2,5‐Bis(4‐aminophenyl)‐3,4‐diphenylthiophene, a polyimide‐forming monomer, was prepared in three steps starting from benzyl chloride and sulfur. Novel polyimides were synthesized from the diamine and pyromellitic dianhydride or 3,3′, 4,4′‐benzophenonetetracarboxylic dianhydride (BTDA). Polymerization was carried out either by the usual two‐step procedure that included ring‐opening polyaddition giving polyamic acids, followed by cyclodehydration to polyimides, or by the direct one‐pot procedure involving cyclodehydration in situ. The polyimide derived from the diamine and BTDA, especially that prepared by the one‐pot procedure in m‐cresol containing isoquinoline, is soluble in various organic solvents and gave a yellow, transparent, tough, and flexible film. Solubility of this polyimide varied by the preparative method and by the copolymerization with bis(4‐aminophenyl) ether. All the polyimides are highly thermally stable and exhibited no appreciable decomposition up to 450°C in air and nitrogen atmospheres.

Wholly aromatic polyamid&mides are well known as high-temperature plastics with good solubility in organic so1vents.14 Recently, we have synthesized soluble and highly thermally stable p01yimides.Q polyazoznethines,10 and poiyamidesl' from a highly phenylated diamine, 2 ,~b~~o p h e n y l ) -3,~phenylthiophene. This article constitutes the fourth in this series dealing with a synthesis of novel aromatic polyamidedmides by the polymerization of the tetraphenylthiophenediamine with 4-chloroformylphthalic anhydride. Materiala2,5Bia(4-aminophenyl) -3,4diphenyIthiophene CrPTDA) waa synthesized according to the method reported previousiy? Bid4aminophenyl) ether (ODAf waa purified by m a y h l h a ' tion from tetrahydrofuran. ~o r o f o~y~p h~c anhydride (CPA) was prepared by the reaction of trimeiIitic anhydride and thionyl chloride, followed by purification by vacuum distillation.Solvents such aa N,N-dimethylacetamide (DMAc) were purified by distillation. Polyamide-ImideIIa from TPTDA and CPA: In a threenecked flask. a solution of 2.090 g (5.000 mmol) of TPTDA and 0.51 g (5 mmol) of triethylamine in 18.3 mL of DMAc was cooled in an ice-water bath. To this solution, 1.0 53 g (5.000 mmol) of solid CPA was added ail at once. The solution waa stimed at mom temperature for 3 h under nitrogen. The VLScoua solution was diluted with 10 mL of DMAc and poured into 500 mL of methanol. The precipitated yellow flake was collected, washed thoroughly with methanol, and dried at lOm: in wrcuo. The yield of polyamide-amic acid Ia waa 2.96 g (98%). The inherent viscosity of the polymer in DMAc waa 0.44 dL/g. measured at a concentration of 0.5 g/dL at 3oy;'. A f~ of the polyamide-amic acid was cast from the DMAc solution, and heated successively at 15OT for 30 min, 2ooy: for 30 min, and then 26oT: for 1 h under nitrogen atmmpizem. The infrared fIR) spectnun ( f h l of polysmide-hide IIa thus prepared exhibited absorptions at 1780 and 1715 cm-1 h i d e C=O), and 1675 cm-L (amide C=O). AN& Wcd for @&H&,Oa MeasurementsI R spectra were recorded on a Hitachi EPCS spectrophotomebr. Differential thermal analysis (DTA), thermogravimetry (XI), and thermomechanical analyaie ("MA) were performed with Shimndar thermal analyzers DTA-3OM, TGA30M, and TMA30M. respectively. Wideangle x-ray diffraction patterns were obtained for film specimens on a Rigakudenki XC x-ray diffhction apparatus with nickel-fatered Cuka radiation (35 kV, 20 mA). Journal of Polymer IIIn the fvst step, the p o l p e r k t i o n of CPA with the diamines waa carried out in D W at room temperature giving polydde-adc acids I. The d t a of the synthesis are sd in Table I. These polymers were obtained in almoclt quantibtive yielda with inherent viecadtie* of 0.44 -0.51 dL/g, which imply the formation of moderate molecular weight polymem Filma of polymers In-Ic were cast from the DMAc eolutiona In the second step, the cyclodehydration of polyamidegmic acicb I to give polyamide4m.idm II was performed in the form of film by Buec8BBivB heating b 26oy: under nitrogen atmotsphere. The...

New soluble aromatic polyamides with inherent viscosities of 1.0–1.7 dL/g were prepared by the low temperature solution polycondensation of 2,5‐bis(4‐aminophenyl)—3,4‐diphenylthiophene, bis(4‐aminophenyl) ether, and aromatic diacid chlorides in N,N‐dimethylacetamide. The polyamides and copolyamides are generally soluble in amide‐type solvents. They have glass transition temperatures in the range of 280–325°C and showed no weight loss below 390°C on thermogravimetry curves in both air and nitrogen atmospheres.

The preparation of nanostructured hierarchical MnxNi1-xCo2O4 metal oxides as efficient supercapacitors of different structures and configurations especially for the miniaturized electronics is still a challenge. In this context, we report template free facile hydrothermal synthesis of hierarchical nanostructured MnxNi1-xCo2O4 with excellent supercapacitive performance. Significantly, the morphology of pure MnCo2O4 transformed from 3D microcubes to 1D nanowires with incorporation of Ni. The electrochemical study shows highest specific capacity i.e. 734 C/g for Mn0.4Ni0.6Co2O4 with high cycling stability of 89.2 % which is much higher than pristine MnCo2O4 and NiCo2O4. Later, asymmetric capacitor has been fabricated successfully using Mn0.4Ni0.6Co2O4 nanowires as positive electrode and activated carbon (AC) as negative electrode in a KOH aqueous electrolyte. An asymmetric cell could be cycled reversibly in the high-voltage range of 0 to 1.5 V and displays intriguing performances with a specific capacitance of 112.8 F/g (6.87 F/cm3) and high energy density of 35.2 Wh/kg (2.1 mWh/cm3). Importantly, this asymmetric capacitor device exhibits an excellent long cycle life along with 83.2 % specific capacitance retained after 2000 cycles.

A series of aromatic polyamides containing an s‐triazine ring with thiophenoxy linkages was synthesized from two new diacids, namely 2,4‐bis‐(4‐carboxyphenoxy)‐6‐thiophenoxy‐s‐triazine and 2,4‐bis‐(3‐carboxyphenoxy)‐6‐thiophenoxy‐s‐triazine, and commercially available aromatic diamines by using Yamazaki's phosphorylation reaction. The polyamides were obtained in good yields and were characterized by solubility tests, viscosity measurements, FTIR, 1H and 13C NMR spectroscopy, X‐ray diffraction studies and thermogravimetric analysis. The polyamides were found to have inherent viscosities in the range of 0.35 to 0.56 dl g−1 in N,N‐dimethylacetamide (DMAc) at 30 ± 0.1 °C. All the polyamides were readily soluble in solvents such as DMAc, N‐methyl‐2‐pyrrolidone (NMP), N,N‐dimethylformamide (DMF) and m‐cresol. Thermogravimetric analysis of the polyamides indicated no weight loss below 345 °C under a nitrogen atmosphere. Copyright © 2004 Society of Chemical Industry