemical structure demonstrate the viability of the 'tunable' fractional free volume by introducing various substituents onto the polymer backbone. All the polyimides synthesized exhibited film-forming high molecular weight, high solubility, and excellent thermal properties, with glass transition temperatures ranging from 280 °C to 300 °C and thermal stability up to 500 °C. Compared to other classes of glassy polymers, these triptycene-polyimides had high combinations of permeability and selectivity, suggesting that a favorable free volume size distribution in these triptycene polyimides was induced by the unique chain packing mechanism of triptycene units. The correlation between gas transport properties and the polymer chemical structure was also investigated. Altering the size of the substituents neighboring the triptycene units provides greater opportunity to fine-tune the fractional free volume and free volume size distribution in the polymer, which in turn can change the transport properties effectively to meet various separation needs. It is expected that additional design modifications made by exploiting the chemistry versatility of the triptycene moiety and by selectively adding other components may improve these membranes to break the gas permeability-selectivity trade-off barrier. This journal is the Partner Organisations 2014.
- Wiegand, Jennifer R.,Smith, Zachary P.,Liu, Qiang,Patterson, Christopher T.,Freeman, Benny D.,Guo, Ruilan
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p. 13309 - 13320
(2014/08/18)
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- Synthesis of highly sulfonated poly(arylene ether sulfone)s with sulfonated triptycene pendants for proton exchange membranes
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A series of poly(aryl ether sulfone)s containing triptycene groups PES-x-TPD (x refers to molar percentage of TPD) were firstly synthesized through nucleophilic aromatic substitution polycondensation by using 2,5-triptycenediol (TPD), bis(4-hydroxyphenyl) sulfone (BHPS) and 4,4′-difluorodiphenyl sulfone (DFDPS). The sulfonation of copolymers was conducted at room temperature by using a mild sulfonating reagent (98% H2SO4), and the degree of sulfonation was readily and accurately controlled by adjusting the ratio of TPD and BHPS. The structures of PES-x-TPD and SPES-x-TPD were characterized by IR, 1H NMR and 13C NMR spectra. These ionomers generally showed high thermal stability and mechanical strength at low humidity regardless of high IEC value. Meanwhile, it is noteworthy that these novel SPES-x-TPD membranes with high IEC value achieved high proton conductivity in a wide range of humidity at 80 °C. For example, SPES-60-TPD with the highest IEC value 2.86 mmol/g displays the conductivity of 2.5 × 10 -1 S/cm which is much higher than that of the perfluorinated Nafion membrane (1.1 × 10-1 S/cm) at 80 °C and 94% RH. At 80 °C and 34% RH, SPES-60-TPD displays the conductivity of 4.5 × 10 -3 S/cm which is also higher than that of the Nafion membrane (3.0 × 10-3 S/cm). Microscopic analyses revealed that well-dened phase separated structures and uniform ionic pathway was formed for SPES-45-TPD membrane with the IEC of 2.29 mmol/g. Moreover, a H2/O2 fuel cell using the SPES-55-TPD (IEC = 2.68 mmol/g) also showed better performance than that of Nafion 117 at 40 °C and 30% RH.
- Gong, Feixiang,Mao, Hongchao,Zhang, Yuwei,Zhang, Suobo,Xing, Wei
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experimental part
p. 1738 - 1747
(2012/03/12)
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- Melt-phase synthesis and properties of triptycene-containing copolyesters
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A new triptycene diol (TD), triptycene-1,4-hydroquinone-bis(2-hydroxyethyl) ether, was synthesized and was used to prepare a series of copolyesters with dimethyl 1,4-cyclohexanedicarboxylate (1,4-DMCD) by melt polycondensation. Straight chain aliphatic spacers, including ethylene glycol (EG), 1,4-butanediol (BD), and 1,6-hexanediol (HD), were used as codiols with TD to explore the effects of straight chain flexible spacers on copolyester properties. A concomitant series of non-triptycene copolyesters based on hydroquinone bis(2-hydroxyethyl) ether (HBE), bis[4-(2-hydroxyethoxy)phenyl] sulfone (BHPS), 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane (BHPC), or 1,1-bis(2- hydroxyethoxy)phenyl-3,3,5-trimethylcyclohexane (BHPT) were prepared for comparison. The results demonstrated that the triptycene-containing polyesters in this study have higher thermal stability and higher glass transition temperatures (Tg's) than the corresponding non-triptycene analogues. For triptycene-containing copolyesters, the mechanical properties were found to be dependent on the types and compositions of comonomer diols. A 1,4-butanediol-based triptycene copolyester was observed to have a significant increase in Tg and modulus while maintaining high elongation at ambient temperature (23 °C). However, all the studied 1,4-butanediol-based copolyesters were brittle and had comparable modulus values at low temperatures (-25 or -40 °C).
- Liu, Yanchun,Turner, S. Richard,Wilkes, Garth
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scheme or table
p. 4049 - 4056
(2012/05/04)
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- Synthesis and properties of novel triptycene-based polyimides
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Two new triptycene-containing bis(ether amine)s, 1,4-bis(4-aminophenoxy) triptycene (4) and 1,4-bis(4-amino-2-trifluoromethylphenoxy)triptycene (6), were synthesized, respectively, from the nucleophilic chloro-displacement reactions of p-chloronitrobenzene and 2-chloro-5-nitrobenzotrifluoride with 1,4-dihydroxytriptycene in the presence of potassium carbonate, followed by palladium-catalyzed hydrazine reduction of the dinitro intermediates. The bis(ether amine)s were polymerized with six commercially available aromatic tetracarboxylic dianhydrides to obtain two series of novel triptycene-based polyimides 8a-f and 9a-f by using a conventional two-step synthetic method via thermal and chemical imidizations. All the resulting polyimides exhibited high enough molecular weights to permit the casting of flexible and strong films with good mechanical properties. Incorporation of trifluoromethyl groups in the polyimide backbones improves their solubility and decreases their dielectric constants. The fluorinated polyimides 9d and 9f derived from diamine 6 with 4,4′-oxydiphthalic anhydride and 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), respectively, could afford almost colorless thin films.
- Hsiao, Sheng-Huei,Wang, Hui-Min,Chen, Wen-Jeng,Lee, Tzong-Ming,Leu, Chyi-Ming
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p. 3109 - 3120
(2012/05/05)
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- New Reduction Method of α-Diketones, Oxo amides, and Quinones with Zn-EtOH in the Presence of a Salt
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The reagent, Zn-Salt-EtOH effectively reduces α-diketones, oxo amides, and quinones to hydroxy ketones, hydroxy amides, and hydroquinones, respectively.
- Toda, Fumio,Tanaka, Koichi,Tange, Hiroshi
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p. 1555 - 1556
(2007/10/02)
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