Pentiptycene-based ladder polymers with configurational free volume for enhanced gas separation performance and physical aging resistance.

Polymers of intrinsic microporosity (PIMs) have shown promise in pushing the limits of gas separation membranes, recently redefining upper bounds for a variety of gas pair separations. However, many of these membranes still suffer from reductions in permeability over time, removing the primary advantage of this class of polymer. In this work, a series of pentiptycene-based PIMs incorporated into copolymers with PIM-1 are examined to identify fundamental structure-property relationships between the configuration of the pentiptycene backbone and its accompanying linear or branched substituent group. The incorporation of pentiptycene provides a route to instill a more permanent, configuration-based free volume, resistant to physical aging via traditional collapse of conformation-based free volume. PPIM-ip-C and PPIM-np-S, copolymers with C- and S-shape backbones and branched isopropoxy and linear n-propoxy substituent groups, respectively, each exhibited initial separation performance enhancements relative to PIM-1. Additionally, aging-enhanced gas permeabilities were observed, a stark departure from the typical permeability losses pure PIM-1 experiences with aging. Mixed-gas separation data showed enhanced CO2/CH4 selectivity relative to the pure-gas permeation results, with only ∼20% decreases in selectivity when moving from a CO2 partial pressure of ∼2.4 to ∼7.1 atm (atmospheric pressure) when utilizing a mixed-gas CO2/CH4 feed stream. These results highlight the potential of pentiptycene's intrinsic, configurational free volume for simultaneously delivering size-sieving above the 2008 upper bound, along with exceptional resistance to physical aging that often plagues high free volume PIMs.

Disulfonated Poly(arylene ether sulfone) Random Copolymers Containing Hierarchical Iptycene Units for Proton Exchange Membranes.

Two series of disulfonated iptycene-based poly(arylene ether sulfone) random copolymers, i.e., TRP-BP (triptycene-based) and PENT-BP (pentiptycene-based), were synthesized via condensation polymerization from disulfonated monomer and comonomers to prepare proton exchange membranes (PEMs) for potential applications in electrochemical devices such as fuel cell. To investigate the effect of iptycene units on membrane performance, these copolymers were systematically varied in composition (i.e., iptycene content) and the degree of sulfonation (i.e., 30-50%), which were characterized comprehensively in terms of water uptake, swelling ratio, oxidative stability, thermal and mechanical properties, and proton conductivity at various temperatures. Comparing to copolymers without iptycene units, TRP-BP and PENT-BP ionomers showed greatly enhanced thermal and oxidative stabilities due to strong intra- and inter-molecular supramolecular interactions induced by hierarchical iptycene units. In addition, the introduction of iptycene units in general provides PEMs with exceptional dimensional stability of low volume swelling ratio at high water uptakes, which is ascribed to the supramolecularly interlocked structure as well as high fractional free volume of iptycene-based polymers. It is demonstrated that the combination of high proton conductivity and good membrane dimension stability is the result of the synergistic effects of multiple factors including free volume (iptycene content), sulfonation degree, hydrophobicity, and swelling behavior (supramolecular interactions).

Exfoliated Graphene Leads to Exceptional Mechanical Properties of Polymer Composite Films.

Polymers with superior mechanical properties are desirable in many applications. In this work, polyethylene (PE) films reinforced with exfoliated thermally reduced graphene oxide (TrGO) fabricated using a roll-to-roll hot-drawing process are shown to have outstanding mechanical properties. The specific ultimate tensile strength and Young's modulus of PE/TrGO films increased monotonically with the drawing ratio and TrGO filler fraction, reaching up to 3.2 ± 0.5 and 109.3 ± 12.7 GPa, respectively, with a drawing ratio of 60× and a very low TrGO weight fraction of 1%. These values represent by far the highest reported to date for a polymer/graphene composite. Experimental characterizations indicate that as the polymer films are drawn, TrGO fillers are exfoliated, which is further confirmed by molecular dynamics (MD) simulations. Exfoliation increases the specific area of the TrGO fillers in contact with the PE matrix molecules. Molecular dynamics simulations show that the PE-TrGO interaction is stronger than the PE-PE intermolecular van der Waals interaction, which enhances load transfer from PE to TrGO and leverages the ultrahigh mechanical properties of TrGO.

Highly Proton Conducting Polyelectrolyte Membranes with Unusual Water Swelling Behavior Based on Triptycene-containing Poly(arylene ether sulfone) Multiblock Copolymers.

Multiblock poly(arylene ether sulfone) copolymers are attractive for polyelectrolyte membrane fuel cell applications due to their reportedly improved proton conductivity under partially hydrated conditions and better mechanical/thermal stability compared to Nafion. However, the long hydrophilic sequences required to achieve high conductivity usually lead to excessive water uptake and swelling, which degrade membrane dimensional stability. Herein, we report a fundamentally new approach to address this grand challenge by introducing shape-persistent triptycene units into the hydrophobic sequences of multiblock copolymers, which induce strong supramolecular chain-threading and interlocking interactions that effectively suppress water swelling. Consequently, unlike previously reported multiblock copolymer systems, the water swelling of the triptycene-containing multiblock copolymers did not increase proportionally with water uptake. This combination of high water uptake and low swelling behavior of these copolymers resulted in excellent proton conductivity and membrane dimensional stability under fully hydrated conditions. In particular, the triptycene-containing multiblock copolymer film with the longest hydrophilic block length (i.e., BPSH100-TRP0-15k-15k) had a water uptake of 105%, an excellent proton conductivity of 0.150 S/cm, and a volume swelling ratio of just 29% (more than 42% reduction compared to Nafion 212).

Water and Salt Transport Properties of Triptycene-Containing Sulfonated Polysulfone Materials for Desalination Membrane Applications.

A series of triptycene-containing sulfonated polysulfone (TRP-BP) materials was prepared via condensation polymerization, and the desalination membrane-relevant fundamental water and salt transport properties (i.e., sorption, diffusion, and permeability coefficients) of the polymers were characterized. Incorporating triptycene into sulfonated polysulfone increased the water content of the material compared to sulfonated polysulfone materials that do not contain triptycene. No significant difference in salt sorption was observed between TRP-BP membranes and other sulfonated polysulfone membranes, suggesting that the presence of triptycene in the polymer did not dramatically affect thermodynamic interactions between salt and the polymer. Both water and salt diffusion coefficients in the TRP-BP membranes were suppressed relative to other sulfonated polysulfone materials with comparable water content, and these phenomena may result from the influence of triptycene on polymer chain packing and/or free-volume distribution, which could increase the tortuosity of the transport pathways in the polymers. Enhanced water/salt diffusivity selectivity was observed for some of the TRP-BP membranes relative to those materials that did not contain triptycene, and correspondingly, incorporation of triptycene into sulfonated polysulfone resulted in an increase, particularly for acid counterion form TRP-BP materials, in water/salt permeability selectivity, which is favorable for desalination membrane applications.

Facile Synthesis of a Pentiptycene-Based Highly Microporous Organic Polymer for Gas Storage and Water Treatment.

Rigid H-shaped pentiptycene units, with an intrinsic hierarchical structure, were employed to fabricate a highly microporous organic polymer sorbent via Friedel-Crafts reaction/polymerization. The obtained microporous polymer exhibits good thermal stability, a high Brunauer-Emmett-Teller surface area of 1604 m2 g-1, outstanding CO2, H2, and CH4 storage capacities, as well as good adsorption selectivities for the separation of CO2/N2 and CO2/CH4 gas pairs. The CO2 uptake values reached as high as 5.00 mmol g-1 (1.0 bar and 273 K), which, along with high adsorption selectivity values (e.g., 47.1 for CO2/N2), make the pentiptycene-based microporous organic polymer (PMOP) a promising sorbent material for carbon capture from flue gas and natural gas purification. Moreover, the PMOP material displayed superior absorption capacities for organic solvents and dyes. For example, the maximum adsorption capacities for methylene blue and Congo red were 394 and 932 mg g-1, respectively, promoting the potential of the PMOP as an excellent sorbent for environmental remediation and water treatment.

Highly CO2-Selective Gas Separation Membranes Based on Segmented Copolymers of Poly(Ethylene oxide) Reinforced with Pentiptycene-Containing Polyimide Hard Segments.

Poly(ethylene oxide) (PEO)-containing polymer membranes are attractive for CO2-related gas separations due to their high selectivity toward CO2. However, the development of PEO-rich membranes is frequently challenged by weak mechanical properties and a high crystallization tendency of PEO that hinders gas transport. Here we report a new series of highly CO2-selective, amorphous PEO-containing segmented copolymers prepared from commercial Jeffamine polyetheramines and pentiptycene-based polyimide. The copolymers are much more mechanically robust than the nonpentiptycene containing counterparts due to the molecular reinforcement mechanism of supramolecular chain threading and interlocking interactions induced by the pentiptycene structures, which also effectively suppresses PEO crystallization leading to a completely amorphous structure even at 60% PEO weight content. Membrane transport properties are sensitively affected by both PEO weight content and PEO chain length. A nonlinear correlation between CO2 permeability with PEO weight content was observed due to the competition between solubility and diffusivity contributions, whereby the copolymers change from being size-selective to solubility-selective when PEO content reaches 40%. CO2 selectivities over H2 and N2 increase monotonically with both PEO content and chain length, indicating strong CO2-philicity of the copolymers. The copolymer film with the longest PEO sequence (PEO2000) and highest PEO weight content (60%) showed a measured CO2 pure gas permeability of 39 Barrer, and ideal CO2/H2 and CO2/N2 selectivities of 4.1 and 46, respectively, at 35 °C and 3 atm, making them attractive for hydrogen purification and carbon capture.