Synthesis and Characterization of Linear and Crosslinked Sulfonated Poly(arylene ether sulfone)s: Hydrocarbon-based Copolymers as Ion Conductive Membranes for Electrochemical Systems

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Virginia Tech

Sulfonated poly(arylene ether sulfone)s as ion conductive copolymers have numerous potential applications. Membranes cast from these copolymers are desirable due to their good chemical and thermal stability, excellent mechanical strength, satisfactory conductivity, and excellent transport properties of water and ions. These copolymers can be used in a variety of topologies. Structure-property-performance relationships of these membranes as candidates for electrolysis of water for hydrogen production and for purification of water from dissolved ions have been studied.

Linear and multiblock sulfonated poly(arylene ether sulfone)s are potential alternative candidates to Nafion membranes for hydrogen gas production via electrolysis of water. In this investigation, these copolymers were prepared from the direct polymerization of di-sulfonated and non-sulfonated comonomers with bisphenol monomers. In systematic investigations, a series of copolymers with modified properties were synthesized and characterized by changing the ratio of the sulfonated/non-sulfonated comonomers in each reaction. These copolymers were investigated in terms of mechanical stability, proton conductivity and H2 gas permeability at a range of temperatures and under fully hydrated conditions.

A multiblock copolymer was synthesized and evaluated for its potential as membranes for electrolysis of water and for fuel cell applications. The multiblock copolymer contained some fluorinated repeat units in the hydrophobic blocks, and these were coupled with a fully disulfonated hydrophilic block prepared from 3,3'-disulfonate-4,4'-dichlorodiphenyl sulfone and biphenol. After annealing, the multiblock copolymer showed enhanced proton conductivity and a more ordered morphology in comparison to the random copolymer counterparts. At 90 oC and under fully hydrated conditions, improved proton conductivity and controlled H2 gas permeability was observed. Finally, the performance of the multiblock copolymer, which was measured as the ratio of proton conductivity to H2 gas permeability, was improved when compared to the state-of-the-art membrane, Nafion 212, by a factor of 3.

In another systematic study, two series of random copolymers were synthesized and characterized, and then cast into membranes to evaluate for electrolysis of water. One series contained solely hydroquinone as the phenolic monomer, while the second series contained a mixture of resorcinol and hydroquinone as phenolic comonomers. The polymers that contained only the hydroquinone monomer showed exceptionally good mechanical properties due to the para-substituted comonomer in the composition of the polymer. In the resorcinol-hydroquinone series, gas permeability was constrained due to the presence of 25% of the meta-substituted comonomer incorporated into its structure. Low gas permeability and high proton conductivity at elevated temperatures were obtained for both the linear random and multiblock copolymers. Performance of these copolymers was superior to Nafion at elevated temperatures (80-95°C). In order to enhance the durability of these materials in their hydrated states at elevated temperatures, the surfaces of these copolymer films were treated with fluorine gas. In comparison with pristine non-fluorinated membranes, the modified membranes showed decreased water uptake and longer durability in Fenton's reagent.

A series of linear and crosslinked copolymers were investigated with respect to their potential for use as membranes for desalination of water by electrodialysis and reverse osmosis. The crosslinked membranes were prepared by reacting controlled molecular weight, disulfonated oligomers that were terminated with meta-aminophenol with an epoxy reagent. The oligomers had systematically varied degrees of disulfonation and either 5000 or 10,000 Da controlled molecular weights. Membrane casting conditions were established to fabricate highly crosslinked systems with greater than 90% gel fractions. At such a high gel fraction, the water uptake of the crosslinked membranes was lower than that of the linear biphenol-based, disulfonated random copolymer with a similar IEC. Among these series of copolymers, it was shown that the crosslinked membranes cast from the oligomers with 50% degree of disulfonation and a molecular weight of 10,000 Da had the lowest salt permeability of 10-8 cm2/sec.

For desalination applications, a comonomer was synthesized with one sulfonate substituent on 4,4'-dichlorodiphenyl sulfone. This new monosulfonated comonomer allows for even distribution of the ions on the linear copolymer backbone, and this may be important for controlling ion transport. Mechanical tests were conducted on the membranes while they were submerged in a water bath. The ultimate strength of a fully hydrated copolymer with an IEC of 1.36 meq/g was approximately 60 MPa with an elongation at break of 160%. Moreover, in a monovalent/divalent mixed salt solution, the monosulfonated linear copolymer exhibited a constant Na+ passage of less than 1.0%.

Polymer Synthesis, Sulfonated Monomer Synthesis, Poly(arylene ether sulfone), Proton Exchange Membrane, Water Electrolysis, Electrodialysis of Water, Reverse Osmosis Water Purification, Random Copolymer, Crosslinked Copolymer, Multiblock Copolymer, M