New polymer syntheses. XC. A–B–A triblock copolymers with hyperbranched polyester A-blocks

Telechelic oligo(ether–ketone)s containing two trimethylsiloxy end groups and one methyl group per repeating unit were prepared by polycondensation of 4-fluoro-2′-methyl-4′-(trimethylsiloxy)benzophenone. The telechelic character was achieved by cocondensation of a small amount of silylated bisphenol-P. The end groups of the silylated oligo(ether–ketone)s were acetylated by means of acetyl chloride. On the basis of ¹H-NMR end group analyses two samples of α,ω-bis(acetoxy) oligo(ether–ketone)s with DP = 14 and DP ∼ 28 were obtained. These oligo(ether-ketone)s and a 70 or 140 fold molar amount of silylated 3,5-bis(acetoxy)benzoic acid were polycondensed at 270°C in bulk. The resulting A–B–A triblock copolymers were fractionated by dissolution in tetrahydrofuran. In three out of four experiments a small fraction of precipitated material rich in oligo(ether–ketone) was isolated. The purified triblock copolymers were characterized by inherent viscosities and NMR spectra. For those samples containing the long oligo(ether–ketone) block a low degree of crystallinity was observed after annealing. Four additional polycondensations were conducted with an initial reaction temperature of 290°C. In this way a completely soluble and amorphous triblock copolymer was obtained. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 31–38, 1998     

Multicyclic Polythioesters Derived from Pentaerythritol Tetra(mercaptoacetate)

Dry pentaerythritol tetra(mercaptoacetate), PETMA, was polycondensed with double molar amounts of phthaloyl chloride, isophthaloyl chloride, tetraphthaloyl chloride, adipoyl, suberoyl, sebacoyl and 1,10‐decanedioyl chloride. Pyridine served as HCl‐acceptor and catalyst. The concentration of PETMA was varied between 0.1 mol/L and 0.0125 mol/L. With the aromatic dicarboxylic acid, dichlorides gelation occurred in all experiments. With aliphatic dicarboxylic acid dichlorides (ADADs), soluble multicyclic polythioesters were obtained at concentrations of 0.025 or 0.0125 mol/L. These multicyclic polythioesters were characterized by viscosity measurements,¹H‐NMR spectroscopy and MALDI‐TOF mass spectrometry. A few experiments with pentaerythritol tetra(mercaptopropionate) showed a lower cyclization tendency relative to PETMA. Polycondensations of PETMA with α,ω‐dibromoalkanes or tri(ethylene glycol) bistosylate all ended with gelation.     

Copoly(arylene ether nitrile) and copoly(arylene ether sulfone) ionomers with pendant sulfobenzoyl groups for proton conducting fuel cell membranes

Three series of fully aromatic ionomers with naphthalene moieties and pendant sulfobenzoyl side chains were prepared via K₂CO₃ mediated nucleophilic aromatic substitution reactions. The first series consisted of poly(arylene ether)s prepared by polycondensations of 2,6‐difluoro‐2′‐sulfobenzophenone (DFSBP) and 2,6‐dihydroxynaphthalene or 2,7‐dihydroxynaphthalene (2,7‐DHN). In the second series, copoly(arylene ether nitrile)s with different ion‐exchange capacities (IECs) were prepared by polycondensations of DFSBP, 2,6‐difluorobenzonitrile (DFBN), and 2,7‐DHN. In the third series, bis(4‐fluorophenyl)sulfone was used instead of DFBN to prepare copoly(arylene ether sulfone)s. Thus, all the ionomers had sulfonic acid units placed in stable positions close to the electron withdrawing ketone link of the side chains. Mechanically strong proton‐exchange membranes with IECs between 1.1 and 2.3 meq g⁻¹ were cast from dimethylsulfoxide solutions. High thermal stability was indicted by high degradation temperatures between 266 and 287 °C (1 °C min⁻¹ under air) and high glass transition temperatures between 245 and 306 °C, depending on the IEC. The copolymer membranes reached proton conductivities of 0.3 S cm⁻¹ under fully humidified conditions. At IECs above ∼1.6 meq g⁻¹, the copolymer membranes reached higher proton conductivities than Nafion^® in the range between −20 and 120 °C. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011