Naphthalene-Based Poly(arylene ether ketone) Copolymers Containing Sulfobutyl Pendant Groups for Proton Exchange Membranes

A new monomer 1,5-bis(4-fluorobenzoyl)-2,6-dimethoxynaphthalene (DMNF) was prepared and further polymerized to form naphthalene-based poly(arylene ether ketone) copolymers containing methoxy groups (MNPAEKs). The side-chain-type sulfortated naphthalene-based poly(arylene ether ketone) copolymers (SNPAEKs) were obtained by demethylation and sulfobutylation. Flexible and tough membranes with reasonably high mechanical strength were prepared. The SNPAEKs membrane showed anisotropic membrane swelling with larger swelling in thickness than in plane. Transmission electron microscopy (TEM) analysis revealed clear nano-phase separated structure of SNPAEKs membranes, which composed of hydrophilic side chain and hydrophobic main-chain domains.

Synthesis of Soluble Poly(arylene ether sulfone) Ionomers with Pendant Quaternary Ammonium Groups for Anion Exchange Membranes

A new bisphenol monomer, 2,2'-dimethylaminemetllylene-4,4'-biphenol (DABP), was easily prepared by Mannich reaction of dimethylamine and formaldehyde with 4,4'-biphenol. Novel partially fluorinated poly(arylene ether sulfone)s with pendant quaternary ammonium groups were prepared by copolymerization of DABP, 4,4'-biphenol, and 3,3',4,4'- tetrafluorodiphenylsulfone, followed by reaction with iodomethane. The resulting copolymers PSQNI-x (where x represents the molar fraction of DABP in the feed) with high molecular weight exhibited outstanding solubility in polar aprotic solvents; thus, the flexible and tough membranes of PSQNI-x with varying ionic content could be prepared by casting from the DMAc solution. Novel anion exchange membranes, PSQNOH-x, were obtained by an anion exchange of PSQNI-x with 1 N NaOH.

Novel hydrophilic-hydrophobic multiblock copolyimides as proton exchange membranes: Enhancing the proton conductivity

A series of novel multiblock copolymers based on sulfonated copolyimides were developed and evaluated for use as proton exchange membranes (PEMs). In these multiblock copolyimides, the hydrophilic blocks were composed of the sulfonated dianhydride and the sulfonated diamine, with sulfonic acid groups on every aromatic ring (i.e., fully sulfonated). This molecular design was implemented to effectively enhance the proton conductivity. The properties of the multiblock copolyimides with varying IEC values or block lengths were investigated to obtain a better understanding of the relationship between molecular structure and properties of proton exchange membranes. The water uptake and proton conductivity were found to be highly dependent upon their structure. The block copolymers displayed significantly higher proton conductivities, especially at low relative humidity than the random copolymers with a similar IEC.

Synthesis and properties of novel sulfonated poly(phenylquinoxaline)s as proton exchange membranes

Two series of sulfonated poly(phenylquinoxaline)s (SPPQ-x and SPPQ(O)-x, x refers to molar percentage of sulfonated tetraamine monomer) were first synthesized from a sulfonated tetraamine (4,4'-bis(3,4-diaminophenoxy)biphenyl-3.3'-disulfonic acid) and two aromatic bisbenzils (4-phenylglyoxalylbenzil and p,p'-oxydibenzil) in a mild condition. The structures of SPPQ-x and SPPQ(0)-x were characterized by IR and H-1 NMR spectra. The properties of these polymer films, such as water uptake, water swelling ratio, proton conductivity, thermal properties, methanol permeability, hydrolytic and oxidative stability were also investigated. The resulting polymers generally showed good solubility in DMAc and DMSO. Flexible and tough membranes with high mechanical strength were prepared. They show very high thermal, thermooxidative, hydrolytic stabilities and low methanol permeability. SPPQ-100 with the IEC value (2.41 mmol/g) displays the conductivity of 0.1 S/cm and a swelling ratio of 7.3% at 100 degrees C.

Synthesis and properties of water stable poly[bis(benzimidazobenzisoquinolinone)] ionomers for proton exchange membranes fuel cells

A novel sulfonated tetraamine, di(triethylammonium)-4,4'-bis(3,4-diaminophenoxy)biphenyl-3,3'-disulfonate (BAPBDS), was successfully synthesized by nucleophilic aromatic substitution of 4,4'-dihydroxybiphenyl with 5-chloro-2-nitroaniline, followed by sulfonation and reduction. A high-temperature polycondensation of sulfonated tetraamine, non-sulfonated tetraamine (4,4 -bis(3,4-aminophenoxy)biphenyl) and 1,4,5,8-naphthalenetetracarboxylic dianhydride (a) or 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic dianydride (b) gave the poly[bis(benzimidazobenzisoquinolinones)] ionomers SPBIBI-a(x) or SPBIBI-b(x), where x refers to the molar percentage of the sulfonated tetraamine monomer. Flexible and tough membranes of high mechanical strength were obtained by solution casting and the electrolyte properties of the polymers were intensively investigated. The ionomer membranes displayed excellent dimensional and hydrolytic stabilities.

Novel proton exchange membranes based on water resistant sulfonated poly[bis(benzimidazobenzisoquinolinones)]

Novel water resistant sulfonated poly[bis(benzimidazobenzisoquinolinones)] (SPBIBIs) were synthesized from 6,6'-disulfonic-4,4'-binaphthy]-1,1',8,8'-tetracarboxylic dianhydride (SBTDA) and various aromatic ether tetraamines. The resulting polymers with IEC in the range of 2.17-2.87 mequiv g(-1) have a combination of desired properties such as high solubility in common organic solvents, film-forming ability, and excellent thermal and mechanical properties. Flexible and tough membranes, obtained by casting from m-cresol solution, had tensile strength, elongation at break, and tensile modulus values in the range of 87.6-98.4 MPa, 35.8-52.8%, and 0.94-1.07 GPa. SPBIBI membranes with a high degree of sulfonation displayed high proton conductivity and a good resistance to water swelling as well. SPBIBI-b with IEC of 2.80 mequiv g(-1) displayed the conductivity of 1.74 x 10(-1) S cm(-1) at 100 degrees C, which was comparable to that of Nafion (R) 117 (1.78 x 10(-1) S cm(-1), at 100 degrees C).

Novel sulfonated poly(arylene ether ketone) copolymers bearing carboxylic or benzimidazole pendant groups for proton exchange membranes

A novel strategy in which the benzimidazole group and sulfonic group are simultaneously attached to an aromatic polymer has been reported in this paper. For this purpose, sulfonated poly(arylene ether ketone) copolymers containing carboxylic acid groups (SPAEK-x-COOH, x refers to the molar percentage Of sulfonated repeating units) are prepared by the aromatic nucleophilic polycondensation of sodium 5,5'-carbonyl-bis(2-fluobenzene-sulfonate) (SDFBP), 4,4'-difluorobenzophenone (DFBP) and phenolphthalin (PPL). Then the carboxylic acid groups attached to the SPAEK-x-COOH are transformed to benzimidazole units through condensation reactions (referred to as SPAEK-x-BI). Fourier transform infrared spectroscopy and H-1 NMR measurements are used to characterize and confirm the structures of these copolymers.

Synthesis and characterization of novel sulfonated poly(arylene ether ketone) copolymers with pendant carboxylic acid groups for proton exchange membranes

A series of novel side-chain-type sulfonated poly(arylene ether ketone)s with pendant carboxylic acid groups copolymers (C-SPAEKs) were synthesized by direct copolymerization of sodium 5,5'-carbonyl-bis(2-fluorobenzenesulfonate), 4,4'-difluorobenzophenone and 4,4'-bis(4-hydroxyphenyl) valeric acid (DPA). The expected structure of the sulfonated copolymers was confirmed by FT-IR and H-1 NMR. Membranes with good thermal and mechanical stability could be obtained by solvent cast process. It should be noted that the proton conductivity of these copolymers with high sulfonation degree (DS > 0.6) was higher than 0.03 S cm(-1) and increased with increasing temperature. At 80 degrees C, the conductivity of C-SPAEK-3 (DS = 0.6) and C-SPAEK-4 (DS = 0.8) reached up to 0.12 and 0.16 S cm-1, respectively, which were higher than that of Nafion 117 (0.10 S cm(-1)).

Incorporation of Nanoparticles into Polyelectrolyte Multilayers via Counterion Exchange and in situ Reduction

We report a general method for incorporation of nanoparticles into polyelectrolyte multilayer (PEM) thin films by utilizing the excess charges and associated counterions present in the PEMs. Silver ions were introduced directly into multilayers assembled from poly(diallyldimethylammonium chloride) (PDDA) and poly(styrene sulfonate) (PSS), (PDDA/PSS)(n), by a rapid ion exchange process, which were then converted into silver nanoparticles via in situ reduction to create composite thin films. The size and the content of the nanoparticles in the film call be tuned by adjusting the ionic strength in the polyelectrolyte solutions used for the assembly. Spatial control over the distribution of the nanoparticles in the PEM was achieved via the use of multilayer heterostructure containing PDDA/PSS bilayer blocks assembled at different salt concentrations. Because excess charges and counterions are always present in any PEM, this approach can be applied to fabricate a wide variety of composite thin Films based on electrostatic self-assembly.

Counterion exchange at the surface of polyelectrolyte multilayer film for wettability modulation

Counterions present at the surface of polyelectrolyte multilayers (PEMs) were utilized for modulation of surface wettability via ion exchange. The PEM film was dipped in aqueous solutions of different anions, respectively, and the water contact angle of the surface varied from about 10 degrees to 120 degrees, depending on the hydration characteristics of the anion. The ion exchange mechanism was verified by X-ray photoelectron spectroscopy. The process was rapid and reversible. Ionic strength of the polyelectrolyte solution used for preparing the PEMs was found to be crucial to the surface wetting properties and the reversibility and kinetics of the process, and the effects were correlated to the surface density of the excess charge and counterion. This work provides a general, facile and rapid approach of surface property modulation.

Synthesis and characterization of rigid-rod sulfonated polyimides bearing sulfobenzoyl side groups as proton exchange membranes

A novel wholly aromatic diamine, 2,2 '-bis(3-sulfobenzoyl)benzidine (2,2 '-BSBB), was successfully prepared by the reaction of 2,2 '-dibenzoylbenzidine (2,2 '-DBB) with fuming sulfuric acid. Copolymerization of 1,4,5,8-naphathlenetetracarboxylic dianhydride with 2,2 '-BSBB and 2,2 '-DBB generated a series of rigid-rod sulfonated polyimides. The synthesized copolymers with the -SO3H group on the side chain of polymers possessed high molecular weights revealed by their high viscosity and the formation of tough and flexible membranes. The copolymer membranes exhibited excellent oxidative stability and mechanical properties due to their fully aromatic structure extending through the backbone and pendent groups. They displayed clear anisotropic membrane swelling in water with negligibly small dimensional changes in the plane direction of the membrane. The proton conductivities of copolymer membranes increased with increasing IEC and temperature, reaching value above 1.25 x 10(-1) S/cm at 20 degrees C, which is higher than that of Nafion (R) 117 at the same measurement condition. They displayed reasonably high proton conductivity due to the higher acidity of benzoyl sulfonic acid group, the larger interchain spacing, which is available for water to occupy, taking their lower water uptake (WU) into account. Consequently, these materials proved to be promising as proton exchange membrane.

Preparation and evaluation of a proton exchange membrane based on oxidation and water stable sulfonated polyimides

A series of novel oxidation and water stable sulfonated polyimides (SPIs) were synthesized from 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic dianhydride (BTDA), and wholly aromatic diamine 2,2'-bis(3-sulfobenzoyl) benzidine (2,2'-BSBB) for proton exchange membrane fuel cells. These polyimides could be cast into flexible and tough membranes from m-cresol solutions. The copolymer membranes exhibited excellent oxidative stability and mechanical properties due to their fully aromatic structure extending through the backbone and pendant groups. Moreover, all BTDA-based SPI membranes exhibited much better water stability than those based on the conventional 1,4,5,8-naphthalenecarboxylic dianhydride. The improved water stability of BTDA-based polyimides was attributed to its unique binaphthalimide structure. The SPI membranes with ion exchange capacity (IEC) of 1.36-1.90 mequiv g(-1) had proton conductivity in the range of 0.41 x 10(-1) to 1. 12 x 10(-1) S cm(-1) at 20 degrees C. The membrane with IEC value of 1.90 mequiv g(-1) displayed reasonably higher proton conductivity than Nafion((R)) 117 (0.9 x 10(-1) S cm(-1)) under the same test condition and the high conductivity of 0.184 S cm(-1) was obtained at 80 degrees C. Microscopic analyses revealed that well-dispersed hydrophilic domains contribute to better proton conducting properties. These results showed that the synthesized materials might have the potential to be applied as the proton exchange membranes for PEMFCs.

Sulfonated polyimides bearing benzimidazole groups for proton exchange membranes

A series of sulfonated polymides containing benzimidazole groups were synthesized using 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic dianhydride (BTDA), 4,4'-diaminodiphenyl ether-2,2'-disulfonic acid (ODADS) as the sulfonated diamine, and 2-(3',5-diaminophenyl)benzimidazole (a) or 6,4'-diamino-2-phenylbenzimidazole (b) as the nonsulfortated diamine. The electrolyte properties of the synthesized polyimides Ia-x, Ib-x, x refers to molar percentage of the sulfonated diamine) were investigated and compared with those of polyimides (Ic-x) from BTDA, ODADS, and m-phenylenediamine (c). All synthesized polyimides possessed high molecular weights revealed by their high viscosity, and formation of tough and flexible membranes. Polyintides with benzimidazole groups exhibited much better swelling capacity than those without benzimiclazole groups. This was attributed to the strong interchain interaction through basic benzimidazole functions and sulfonic acid groups. The sulfortated polyimides that are incorporated with 1, 1',8,8'-binaphthalimide exhibited better hydrolytic stability than that with 1,4,5,8-naphthalimide. Polyimide membranes with good water stability as well as high proton conductivity were developed. Polyimide membrane (Ia - 90), for example, did not lose mechanical properties after being soaked in boiling water for tOOO h, while its proton conductivity was still at a high level (compared to that of Nafion 117).

Synthesis and properties of novel sulfonated polyimides containing binaphthyl groups as proton-exchange membranes for fuel cells

A novel sulfonated diamine monomer, 2,2'-bis(p-aminophenoxy)-1,1'-binaphthyl-6,6'-disulfonic acid (BNDADS), was synthesized. A series of sulfonated polyimide copolymers containing 30-80 mol % BNDADS as a hydrophilic component were prepared. The copolymers showed excellent solubility and good film-forming capability. Atomic force microscopy phase images clearly showed hydrophilic/hydrophobic microphase separation. The relationship between the proton conductivity and degree of sulfonation was examined. The sulfonated polyimide copolymer with 60 mol % BNDADS showed higher proton conductivity (0.0945-0.161 S/cm) at 20-80 degrees C in liquid water. The membranes exhibited methanol permeability from 9 x 10(-8) to 5 X 10(-7) cm(2)/s at 20 degrees C, which was much lower than that of Nafion (2 x 10(-6) cm(2)/s). The copolymers were thermally stable up to 300 degrees C. The sulfonated polyimide copolymers with 30-60 mol % BNDADS showed reasonable mechanical strength; for example, the maximum tensile strength at break of the sulfonated polyimide copolymer with 40 mol % BNDADS was 80.6 MPa under high moisture conditions. The optimum concentration of BNDADS was found to be 60 mol % from the viewpoint of proton conductivity, methanol permeability, and membrane stability.

Water resistant sulfonated polyimides based on 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic dianhydride (BNTDA) for proton exchange membranes

A series of sulfonated polyimides (SPIs) were synthesized in in-cresol from 4,4'-binaphthyl- 1,11,8,8'-tetracarboxylic dianhydride (BNTDA), 4.4'-diaminodiphenylether-2,2-disulfonicacid (ODADS), and 4.4'-diamino-diphenyl ether (ODA) in the presence of triethylamine and benzoic acid. The resulted polyimides showed much better water resistance than the corresponding sulfonated polyimides from 1,4,5,8-naphthatenetetracarboxylic dianhydride (NTDA) and ODADS, which is contributed to the higher electron density in the carbonyl carbon atoms of BNTDA. Copolyimides S-75 and S-50 maintained their mechanical properties and proton conductivities after aging in water at 100 degrees C for 800 h. The proton conductivity of these SPIs was 0.0250-0.3565 S/cm at 20 degrees C and 100% relative humidity (RH), and increased to 0.11490.9470 S/cm at 80 degrees C and 100% RH. The methanol permeability values of these SPIs were in the range of 0.99-2.36 x 10(-7) cm(2)/S, which are much lower than that of Nafion 117 (2 x 10(-6) cm(2)/s).