The propensity of hydrogen-bonded guanidinium (G) organodisulfonates (S) to form crystalline inclusion compounds has been investigated in the context of separating isomeric mixtures of xylenes and dimethylnaphthalenes via selective inclusion. Pairwise competition experiments, in which inclusion compounds are grown from solutions containing an isomeric mixture of guests, map the inclusion selectivity of a particular host as a function of guest content in solution. Whereas the G2[4,4‘-biphenyldisulfonate] host is minimally selective with respect to inclusion of o-, m-, or p-xylene, the homologous G2[2,6-naphthalenedisulfonate] is highly selective toward the inclusion of p-xylene, by a factor of 36 and 160 versus o-xylene and m-xylene, respectively. Similarly, the hosts of the homologous series G2[2,6-naphthalenedisulfonate], G2[4,4‘-biphenyldisulfonate], G2[2,6-anthracenedisulfonate], and G2[4,4‘-azobenzenedisulfonate] display different selectivity for the 10 isomers of dimethylnaphthalene. The details of t...

Shape-Selective Separation of Molecular Isomers with Tunable Hydrogen-Bonded Host Frameworks

A series of sulfonated poly(aryl ether ketone)s (SPAEKs) were prepared by aromatic nucleophilic polycondensation of 2,6-dihydroxynaphthalene with 5,5′-carbonyl-bis(2-fluorobenzenesulfonate) and 4,4′-difluorobenzophenone. The structure and degree of sulfonation (DS) of the SPAEKs were characterized using 1H NMR spectroscopy. The experimentally observed DS values were close to the expected values derived from the starting material ratios. The thermal stabilities of the SPAEKs were characterized by thermogravimetric analysis, which showed that in acid and sodium salt forms they were thermally stable in air up to about 240 and 380 °C, respectively. Transparent membranes cast from the directly polymerized SPAEKs exhibited good mechanical properties in both dry and hydrated states. The dependence of water uptake and of membrane swelling on the DS at different temperatures was studied. SPAEK membranes with a DS from 0.72 to 1.60 maintained adequate mechanical properties after immersion in water at 80 °C for 24 h. The proton conductivity of SPAEK membranes with different degrees of sulfonation was measured as a function of temperature. The proton conductivity of the SPAEK films increased with increased DS, and the highest room temperature conductivity (4.2 × 10−2 S/cm) was recorded for a SPAEK membrane with a DS of 1.60, which further increased to 1.1 × 10−1 S/cm at 80 °C. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2866–2876, 2004

/pdf/sulfonated-poly-aryl-ether-ketone-s-containing-naphthalene-48zsetcwph.pdf

Sulfonated poly(aryl ether ketone)s containing naphthalene moieties obtained by direct copolymerization as novel polymers for proton exchange membranes

New bisphenol monomers, (3-methyl)phenylhydroquinone and (3-trifluoromethyl)phenylhydroquinone, were prepared in a two-step synthesis. A series of poly(aryl ether ketone)s were derived from these bisphenols via a nucleophilic aromatic substitution polycondensation with various bisfluoro compounds. The polycondensation proceeded quantitatively in tetramethylene sulfone in the presence of anhydrous potassium carbonate and afforded the polymers with inherent viscosities of 0.63–0.91 dL/g. The fluorinated polymers showed lower glass-transition temperatures and higher thermal-decomposition temperatures than the corresponding nonfluorinated polymers. The solubility of the polymers was improved by the introduction of bulky pendant groups. All the polymers formed transparent, strong, and flexible films, with tensile strengths of 86.4–102.0 MPa, Young's moduli of 2.28–3.03 GPa, and elongations at break of 14–42%. All the polymers had low dielectric constants of 2.70–2.83 at 1 MHz. Compared with the methylated polymers, the trifluoromethylated polymers exhibited lower water sorption, which was attributed to the stronger hydrophobicity of the fluorine-containing groups. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3392–3398, 2002

Poly(aryl ether ketone)s with (3‐methyl)phenyl and (3‐trifluoromethyl)phenyl side groups

Sulfonated poly(fluorenyl ether ketone) membrane prepared via direct polymerization for PEM fuel cell application

Naphthalene-based poly(arylene ether ketone)s were obtained through a three-step process involving polymerization of methylated polymers, followed by bromination and derivatization with a diquaternary-ammonium group. The ionic conductivities of the anion exchange membranes were above 10−2 S cm−1 at room temperature and the membrane with an IEC = 1.46 mequiv. g−1 attained an ion conductivity of 7.4 × 10−2 S cm−1 at 100 °C, which is higher than many reported results. The membrane series had low water uptake and excellent dimensional stability, even at the highest IEC values. In addition, the membranes were insoluble in organic solvents and concentrated alkaline solutions for many days, even under heating, suggesting their excellent stability. These combined data suggest that the membranes have potential to be used as anion exchange membranes for fuel cells applications.

/pdf/naphthalene-based-poly-arylene-ether-ketone-anion-exchange-2g5rxhrat5.pdf

Naphthalene-based poly(arylene ether ketone) anion exchange membranes

Polymer [OPhC(Me) 2 PhOPhCO-Ar-COPh] n (Ar= 2,6-dimethylnaphtylene) has been synthesized by solution polycondensation of bisphenol A with difluorinated dimethylnaphtalene. The polymer is readily soluble in DMSO, CHCl 3 and THF and has 5% weight loss temperature of 457°C in air

Synthesis of a novel naphthalene-based poly(arylene ether ketone) with high solubility and thermal stability

Synthesis of 1,5-bis(4-fluorobenzoyl)-2,6-dimethylnaphthalene (1), polycondensation of 1 with Bisphenol A, and properties of the obtained polymer were studied. Friedel-Crafts acylation of 2,6-dimethylnaphthalene with 4-fluorobenzoyl chloride in nitrobenzene selectivity afforded 1 in 82% yield. X-ray single crystal structural analysis of 1 confirmed that the dibenzoylation proceeded regioselectively and two methyl groups sterically inhibited the coplanarity of the two aromatic planes. The polycondensation of 1 with Bisphenol A in toluene/N-methyl-2-pyrrolidone (NMP) mixed solvent in the presence of excess potassium carbonate as a condensation reagent was carried out at 180°C for 4 h to quantitatively afford the corresponding poly(arylene ether-ketone) (PEK) 3 with high molecular weight (M n ∼ 30,000) as a slightly yellow powder. As the reaction time was prolonged, both M n and MWD of 3 increased and the solubility of 3 in chloroform clearly decreased. By GPC-LALLS, M n of 3 obtained by the polycondensation for 16 h, was 85,000. The PEK 3 with high molecular weight was produced in a quantitative yield in a variety of solvents such as sulfolane. Water formed during the polycondensation hardly affected the yield and molecular weight of 3, although a small molecular weight decrease took place. To evaluate the special effect of the methyl groups of 3, polycondensation of 2,6-bis(4-fluorobenzoyl)naphthalene 2 with bisphenol A was carried out for comparison and the corresponding PEK 4 was quantitatively obtained. Whereas 3 was soluble in ordinary organic solvents such as tetrahydrofuran (THF), chloroform, and NMP at room temperature, 4 was insoluble in most solvents except for strong acids such as conc. sulfonic acid. The polymer 3 showed high glass transition temperature (238°C) and 5% weight loss temperature (457°C). Casting of the polymer from THF solution gave a transparent, tough, flexible, and amorphous film.

Synthesis of a novel naphthalene‐based poly(arylene ether‐ketone) by polycondensation of 1,5‐bis(4‐fluorobenzoyl)‐2,6‐dimethylnaphthalene with bisphenol a

The synthesis of novel dihaloarenes (1,5-bis(4-halophenyl)-2,6-dimethylnaphthalenes, 1), polycondensation of 1 with biphenols, and properties of the obtained polymers were described. Selectively Friedel-Crafts acylation of 2,6-dimethylnaphthalene with 4-halobenzoyl chlorides in nitrobenzene afforded 1 in high yields. X-Ray single-crystal structural analysis of 1 supported that the dibenzoylation proceeded regioselectively at the 1- and 5-positions and the two methyl groups sterically inhibited the coplanarity of the aromatic planes. The polycondensation of 1a with Bisphenol A in toluene/N-methyl-2-pyrrolidone (NMP) mixed solvent in the presence of excess potassium carbonate as a condensation reagent was carried out at 180°C for several hours to quantitatively afford the corresponding poly(arylene-ether-ketone) (PEK) 3 with a high molecular weight (Mn −30,000) as a slightly yellow powder. To evaluate the effect of the methyl groups of 3, polycondensation of 2,6-bis(4-fluorobenzoyl)naphthalene 2 with Bisphenol A was carried out for comparison and the corresponding PEK 4 was obtained quantitatively. Whereas 3 was soluble in ordinary organic solvents such as tetrahydrofuran (THF) and chloroform at room temperature, 4 was insoluble in common solvents except for strong acids such as conc. sulfonic acid. 3 showed a high glass-transition temperature (238°C) and a 5% weight loss temperature of 457°C. The polycondensations of 1a with various biphenols such as dihydroxybenzophenone were carried out to examine the properties of the obtained polymers. The obtained PEKs showed high glass transition temperatures and 5% weight loss temperatures as well as good solubilities in ordinary organic solvents at room temperature. Casting of the polymers from THF solution gave transparent, tough, flexible, and amorphous films. 1,5-Bis(4-chlorobenzoyl)-2,6-dimethylnaphthalene 1b similarly underwent a polycondensation reaction with Bisphenol A to give the corresponding polymer quantitatively.

Mami Ohno

Papers

Synthesis of a novel naphthalene-based poly(arylene ether ketone) with high solubility and thermal stability

Synthesis of a novel naphthalene‐based poly(arylene ether‐ketone) by polycondensation of 1,5‐bis(4‐fluorobenzoyl)‐2,6‐dimethylnaphthalene with bisphenol a

Synthesis and properties of poly(arylene-ether-ketone)s containing a dimethylnaphthalene skeleton in the main chain