Incorporation of Metal–Organic Frameworks onto Polypropylene Fibers Using a Phase Inverted Poly(ether-block-amide) Glue

Abstract

The metal–organic frameworks (MOFs) UiO-66-NH2 and HKUST-1 were adhered to chemically inert polypropylene (PP) fibrous mats with poly­(ether-block-amide), aka PEBA or PeBax, using a phase inversion technique. Two types of PeBax were used to investigate the effects of a hydrophilic vs hydrophobic treatment on uptake and permeation properties of the chemical warfare agent simulant 2-chloroethyl ethyl sulfide (CEES). Furthermore, the underlying PP fiber density was altered to understand CEES permeation properties. It was found that using the hydrophobic PeBax 2533 and a higher fiber density led to better barrier properties, with the best material providing ∼250 min protection to a permeation rate of 0.1 μg/min/cm2 in comparison to ∼150 min for the activated carbon fiber Stedcarb. CEES uptake ranged from ∼1.0 to 2.4 mol/kg for composites in comparison to 3.6 mol/kg for the pure MOF. Furthermore, the technique allowed for incorporation of different MOFs, and even a mixture of MOFs, on the same fiber substrate. Finally, the PeBax formulation was able to stabilize HKUST-1 against moisture, potentially opening the door for applications of this MOF in high-humidity environments.

Factors and Limitations of Green, Rapid Metal–Organic Framework-Fabric Synthesis and Effects on Dual Chemical Warfare Agent Protection

“…This can be attributed to the larger crystals on the PET@UiO-66-NH 2 (x6) leading to a decrease in interparticle diffusion resistance due to the larger spacing between crystals. The PET@UiO-66-NH 2 composites presented in this work outperformed previously reported UiO-66-NH 2 fabrics in GD permeation with previous protection times of <25 min for one layer of MOF-fabric. , The CEES permeation time reported here is slightly faster than previously reported UiO-66-NH 2 fabrics with protection times of 50–252 min. , Activated carbon cloth StedCarb outperformed the MOF-fabric in both GD and CEES permeation, but it is hypothesized based on previous studies that stacking multiple layers of MOF-fabric will allow enhanced barrier properties compared to StedCarb. , …”

“…14,17 The CEES permeation time reported here is slightly faster than previously reported UiO-66-NH 2 fabrics with protection times of 50−252 min. 13,33 Activated carbon cloth StedCarb outperformed the MOF-fabric in both GD and CEES permeation, but it is hypothesized based on previous studies that stacking multiple layers of MOF-fabric will allow enhanced barrier properties compared to Sted-Carb. 14,17 ■ CONCLUSIONS In summary, this work explored multiple factors influencing benign, rapid SVS of UiO-66-NH 2 fabric and the effects on CWA protection.…”

“…However, these composites were made using DMF, and GD permeation was not considered. There are very limited reports of UiO-66 fabric tested for the vapor permeation of GD. ,, Spandex@UiO-66-NH 2 and PET@UiO-66-NH 2 composites have been tested for GD hydrolysis and permeation, but no other CWAs were considered in these studies. , Not only is UiO-66-NH 2 effective toward neutralizing and delaying nerve agent permeation, but it has also been repeatedly shown to minimize permeation of 2-chloroethyl ethyl sulfide (CEES), a simulant for distilled mustard (HD). − Song et al tested a UiO-66-NH 2 graphene oxide/polytetrafluorethylene (ePTFE) membrane for both GD and HD permeation; however, that work did not test the composite for toxic chemical decontamination . Hence, UiO-66-NH 2 composites are an excellent candidate for dual agent protection applications, and more studies are needed to correlate both agent neutralization and permeation properties essential for effective personal protective equipment.…”

Polyether Block Amide as Host Matrix for Nanocomposite Membranes Applied to Different Sensitive Fields

“…Recovery of hydrofluorocarbons (HFCs) and hydrofluoroolefins (HFO) from exhausted refrigerant mixtures [17] Pervaporation 2533 on a PDMS support TiO 2 up to 1.5 Recovery of acetone from wastewater [18] 2533 on a PSf-PES blend support TiO 2 nanoparticles 0.01-0.05% in the coating solution Removal of humic acid from water [19] 2533 NaX nano-zeolite 2 Toluene from aqueous solutions [20] 2533 Hollow monocrystalline silicalite-1 (HMS) (200 nm and 350 nm) 10-50 Thiophene/n-octane (gasoline desulfurization) [21] 2533 ZSM-5 (3-5 micron) 10-40 Ethyl acetate from water [22] 2533 on a polyethersulfone (PES) support ZSM-5 (35 nm) 5-15 Ethyl acetate from water [23] 2533 on a PES support ZSM-5 ( Breathable films for packaging [63] and PEG Halloysite nanotubes (HNTs) up to 15 Films for packaging [64] on PP mat UiO-66-NH 2 and HKUST-1 up to 40 Materials for personal protective equipment against toxic chemicals [65] Typically, the exploited additives are solid nanoparticles that range from inorganic salts (e.g., Ag salts), to metal oxides (TiO 2 , Cu 2 O), carbon-based nanomaterials (graphene, graphene oxide, carbon nanotubes), zeolites, metal-organic frameworks (MOFs), clays and layered double hydroxides (LDHs). The addition of organic molecules and ionic liquids to Pebax matrices was investigated as well.…”

“…The adhesive properties of Pebax were exploited to attach MOF particles (UiO-66-NH 2 and HKUST-1) to an inert PP substrate in order to develop materials for personal protective equipment against toxic chemicals [65]. The performance of the composites against the chemical warfare agent simulant 2-chloroethyl ethyl sulfide (CEES) depends on the type of Pebax used.…”