Poly(arylene sulfides) with pendant cyano groups as high-temperature laminating resins

Poly(phenylene sulfides) were synthesized from m-benzenedithiol and aromatic dibromides in a basic medium of potassium carbonate in dimethylformamide or dimethylacetamide. The products obtained were slightly off-white with relatively low melting ranges and had inherent viscosities in the 0.2–0.4 dl/g range in hexamethylphosphoric triamide. Similar poly(phenylene sulfides) containing pendant cyano groups along the polymer chains were obtained by the use of 5 mole-% of either 2,4-dichlorobenzonitrile or 3,5-dichlorobenzonitrile. The products were similar to the pure polyphenylene sulfides, except that they showed lower melting ranges and gave insoluble products when heated alone or in the presence of zinc chloride.     

New poly(arylene ether)s with pendant phosphonic acid groups

Soluble brominated poly(arylene ether)s containing mono‐ or dibromotetraphenylphenylene ether and octafluorobiphenylene units were synthesized. The polymers were high molecular weight (weight‐average molecular weight = 115,100–191,300; number‐average molecular weight = 32,300–34,000) and had high glass‐transition temperatures (>279 °C) and decomposition temperatures (>472 °C). The brominated polymers were phosphonated with diethylphosphite by a palladium‐catalyzed reaction. Quantitative phosphonation was possible when 50 mol % of a catalyst based on bromine was used. The diethylphosphonated polymers were dealkylated by a reaction with bromotrimethylsilane in carbon tetrachloride followed by hydrolysis with hydrochloric acid. The polymers with pendant phosphonic acid groups were soluble in polar solvents such as dimethyl sulfoxide and gave flexible and tough films via casting from solution. The polymers were hygroscopic and swelled in water. They did not decompose at temperatures of up to 260 °C under a nitrogen atmosphere. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3770–3779, 2001     

Poly(arylene ether sulfone)s containing pendant sulfonic acid groups as membrane materials for direct methanol fuel cells

A series of poly(arylene ether sulfone)s containing pendant sulfonic acid groups have been prepared by an aromatic substitution polymerization reaction using 4,4-difluorodiphenylsulfone, 6,7-dihydroxy-2-naphthalenesulfonate, and various hydroxyl terminated monomers in the presence of potassium carbonate. The synthesized sulfonated polymers have been characterized by nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, gel permeation chromatography, ion exchange capacity, thermogravimetric analysis, and proton conductivity measurements. With a molecular weight of 50,000–59,000 g/mol and an ion exchange capacity of 1.17 meq./g, these polymers are thermally stable up to 250 °C. They are found to exhibit better performance at 65 and 80 °C in direct methanol fuel cells than Nafion 115 membrane despite lower proton conductivity due to a significantly lower methanol crossover.     

Poly(arylene ether)s with pendant diphenyl phosphoryl groups: Synthesis,characterization, and thermal properties

A series of poly(arylene ether)s, (PAEs), carrying a pendant diphenyl phosphoryl group were prepared via the nucleophilic aromatic substitution (NAS) reactions of 3,5‐difluorotriphenylphosphine oxide, 6 . The difluoro monomer 6 was synthesized via two‐step reaction sequence and subsequently characterized by ¹H, ¹³C, ¹⁹F, and ³¹P NMR spectroscopy, GC/MS, and elemental analysis. The reactivity of the electrophilic sites in 6 , activated by only a diphenylphosphoryl group located in the meta‐position, in 6 was probed via NMR spectroscopy and model reactions and was determined to be sufficient to undergo typical NAS reactions. High molecular weight, amorphous, organic soluble poly(arylene ether)s, bearing a pendant diphenylphosphoryl group, were prepared via the reaction of 6 with a variety of bis‐phenols under typical NAS conditions. The poly(arylene ether)s were characterized for structure via the use of ¹H, ¹³C, and ³¹P NMR spectroscopy while their thermal properties were evaluated using DSC and TGA analysis. The glass transition temperatures (T_g) of the synthesized PAEs ranged from 143 to 175 °C, while their 5% weight loss temperatures ranged from 467 to 510 °C under nitrogen and from 470 to 526 °C in air. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Poly(N-acylethylenimine) copolymers containing pendant pentamethyldisiloxanyl groups. I. Synthesis

10-(Pentamethyl disiloxanyl) decyl oxazoline ( Si ) was synthesized. It was copolymerized with either undecyl ( U ) or nonyl ( N ) oxazolines using methyl 4-nitrobenzenesulfonate as initiator. Two series of random poly(N-acylethylenimine) copolymers, U/Si and N/Si , were synthesized over the whole composition range of Si monomer with a total degree of polymerization of about 100. Narrow molecular weight distributions were obtained. At a monomer to initator ratio of about 1060, the final degree of polymerization was 374 with a polydispersity index of 1.93. This shows the effect of chain transfer in this system.     

Poly(N-acylethylenimine) copolymers containing pendant pentamethyldisiloxanyl groups. II. Thermal behavior and x-ray diffraction study

Two series of random copolymers of 10-(pentamethyl disiloxanyl) decyl oxazoline ( Si ) with undecyl ( U ) (four copolymer compositions) and nonyl ( N ) (eight copolymer compositions) oxazolines over the whole composition range, with a total degree of polymerization of about 100, were studied by DSC and wide angle X-ray diffraction. All the polymers are crystalline. For the N/Si copolymers, the melting points, normalized ΔH and ΔS of fusion are almost constant in a broad range of copolymer composition from 10 to 65 mol % of Si . The rationale for this behavior is that the copolymers crystallize two dimensionally, with the crystalline polymethylene plates separated by the bulky flexible pentamethyl disiloxanyl ( P ) groups. In this range, increasing Si only increases the distance between the plates. With more than 65 mol % Si , the bulky P groups interfere with the packing of the alkyl chains and change the crystallization behavior; the polymers show disordered packing as demonstrated by their X-ray patterns and extremely low ΔH. In the U/Si copolymers, since the undecyl side chain has one more carbon than the decyl group to which the P group is attached, the P groups interfere much more strongly with the packing of the side chains than in the N/Si polymers. The copolymer melting points uniformly decrease as the concentration of Si increases. The plateau on the plot of normalized ΔH versus polymer composition is only from 10 to 50 mol % of Si . The average long spacings of the annealed polymers increase linearly from 24 Å ( N/Si polymers) or 28 Å ( U/Si polymers) to 34.1 Å with the increase of Si up to 50%. With more than 50% Si , the polymers have an identical lamellar thicknesses of 34 Å, within the experimental error. Copolymers with less than 75 mol % of Si can crystallize from hexadecane solutions forming gels down to polymer concentrations of 2-3 wt %. The long spacings of the gels are almost identical with those of the pure crystalline polymers and independent of the polymer/solvent ratios. When hexamethyl disiloxane is added to the solutions, it can intercalate and the resulting crystalline gels have long spacings larger than those found in the absence of siloxane.     

Aromatic polyethers,polysulfones, and polyketones as laminating resins. II

1,3-Bis(p-phenoxybenzenesulfonyl)benzene and 4,4′-bis(p-phenoxybenzenesulfonyl)-diphenyl ether were polymerized with isophthaloyl and terephthaloyl chloride in Friedel-Crafts type polymerizations. These polymers had 5-cyanoisophthaloyl units in the backbone, obtained by using 5-cyanoisophthaloyl chloride as part of the acid chloride monomer. A number of catalysts were screened to effect the trimerization of the pendant nitrile groups in the polymer to the triazines. Model reactions were carried out for each polymer. Physical and thermal properties of the laminates obtained from these polymers are discussed.     

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     

Poly(N-acylethylenimine) copolymers containing pendant pentamethyldisiloxanyl groups. III. Surface properties and abhesion

The surface properties and abhesion of both N/Si and U/Si series of random copolymers were studied by contact angle and peel strength measurements. When these copolymers are coated on clean glass slides, the contact angles of water on the polymer films are over 105° for copolymers with less than 50 mol % of Si , and 98-104° for those with more than 50 mol % of Si. All the polymers have similar critical surface energies, 21 dyn/cm (from hydrocarbon probes) and 20 dyn/cm (from EtOH/H₂O probes), within the experimental error. This demonstrates that the amide groups in the polymer backbones are buried and all the polymers have methyl surfaces. The copolymers with less than 50 mol % Si (for N/Si copolymers) or 20 mol % (for U/Si copolymers) are stable and show good abhesive properties toward Scotch magic tape at or below 50°C. The peel strengths of Scotch magic tape with the copolymer coated slides rise dramatically as the annealing temperatures approach to the melting points of the polymers.     

Aromatic polyethers,polysulfones, and polyketones as laminating resins. V. Polymers containing acetylenic side groups

1,3-Bis(p-phenoxybenzenesulfonyl)benzene and 4,4′-diphenoxydiphenyl sulfone were polymerized with isophthaloyl and terephthaloyl chloride in Friedel-Crafts type polymerizations. These polymers had 2,4-diphenoxyacetophenone in the backbone. The acetyl group was then converted into an acetylene group. They were crosslinked effectively by cyclization of the acetylene groups with a catalyst or by cyclo-addition with bisnitrile oxides.     

Synthesis and properties of new crystalline poly(arylene ether)s containing pendant benzoyl groups

Poly(arylene ether)s ( 3 ) containing pendant benzoyl groups were prepared by the aromatic substitution reaction of 2,5-difluoro-4-benzoylbenzophenone (2) with hydroquinone ( 1a ) and methylhydroquinone ( 1b ) in the presence of potassium carbonate in N,N-dimethylacetamide. The polycondensation proceeded smoothly at 165°C and produced poly(arylene ether)s with inherent viscosities up to 0.8 dL/g. The polymer ( 3b ) derived from methylhydroquinone was quite soluble in common organic solvents and could be processed into uniform films from solutions. On the other hand, the polymer ( 3a ) derived from hydroquinone was only soluble in pentafluorophenol and methanesulfonic acid and had a high crystallinity. These polymers showed 10% weight losses at around 420 and 490°C in nitrogen. Polymer 3b also showed good tensile strength and tensile moduli. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 605–611, 1997     

Poly(arylene ether) ionomers containing sulfofluorenyl groups: Effect of electron-withdrawing groups on the properties

For polymer electrolyte membrane fuel membrane cell (PEMFC) applications, the effect of electron-withdrawing groups on the properties of sulfonated poly(arylene ether) (SPE) ionomer membranes was investigated. A series of poly(arylene ether)s containing fluorenyl groups and electron-withdrawing groups (sulfone, nitrile, or fluorine) was synthesized, which were sulfonated with chlorosulfonic acid using a flow reactor to obtain the title ionomers. The ionomers had high molecular weight (M_n > 77 kDa, M_w > 238 kDa) and gave tough, ductile membranes by solution casting. The ion exchange capacity (IEC) of the membranes ranged from 1.6 to 3.5 mequiv/g as determined by titration. The electron-withdrawing groups did not appear to affect the thermal properties (decomposition temperature higher than 200 °C). The presence of nitrile groups, especially at positions meta to the ether linkages, improved the oxidative stability of the SPE membranes, while it led to a deterioration of the hydrolytic stability. The perfluorinated biphenylene groups were effective in providing high mechanical strength with reasonable dimensional change, probably due to a somewhat decreased water absorbability. The SPE membrane containing sulfone groups showed the highest proton conductivity (10⁻³-10⁻¹ S/cm) at 20-93% RH (relative humidity) and 80 °C. The nitrile-containing SPE membrane showed smaller apparent activation energies for oxygen and hydrogen permeability and is thus considered to be a possible candidate for applications in PEMFCs.     

Poly(p-phenylene ethynylene)s with facially amphiphilic pendant groups: solvatochromism and supramolecular assemblies

Novel functionalized poly(p-phenylene ethynylene)s (PPEs) bearing facially amphiphilic cholic and deoxycholic acid units are synthesized by a Pd-catalyzed Sonogashira cross-coupling reaction. Some interesting properties, particularly their optical and self-assembly characteristics, are unraveled. The PPEs that carry bile acid substituents exhibit remarkable solvatochromism in a wide range of solvent systems, and judicious choice of the solvents can adjust the size and morphology of the formed nanoscale supramolecular aggregates. The incorporation of these naturally occurring building blocks can also impart biocompatibility to the conjugated system and stimulate the growth of living cells.     

Novel electroactive poly(arylene ether sulfone) copolymers containing pendant oligoaniline groups: Synthesis and properties

We present a series of novel poly(arylene ether sulfone) copolymers containing pendant oligoaniline groups. A novel monomer containing oligoaniline, 2,6‐difluorobenzoyl aniline tetramer (DFAT), was synthesized by reaction of 2,6‐difluorobenzoyl chloride and parent aniline tetramer and incorporated into the aforementioned copolymers via direct copolymerization with 4,4′‐dichlorodiphenyl sulfone (DCDPS), and 4,4′‐isopropylidene diphenol (BPA) using N,N′‐dimethylacetamide as solvent. The structures of these copolymers were confirmed by FTIR, ¹H NMR, and GPC. Spectral analysis of the copolymers in different oxidation states was investigated via UV‐visible spectra. The copolymers exhibited outstanding thermal stability and good solubility in various organic solvents. Their electroactivity, explored with cyclic voltammetry, was found to increase as the content of oligoaniline in the polymer increased. The electric and dielectric properties of the copolymers were also studied in detail. The electrochromic performance of the copolymers was investigated by electrochromic photographs and transmittance spectra; the color of the copolymer thin films changes from grey (at 0.0 V), to green (at 0.4 V), to blue (at 0.6 V) and to pearl blue (at 1.0 V) and the maximum transmittance change (ΔT) at 700 nm is 42.6% (90.7% ? 48.1%). © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Low‐dimensional compounds containing cyano groups. XII.)copper(II) perchlorate

The title compound, [Cu(C₂N₃)(C₃H₁₀N₂)₂]ClO₄, is made up of [Cu(tn)₂{N(CN)₂}]⁺ complex cations (tn is 1,3‐diamino­propane) and ClO₄⁻ anions. The Cu^II atom is coordinated by four N atoms of two equatorial tn ligands, with an average distance of 2.041 (7) Å, and one nitrile N atom of the dicyanamide anion in an axial position, at a distance of 2.236 (3) Å, in a manner approaching square‐planar coordination geometry. The complex has C_s symmetry, with the mirror plane lying through the central C atoms of both tn ligands and the dca ligand. The ClO₄⁻ anion might be considered as very weakly coordinated in the opposite axial position [Cu—O = 2.705 (3) Å], thus completing the Cu^II coordination to asymmetric elongated octa­hedral (4+1+1*). The Cu atom and the perchlorate anion both lie on mirror planes.     

Preparation of macroreticular redox resins with hydroquinone and catechol units as pendant groups and their properties

Macroreticular redox resins with hydroquinone and catechol units as pendant groups were prepared by the Friedel-Crafts reaction of macroreticular styrene/divinylbenzene copolymer with 2,5- and 3,4-dimethoxybenzyl chlorides, followed by removal of the methyl groups with hydrobromic acid. The redox capacity of the macroreticular resins was determined by oxidation of hydrazobenzene with resins in oxidized form. Resins with 1,4-benzoquinone units were capable of oxidizing hydrazobenzene, whereas those with 1,2-benzoquinone (catechol quinone) units exhibited no apparent oxidative ability; this seems to be due to a complex formation between azobenzene and the catechol units in the reduced resins. Adsorption of metallic ions onto catechol-containing resins showed a high selectivity for Hg²⁺ ion. The effects of pH, reaction time, and ion concentration on the adsorption were also studied.     

Synthesis and flammability of copoly(isophthalamide)s. II. With pendant phosphorus groups

A series of copoly(isophthalamide)s containing pendant phosphorus, dialkoxyphosphinylphenylene, diphenylphosphinylphenylene, and diphenylphosphinylamino groups were prepared. The introduction of phosphorus groups was performed to a degree of ca. 5–17 mol %. From the limiting oxygen index (LOI) measurements, it was found that the LOI of P-substituted polyamides increased by ca. 14–40%. From TG and DTG analysis the maximum rate and the percentage of mass loss of the decomposition stages were evaluated. From these measurements the mode of action of phosphorus groups in the solid or gas phase was assessed. In the solid phase, due to crosslinking reactions, a reduction of the maximum rate and the percentage of mass loss in the decomposition stage of main chain amide bonds was observed. In this case the increase of the char yield at 700°C of the P-substituted polyamides was in the range of 21–36%. © 1993 John Wiley & Sons, Inc.     

Synthesis and properties of poly(arylene ether)s bearing sulfonic acid groups on pendant phenyl rings

Two kinds of new aromatic poly(arylene ether)s containing sulfonic acid groups were synthesized. Polymer 1 composed of tetraphenylphenylene ether and perfluorobiphenylene units was sulfonated with chlorosulfonic acid. Sulfonation took place only at the para position of the pendant phenyl rings. The average degree of sulfonation per repeating unit (m) was controlled from 1 to 4. Sulfonated polymer 2 with m = 3 was soluble in methanol and dimethyl sulfoxide and swelled in water. Incorporating bis(3,5‐dimethylphenyl)sulfone moieties into the sulfonated polymer imparts less methanol affinity. Polymers 4 with 30–65 mol % tetrakis(sulfophenyl)phenylene ether units has high decomposition temperatures above 300 °C, hydrophilicity, and good hydrolytic stability. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3211–3217, 2001     

Organic electroluminescent device with aromatic amine-containing polymer as a hole transport layer (II): Poly(arylene ether sulfone)-containing tetraphenylbenzidine

Organic electroluminescent devices were fabricated using a poly(arylene ether sulfone)-containing tetraphenylbenzidine (PTPDES) and tris(8-quinolinolato)-aluminum(III) complex, Alq, as the hole transport layer and the electron-transporting emitter layer, respectively. A device structure of glass substrate/indium—tin oxide (ITO)/PTPDES/Alq/Mg : Ag was employed. Hole injection from ITO through the PTPDES layer to the Alq layer and concomitant electroluminescence from the Alq layer were observed. Bright green light with a luminance of 14,000 cd/m² was observed at a drive voltage of 14 V, indicating that the polymer possesses a high hole mobility and a high electron-blocking capability.