Synthesis of furan dimer‐based polyamides with a high melting point

Polyamide composed of furan dimer, which is prepared from biomass‐derived organic molecule 2‐furfural, is synthesized. The reaction of 2,2′‐furan dimer 5,5′‐dicarbonyl chloride with several 1,ω‐diamines was carried out with a solution or interfacial polycondensation leading to the corresponding polyamide. Measurement of the melting point was performed resulting to exhibit a higher temperature compared with the related polyamide bearing a single furan ring composed of furan‐2,5‐dicarboxylic acid (FDCA). Thermal analyses (TG–DTA) also indicated higher temperatures of decomposition than those of FDCA‐derived polyamide. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1516–1519     

A highly rigid diamine monomer derived from naturally occurring myo‐inositol and its use for polyamide synthesis

A rigid diamine was synthesized from myo‐inositol, a naturally occurring cyclic hexaol, and used as a monomer to synthesize polyamides. myo‐Inositol was treated with 1,1‐dimethoxycyclohexane to yield a bisketal bearing two hydroxyl groups, and from this bisketal, the target diamine was synthesized in three steps: (1) derivation of the diol into the corresponding bistriflate, (2) nucleophilic substitution of the bistriflate with sodium azide yielding a diazide, and (3) reduction of the diazide to the target diamine. The target diamine readily underwent polycondensation with dicarboxylic acid chloride in solution. The resulting polyamides, whose main chain inherited the rigid 5‐6‐5 system from the diamine monomers, have high glass transition temperatures. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3436–3443     

Direct Toner Printing: A Versatile Technology for Easy Fabrication of Flexible Miniaturized Electrodes

We reported here three simple, low cost and easy to accomplish strategies for the fabrication of microelectrodes and other conductive patterns using ordinary office laser‐printers. In this work, toner patterns were directly printed onto the flexible substrate, acting as a mask to create the intended conductive design. To highlight the versatility of such technology, toner‐printed patterns were employed in two diverse ways: one in which the patterned toner had the exact design of the electrode and other employing a reverse toner‐printed pattern. The first one was used for the adaptation of the well‐known printed circuit board (PCB) fabrication technique, but using direct toner printing (DTP) in an already conductive flexible substrate. The second was employed for the two remaining strategies: one based on the deposition of conductive film, followed by lift‐off process; and another based on drop‐casting of a conductive ink into the formed toner cavities, followed by thermal cure. As proof‐of‐concept, all three DTP strategies were used for the fabrication of miniaturized gold electrodes in polyimide substrate, and electrochemical performance of each obtained electrode was evaluated by cyclic voltammetry. Insights about DTP technology, alignment issues, advantages, limitations and resolution of each presented approach were provided. Finally, direct toner printing showed to be a simple, affordable and quite promising technology for the fabrication of low cost point‐of‐care electrochemical devices using flexible platforms.     

Synthesis and properties of hyperbranched poly(ether sulfone)s prepared by self‐polycondensation of novel AB2 monomer

Hyperbranched poly(ether sulfone)s were prepared by the self‐polycondensation of the novel AB₂ monomer, 4‐(3,5‐hydroxyphenoxy)‐4′‐fluorodiphenylsulfone. The high‐molecular‐weight polymers were isolated in good yields. The degree of branching (DB) of the resulting polymers was investigated by the preparation of dendritic and linear model compounds. The DB determined by gated decoupling ¹³C NMR measurements was in the range 0.17–0.41 and was dependent on the base used for the self‐polycondensation. It was found that cesium fluoride was an effective base to form the polymer having the DB of 0.41. The resulting hyperbranched poly(ether sulfone)s showed good solubility in organic solvents. The solubility and the glass transition temperature of the polymers were influenced by the terminal functional groups. The unique thermal crosslinking phenomenon was observed during the DSC measurements of the hydroxyl‐terminated hyperbranched poly(ether sulfone) under air condition. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Twin liquid crystals and segmented thermotropic polyesters containing azobenzene—effect of spacer length on LC properties

We report systematic studies on a homologous series of twin liquid crystalline (LC) molecules based on phenyl and naphthyl azobenzene ( PnP and NpnNp ) as well as segmented copolyesters based on them. The twin series had the structure azobenzene–oligooxyethylene–azobenzene, where the ethyleneoxy length was varied from 2 to 6 units. The LC properties of the twin series depended on the chemical structure of the azochromophore and also the length of the central oligooxyethylene segment. The PnP series exhibited smectic LC properties for n > three oligooxyethylene units. Conversely, NpnNp series exhibited spherulitic phases only for the shortest member – Np2Np . One non‐LC short spacer twin ( P2P ) and one LC long spacer twin ( P6P ) were incorporated as part of a main chain polyester composed of fully aliphatic segments of sebacate and di or tetraethylene glycol (DEG/TEG) units by melt polycondensation. Non‐LC P2P formed LC polymers even at low (5 mol %) incorporation in DEG‐based copolymers, whereas the LC‐ P6P could do so only at 30 mol % incorporation. The LC properties of the twin molecules as well as copolymers were studied using differential scanning calorimetry, polarized light microscopy (PLM) along with variable temperature wide angle X‐ray diffraction. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Perfluorocyclohexenyl aryl ether polymers via polycondensation of decafluorocyclohexene with bisphenols

A novel class of semifluorinated perfluorocyclohexenyl (PFCH) aryl ether homo/copolymers was successfully synthesized with high yield through the step‐growth polymerization of commercially available bisphenols and decafluorocyclohexene in the presence of a triethylamine base. The synthesized polymers exhibit variable thermal properties depending on the functional spacer group (R). PFCH aryl ether copolymers with random and alternating architectures were also prepared from versatile bis‐perfluorocyclohexenyl aryl ether monomers. The PFCH polymers show high thermal stabilities with a 5% decomposition temperature ranging from 359 to 444 °C in air and nitrogen atmosphere. These semifluorinated PFCH aromatic ether polymers contain intact enchained PFCH olefin moieties, making further reactions such as crosslinking and application specific functionalization possible. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 232–238     

Synthesis and proton conductivity of sulfonated,multi‐phenylated poly(arylene ether)s

A series of sterically‐encumbered, sulfonated, poly(arylene ether) copolymers were synthesized and their proton conductivity examined. The series was prepared by copolymerizing a novel monomer, 2″,3″,5″,6″‐tetraphenyl‐[1,1′:4',1″:4″,1″':4″',1″″‐quinquephenyl]‐4,4″″‐diol, with 4,4'‐difluorobenzophenone and bisphenol A. Subsequent sulfonation and solution casting provided membranes possessing ion exchange capacities of 1.9 to 2.7 mmol/g and excellent mechanical properties (Young's modulus, 0.2–1.2 GPa; tensile strength, 35–70 MPa; elongation at break, 62–231%). Water uptake ranged from 34 to 98 wt% at 80 °C/100% RH. Proton conductivities ranged between 0.24 to 16 mS/cm at 80 °C/60% RH, and 3 to 167 mS/cm at 80 °C/95% RH. TEM analysis of the polymers, in the dehydrated state, revealed isolated spherical aggregates of ions, which presumably coalesce when hydrated to provide highly conductive pathways. The strategy of using highly‐encumbered polymer frameworks for the design of mechanically‐robust and dimensionally‐stable proton conducting membranes is demonstrated. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2579‐2587     

Random Poly(Lactic Acid-co-β-Alanine): Synthesis and Characterizations

A series of random polyesteramides (PEAs) within a range of molar composition from 90/10 to 10/90 were synthesized by a direct melt polycondensation of lactic acid and β-alanine. Their structures were fully characterized by NMR spectroscopy. The resulting copolymers are amorphous; they are thermally stable to temperatures up to 254°C, and present increasing glass transition temperatures at increasing amide content. The copolymers were also characterized by FTIR and viscosimetry measurements.