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Bara, Jason E.

Publications and source records attributed to Bara, Jason E..

8 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Upcycling of Polystyrene Waste to Poly(ionic liquid) Materials

The C–H functionalization of commodity polymers could be a promising approach for upcycling plastic waste into advanced materials, which can alter the properties of the original materials through the introduction of different functionalities onto the existing backbone structures. In this study, waste polystyrene (PS) was modified by Friedel–Crafts acylation using 4-chlorobutyryl chloride (4-CBC) followed by reaction with N-alkylimidazoles to form cationic polyelectrolytes. These methods provide access to what are essentially poly(ionic liquid) (poly(IL)) materials with properties that are distinctly different from those of the PS from which they were formed. In one notable example, the glass transition temperature (T g ) of imidazolium-functionalized PS was ∼16 °C, which is a nearly 90 °C reduction from PS. This is also evidenced by macroscopic mechanical properties where the poly(IL) product is highly elastic in stark contrast to brittle PS. Moreover, the resulting ionomers showed self-healing behaviors in the presence of a “free” IL further contributing to the utility of the materials. Here, the methods in this work can open opportunities to utilize waste PS to obtain a vast array of poly(IL) materials with highly tailored structures and properties.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Polymeric ionic liquids containing copper(I) and copper(II) ions as gas chromatographic stationary phases for olefin separations

Copper(I) ions (Cu + ) are used in olefin separations due to their olefin complexing ability and low cost, but their instability in the presence of water and gases limits their widespread use. Ionic liquids (ILs) have emerged as stabilizers of Cu + ions and prevent their degradation, providing high olefin separation efficiency. There is limited understanding into the role that polymeric ionic liquids (PILs), which possess similar structural characteristics to ILs, have on Cu + ion-olefin interactions. Moreover, copper ions with diverse oxidation states, including Cu + and Cu 2+ ions, have been rarely employed for olefin separations. In this study, gas chromatography (GC) is used to investigate the interaction strength of olefins to stationary phases composed of the 1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C 6 MIM + ][NTf 2 – ]) IL and the poly(1-hexyl-3-vinylimidazolium [NTf 2 – ]) (poly([C 6 VIM + ][NTf 2 – ])) PIL containing monovalent and divalent copper salts (i.e., [Cu + ][NTf 2 – ] and [Cu 2+ ]2[NTf 2 – ]). The chromatographic retention of alkenes, alkynes, dienes, and aromatic compounds was examined. Incorporation of the [Cu 2+ ]2[NTf 2 – ] salt into a stationary phase comprised of poly(dimethylsiloxane) resulted in strong retention of olefins, while its addition to the [C 6 MIM + ][NTf 2 – ] IL and poly([C 6 VIM + ][NTf 2 – ]) PIL allowed for the interaction strength to be modulated. Olefins exhibited greater affinities toward IL and PIL stationary phases containing the [Cu 2+ ]2[NTf 2 – ] salt compared to those with the [Cu + ][NTf 2 – ] salt. Elimination of water from both copper salts was observed to be an important factor in promoting olefin interactions, as evidenced by increased olefin retention upon exposure of the stationary phases to high temperatures. Furthermore, to evaluate the long-term thermal stability of the stationary phase, chromatographic retention of probes was measured on the [Cu 2+ ]2[NTf 2 – ]/[C 6 MIM + ][NTf 2 – ] IL stationary phase after its exposure to helium at a temperature of 110°C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Polymers derived from 2,2′-bisimidazoles

Disclosed are compositions derived from 2,2′bisimidazoles building blocks and methods of making the same. The disclosed compositions are capable of withstanding temperatures up to 600° C. and substantially flame resistant.

Bara, Jason E.↗
DOE OSTI2024

In-house synthesized poly(ether ether ketone) ionenes. I. ToF-SIMS spectra in the positive ion mode

Static time-of-flight secondary ion mass spectrometry (ToF-SIMS) was performed for acquiring the high-resolution surface spectra of four types of synthesized imidazolium ionene membranes. These novel membranes have aromatic ether–ketone–ether linkages inspired by poly(ether ether ketone) (PEEK). The PEEK-ionenes synthesized for this study have imidazolium cations placed in the polymeric backbone with bistriflimide [Tf 2 N]- counterions. The attention given to synthetically modified PEEK derivatives, such as PEEK-ionenes, is considerable due to their ability to selectively capture CO 2 molecules and other light gases. Therefore, it is important to characterize the surface of these synthesized novel PEEK-ionenes. In this work, characteristic and unique peaks were identified in the positive spectra of each sample. The differences in mass spectra among the samples provide insights for optimizing or fine-tuning the PEEK-ionenes synthesis to achieve a high-performance CO 2 separation membrane with enhanced permeability, selectivity, and mechanical stability. The SIMS spectra and identified characteristic peaks of these synthesized ionenes will serve as a reference in the positive mode, complementing the corresponding spectra reported in the negative ion mode (Paper II).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

In-house synthesized poly(ether ether ketone) ionenes. II. ToF-SIMS spectra in the negative ion mode

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to analyze poly(ether ether ketone) (PEEK) based membranes. PEEK membranes have been shown to be effective in the separation of CO 2 from flue gases (post-combustion technique). The PEEK membranes were synthesized using novel aromatic ether-ketone linkages inspired by PEEK with polymeric backbone bistriflimide [Tf2N]− counterions. One of the keys to advancing this technology is developing membranes that are selective and permeable toward CO 2 , in which PEEK based membranes have been shown to be. Furthermore, the compatibility between various water lean solvents also needs to be investigated. Surface analytical techniques such as x-ray photoelectron spectroscopy and ToF-SIMS are useful for investigating chemical changes between membranes. Herein, we present ToF-SIMS data obtained in the negative ion mode for four different PEEK membranes designed for use in CO 2 capture systems. Positive ion mode spectra are reported in Paper I.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Precisely segmented PEEK–ionene + ionic liquid composite membranes for CO 2 separation

Ionenes, polymers with ionic groups incorporated directly within the backbone are a highly versatile class of materials, although they have received much less attention than polyelectrolytes which have ionic groups pendant from the polymer backbone. By designing ionenes that incorporate robust properties of poly(ether ether ketone) (PEEK), we have achieved new imidazolium-containing PEEK–ionene architectures that create opportunities for enhanced CO 2 separation membranes. To achieve these materials, an new imidazole-functionalized PEEK oligomer (ImK(EEK) 2 KIm) was synthesized through facile and straightforward routes. This molecule was then polymerized via condensation reactions with two different aromatic (α,α'-dibromo-p-xylene) and aliphatic (dibromohexyl containing-bis(imidazolium)hexane dibromide salt) comonomers and exchanged with bistriflimide ([Tf 2 N]) anion to obtain two unique PEEK–ionenes containing distinct PEEK and ionic segments: p([ImK(EEK) 2 Im-p-xyl][Tf 2 N] 2 ) and p([ImK(EEK) 2 (ImC 6 ) 3 ][Tf 2 N] 4 ). While the neat PEEK–ionenes exhibited high molecular weight but were not able to form high-quality films, adding stoichiometric amounts of “free” IL (1-methyl-3-butylimidazolium bistriflimide, [C 4 mIm][Tf 2 N]), greatly improved the flexibility and processability of the resultant membranes. Further, the structure–property relationships of bulk PEEK–ionenes and corresponding composites were extensively characterized by different analytical techniques (thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction, and solid-state NMR). In conclusion, the gas separation properties were investigated, with the PEEK–ionenes + IL composites exhibiting CO 2 permeabilities of 14–94 barrer and good CO 2 /N 2 permselectivities of 26–35, indicating that new designs of segmented ionenes and composites with ILs a promising material design strategy for developing gas separation membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2019

Synthesis and Performance of 6FDA-Based Polyimide-Ionenes and Composites with Ionic Liquids as Gas Separation Membranes

Three new isomeric 6FDA-based polyimide-ionenes, with imidazolium moieties and varying regiochemistry (para-, meta-, and ortho- connectivity), and composites with three different ionic liquids (ILs) have been developed as gas separation membranes. The structural-property relationships and gas separation behaviors of the newly developed 6FDA polyimide-ionene + IL composites have been extensively studied. All the 6FDA-based polyimide-ionenes exhibited good compatibility with the ILs and produced homogeneous hybrid membranes with the high thermal stability of ~380 °C. Particularly, [6FDA I4A pXy][Tf2N] ionene + IL hybrids having [C4mim][Tf2N] and [Bnmim][Tf2N] ILs offered mechanically stable matrixes with high CO2 affinity. The permeability of CO2 was increased by factors of 2 and 3 for C4mim and Bnmim hybrids (2.15 to 6.32 barrers), respectively, compared to the neat [6FDA I4A pXy][Tf2N] without sacrificing their permselectivity for CO2/CH4 and CO2/N2 gas pairs.

Ionenes↗