Fluorinated,crosslinkable terpolymers based on vinylidene fluoride and bearing sulfonic acid side groups for fuel‐cell membranes

The radical terpolymerization of 8‐bromo‐1H,1H,2H‐perfluorooct‐1‐ene with vinylidene fluoride (VDF) and perfluoro(4‐methyl‐3,6‐dioxaoct‐7‐ene) sulfonyl fluoride is presented. Changing the feed compositions of these three fluorinated comonomers enabled us to obtain different random‐type poly[vinylidene fluoride‐ter‐perfluoro(4‐methyl‐3,6‐dioxaoct‐7‐ene) sulfonyl fluoride‐ter‐8‐bromo‐1H,1H,2H‐perfluorooct‐1‐ene] terpolymers containing various sulfonyl fluoride and brominated side groups. Yields higher than 70% were reached in all cases. The hydrolysis of the sulfonyl fluoride group into the ? SO₃Li function in the presence of lithium carbonate was quantitatively achieved without the content of VDF being affected, and so dehydrofluorination of the VDF base unit was avoided. These original terpolymers were then crosslinked via dangling bromine atoms in the presence of a peroxide/triallyl isocyanurate system, which produced films insoluble in organic solvents such as acetone and dimethylformamide (which totally dissolved uncured terpolymers). The acidification of ? SO₃Li into the ? SO₃H function enabled protonic membranes to be obtained. The thermal stabilities of the crosslinked materials were higher than those of the uncured terpolymers, and their electrochemical performances were investigated. According to the contents of the sulfonic acid side functions, the ion‐exchange capacities ranged from 0.6 to 1.5 mequiv of H⁺/g, whereas the water uptake and conductivities ranged from 5–26% (±11%) and from 0.5 to 6.0 mS/cm, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4566–4578, 2006     

Colossal magnetoresistance manganites: A new approach

Manganites of the LA_1−x Ca _x MnO₃ family show a variety of new and poorly understood electronic, magnetic and structural effects. Here we outline a new approach recently proposed by us, where we argue that due to strong Jahn-Teller (JT) coupling with phonons the twofold degeneratee _g states at the Mn sites dynamically reorganize themselves into localised, JT polaronsl with exponentially small inter-site hopping, and band-like, nonpolaronic statesb, leading to anew 2-band model for manganites which includes strong Coulomb and Hund’s couplings. We also discuss some results from a dynamical mean-field theory treatment of the model which explains quantitatively a wide variety of experimental results, including insulator-metal transitions and CMR, in terms of the influence of physical conditions on the relative energies and occupation of thel andb states. We argue that this microscopic coexistence of the two types of electronic states, and their relative occupation and spatial correlation is the key to manganite physics. Dedicated to Professor C N R Rao on his 70th birthday     

Oxygen inhibition in thiol–acrylate photopolymerizations

The overall effects of oxygen on thiol–acrylate photopolymerizations were characterized. Specially, the choice of thiol monomer chemistry, functionality, and concentration on the extent of oxygen inhibition were considered. As thiol concentration was increased, the degree of oxygen inhibition was greatly reduced because of chain transfer from the peroxy radical to the thiol. When comparing the copolymerization of 1,6‐hexanediol diacrylate with the alkane‐based thiol (1,6‐hexane dithiol) to the copolymerization with the propionate thiol (glycol dimercaptopropionate), it was found that the propionate system was much more reactive and polymerized to a greater extent in the presence of oxygen. In addition, the functionality was considered where the glycol dimercaptopropionate was compared to a tetrafunctional propionate of similar chemistry (pentaerythritol tetrakis(mercaptopropionate)). Given the same thiol concentration, the higher functionality thiol imparted a faster polymerization rate, due to the increased polymer system viscosity, which limited oxygen diffusion and decreased the extent of overall oxygen inhibition. Thus, preliminary insight is provided into how thiol monomer choice affects the extent of oxygen inhibition in thiol–acrylate photopolymerization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2007–2014, 2006     

Photoinitiated polymerization in bicontinuous microemulsions: Fluorescence monitoring

The photopolymerization of bicontinuous microemulsions was simultaneously monitored with differential scanning calorimetry and fluorescence. The kinetics and mechanism of the reaction were studied throughout the entire photopolymerization reaction. The role played by the surfactant in the kinetics and morphology was studied. The nature of the surfactant changed the autoacceleration process and final conversion. The behavior was explained as a result of the differences in the interfacial properties. Anionic cetyltrimethylammonium bromide (CTAB) gave rise to a more flexible interfacial film than anionic sodium dodecyl sulfate (SDS), resulting in competition between the intramolecular and intermolecular reactions in the former systems. As cyclization did not contribute to the increase in the degree of crosslinking, SDS photopolymerization gave solids with a more rigid microstructure. Fluorescence methodology was applied to monitor bicontinuous microemulsion polymerization and to reveal the microstructure and morphology development during photopolymerization. The microemulsion composition was designed to prepare nanoporous, crosslinked materials. Even though the nanostructure of the precursor microemulsions was not retained because of phase separation during polymerization, mesoporous solids were obtained. Their morphologies depended on the nature of the surfactant, and membranes with open cells were successfully prepared with CTAB, whereas more complex morphologies resulted with SDS. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5291–5303, 2006     

Stereocontrol of diene polymers by topochemical polymerization of substituted benzyl muconates and their crystallization properties

We report the stereocontrol of diene polymers by the topochemical polymerization of alkoxy-substituted benzyl muconates in the solid state. A monomer stacking structure is controlled by the weak intermolecular interactions in the monomer crystals, depending on the structure and position of the alkoxy-substituent. The translational and alternating types of molecular stacking structures in a column provide diisotactic and disyndiotactic polymers, respectively, by the solid-state polymerization under UV and γ-ray irradiation. On the other hand, the meso and racemo structures of the resulting polymers are determined by the molecular symmetry of the used muconate monomers. The various substituted benzyl ester polymers are transformed into the same ethyl ester polymers with the four types of tacticities. The structure and crystallization behavior of the substituted benzyl ester polymers as well as the ethyl ester polymers have been revealed in detail. We clarify the effects of the tacticity on the crystallization property of the stereoregular polymuconates. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4952–4965, 2006     

Facile syntheses of surface-functionalized micelles and shell cross-linked nanoparticles

Block copolymer micelles and shell cross-linked nanoparticles (SCKs) presenting Click-reactive functional groups on their surfaces were prepared using two separate synthetic strategies, each employing functionalized initiators for the controlled radical polymerization of acrylate and styrenic monomers to afford amphiphilic block copolymers bearing an alkynyl or azido group at the α-terminus. The first route for the synthesis of the azide-functionalized nanostructures was achieved via sequential nitroxide-mediated radical polymerization (NMP) of tert-butyl acrylate and styrene, originating from a benzylic chloride-functionalized initiator, followed by deprotection of the acrylic acids, supramolecular assembly of the block copolymer in water and conversion of the benzylic chloride to a benzylic azide. In contrast, the second strategy utilized an alkynyl-functionalized reversible addition fragmentation transfer (RAFT) agent directly for the RAFT-based sequential polymerization of tetrahydropyran acrylate and styrene, followed by selective cleavage of the tetrahydropyran esters to give the α-alkynyl-functionalized block copolymers. These Click-functionalized polymers, with the functionality located at the hydrophilic polymer termini, were then self-assembled using a mixed-micelle methodology to afford surface-functionalized “Clickable” micelles in aqueous solutions. The optimum degree of incorporation of the Click-functionalized polymers was investigated and determined to be ca. 25%, which allowed for the synthesis of well-defined surface-functionalized nanoparticles after cross-linking selectively throughout the shell layer using established amidation chemistry. Functionalization of the chain ends was shown to be an efficient process under standard Click conditions and the resulting functional groups revealed a more “solution-like” environment when compared to the functional group randomly inserted into the hydrophilic shell layer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5203–5217, 2006     

Synthesis and antibacterial activities of water‐soluble methacrylate polymers containing quaternary ammonium compounds

New water‐soluble methacrylate polymers with pendant quaternary ammonium (QA) groups were synthesized and used as antibacterial materials. The polymers with pendant QA groups were obtained by the reaction of the alkyl halide groups of a previously synthesized functional methacrylate homopolymer with various tertiary alkyl amines containing 12‐, 14‐, or 16‐carbon alkyl chains. The structures of the functional polymer and the polymers with QA groups were confirmed with Fourier transform infrared and ¹H and ¹³C NMR. The degree of conversion of alkyl halides to QA sites in each polymer was determined by ¹H NMR to be over 90% in all cases. The number‐average molecular weight and polydispersity of the functional polymer were determined by size exclusion chromatography to be 32,500 g/mol and 2.25, respectively. All polymers were thermally stable up to 180 °C according to thermogravimetric analysis. The antibacterial activities of the polymers with pendant QA groups against Staphylococcus aureus and Escherichia coli were determined with broth‐dilution and spread‐plate methods. All the polymers showed excellent antibacterial activities in the range of 32–256 μg/mL. The antibacterial activity against S. aureus increased with an increase in the alkyl chain length for the ammonium groups, whereas the antibacterial activity against E. coli decreased with increasing alkyl chain length. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5965–5973, 2006     

Synthesis of new thermosetting poly(2,6‐dimethyl‐1,4‐phenylene oxide)s containing epoxide pendant groups

A new class of thermosetting poly(2,6‐dimethyl‐1,4‐phenylene oxide)s containing pendant epoxide groups were synthesized and characterized. These new epoxy polymers were prepared through the bromination of poly(2,6‐dimethyl‐1,4‐phenylene oxide) in halogenated aromatic hydrocarbons followed by a Wittig reaction to yield vinyl‐substituted polymer derivatives. The treatment of the vinyl‐substituted polymers with m‐chloroperbenzoic acid led to the formation of epoxidized poly(2,6‐dimethyl‐1,4‐phenylene oxide) with variable pendant ratios, and the structures and properties were studied with nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and gel permeation chromatography. The ratios of pendant functional groups were tailored for the polymer properties, and the results showed that the glass‐transition temperatures increased as the benzylic protons were replaced by bromo‐, vinyl‐, or epoxide‐functional groups, whereas the thermal stability decreased in comparison with the original polymer. Within a molar fraction of 20–50%, the degree of functionalization had little effect on the glass‐transition temperature; however, it correlated inversely with the thermal stability of each functionalized polymer. The thermal curing behavior of the epoxide‐functionalized polymer was enhanced by the increment of the pendant functionality, which resulted in a significant increase in the glass‐transition temperature as well as the thermal stability after the curing reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5875–5886, 2006     

Thermochemically induced binding of methyl orange to polycations containing primary amine groups

The thermochemical transformation of electrostatically formed complexes of methyl orange (MO) with polycations containing primary amine groups such as ammonium salts afforded new polymers with a high concentration of covalently bound 4‐N,N‐dimethylaminoazobenzene groups in the side chain. Poly(allylamine hydrochloride) and poly(β‐aminoethylene acrylamide hydrochloride) were employed as support polycations for MO. The transformation of sulfonate–ammonium ion pairs into sulfonamide bonds, via heating at an elevated temperature, was supported by the polymer properties before and after the thermal treatment. The polymer structure changes were monitored with elemental analysis, Fourier transform infrared, ¹H NMR, and ultraviolet–visible absorption spectroscopy, and thermogravimetric analysis. The spacer length between the backbone and azobenzene structures used as side chains strongly influenced the polymer properties before and after the heat‐induced reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5898–5908, 2006