Morphological study of the organization behavior of rod-coil copolymers and their blends in thin solid films

A detailed study of the self-assembly ability of triblock coil-rod-coil copolymers containing a rigid di(styryl)-anthracene segment covalently linked to oxadiazole-based blocks and their binary blends with oxadiazole-based homopolymers is presented here. The self-organized microdomains seem to pack into a fascinating ordered hexagonal structure obtained at a critical concentration without any significant influence of the sample preparation method, based on evidence obtained by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and fluorescence microscopy studies. The compatibilization efficiency of these coil-rod-coil copolymers in polymer blends composed of an electron-accepting polyoxadiazole and a luminescent polyanthracene-based pair was studied by atomic force microscopy (AFM). The common feature of all observed morphologies is the compatibilizing function of the rod-coil molecule, which intercalates between the incompatible domains to prevent the formation of well-defined phase separated nanostructured surfaces.     

Blends of Aromatic Polyethers Bearing Polar Pyridine Units and Their Evaluation as High Temperature Polymer Electrolytes

Aromatic polyethers containing polar pyridine units in the main chain have been synthesized using different difluoride monomers. Copolymers of 2,5-(4′,4″dihydroxy biphenyl)-pyridine and 3,3′,5,5′-tetramethyl-[1,1′-biphenyl]-4,4′-diol with bis(4-fluorophenyl) sulfone or phenyl phosphine oxide difluoride or decafluorobiphenyl (PTMPySF, PTMPyPO, PTMPyDF) were synthesized. These polymeric structures despite their common structural characteristics, showed totally different behavior in terms of solubility and acid doping ability. Blends of these copolymers have been prepared in order to be evaluated in terms of fuel cell relevant parameters like acid doping ability and conductivity. In most cases flexible membranes were obtained by solution casting. The acid doping ability was controlled based on the blend constituents and composition. The doped membranes exhibited high conductivity values, in the range of 10⁻³ S/cm at room temperature which is increased at 2.5 × 10⁻² S/cm at temperatures up to 180 °C.     

Synthesis of alternating polystyrene/poly(ethyleneoxide) branched polymacromonomers

Newly designed PS/PEO alternating branched polymacromonomers have been obtained by polycondensation of alpha-dicarboxy-functionalized polystyrene and alpha-dihydroxy-functionalized polyethyleneoxide. 4-[3,5-Bis(methoxycarbonyl)phenoxymethyl]benzyl bromide was used as atom-transfer radical polymerization (ATRP) initiator for the synthesis of alpha-dicarboxy functionalized polystyrenes. These macromonomers possess low polydispersities and molecular weights in the range of 7000 to 100,000, as proved by gel permeation chromatography (GPC) and 1H NMR. Alpha-dihydroxy functionalized polyethyleneoxide (PEO) was synthesized by treatment of monofunctionalized PEO with 3,5-bis(benzyloxy)benzoyl chloride. Polycondensation of the alpha-dicarboxy PS with the alpha-dihydroxy PEO in solution or in bulk resulted in alternating PS/PEO polymacromonomers, which were effectively purified from the unreacted macromonomers and characterized by using 1H NMR, GPC, thermal analysis, and optical microscopy. Light-scattering measurements in organic solvents like THF or dioxane have shown that these polymacromonomers form stable micelles.     

Side chain crosslinking of aromatic polyethers for high temperature polymer electrolyte membrane fuel cell applications

Novel aromatic polymers bearing polar pyridine units in the main chain and side chain crosslinkable hydroxyl and propargyl groups have been successfully synthesized. The polymers have been investigated in terms of their critical properties related to their application in high temperature polymer electrolyte membrane fuel cells, such as doping ability, mechanical properties, and thermal stability. Crosslinked membranes were prepared by direct crosslinking of hydroxyl side chain groups with decafluorobiphenyl used for the first time as a crosslinking agent. However, further functionalization of hydroxyl groups to the propargyl derivative has also led to crosslinked polymers after thermal curing. Both types of crosslinked membranes exhibited higher glass transition temperatures as well as lower doping levels when doped in phosphoric acid compared with the non crosslinked analogs, confirming the formation of a successfully crosslinked network. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Blends of Sulfonated Polysulfone and Poly(ethylene oxide)-Grafted-Polyethersulfone as Proton Exchange Membranes for Fuel Cell Applications

Blends composed of sulfonated polysulfone (SPSF) and poly(ethylene oxide)-grafted-polyethersulfone (PEO-g-PES) in different compositions have been prepared and studied in terms of fuel cell relevant parameters like thermal behaviour, water uptake and ionic conductivity. Moreover, spectroscopic characterization (FT-IR) has also been conducted in order to elucidate their miscibility and to investigate the influence of polymer blending on the crystallinity level of the individual components. These blends exhibit very good mechanical properties, a very high water uptake and a high ionic conductivity (4 × 10⁻³ S/cm) at ambient temperatures and they are amorphous, a property that facilitates their use as polymer electrolytes in fuel cells.     

Novel Polymer Electrolyte Membrane,Based on Pyridine Containing Poly(ether sulfone), for Application in High‐Temperature Fuel Cells

Summary: Novel poly(aryl ether sulfone) copolymers containing 2,5‐biphenylpyridine and tetramethyl biphenyl moieties were synthesized by polycondensation of 4‐fluorophenyl sulfone with 2,5‐(4′,4″ dihydroxy biphenyl)pyridine and tetramethyl biphenyl diol. Copolymers with different molecular weights and different monomer compositions were obtained. These copolymers exhibit excellent film‐forming properties, mechanical integrity, and high modulus up to 250 °C, high glass transition temperatures (above 280 °C) as well as high thermal stability up to 400 °C. In addition to the above properties required for PEMFC application, this novel material shows high oxidative stability and acid doping ability, enabling proton conductivity in the range of 10⁻² S · cm⁻¹ above 130 °C.

Synthesis of copolymers with high acid uptake and ionic conductivity.     

Synthesis and properties of amorphous blue‐light‐emitting polymers with high glass‐transition temperatures

A series of soluble poly(arylene ether)s containing the phenylphosphine oxide moiety were synthesized by the polymerization of substituted oligophenylene diols with bis(fluorophenyl)phenylphosphine oxide. These amorphous polyethers had well‐defined structures and showed blue photoluminescence combined with good thermal stability, especially when phenyl or ethoxy side groups were used. The glass‐transition temperatures increased when the size of the oligophenylene segment increased from three to five rings or when the length of the alkoxy substituents decreased. Polymers with glass‐transition temperatures up to 270 °C were obtained. The absorption and photoluminescent spectra shifted to longer wavelengths with an increase in the oligophenylene block. A redshift was also observed on photoluminescent spectra in the transition from solution to the solid state. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3168–3179, 2001