MOF shaping using 2 or 3 phase technology

Abstract

This disclosure provides compositions, systems and methods for adsorbing contaminants, e.g., in food containers, drug packaging and drug delivery devices, using polymers entrained with metal-organic frameworks (MOFs). Also provided are shaped forms of materials comprising MOFs, and related methods to provide the shaped forms. Such methods include extrusion, injection molding and 3D printing techniques, among others.

Description

Attorney Docket No. CSP-0618PC(310316-02710) PATENTMOF SHAPING USING 2 OR 3 PHASE TECHNOLOGYCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application No. 63 / 759,703, titled “MOF SHAPING USING 2 OR 3 PHASE TECHNOLOGY”, filed February 18, 2025, which is incorporated herein by reference in its entirety.FIELD

[0002] This disclosure relates to compositions, systems and methods for adsorbing contaminants, e.g., in food, drug and cosmetic containers, using polymers entrained with metalorganic frameworks.BACKGROUND

[0003] Molecular contamination is an important problem that can significantly affect the quality and performance of a food, cosmetic formulation or drug, and therefore the health of consumers. Indeed, depending on the thermal environment and the storage conditions of the products, certain polluting and / or odorous molecules coming from the air (humidity), from the degassing of the constituent materials of the packaging as well as from the maturation of certain foods (ethylene in the case of climacteric fruits) can accelerate the processes of ripening, degradation, etc. Thanks to their organized microporous structure, which gives them remarkable adsorption capacities, Metal-Organic Frameworks (MOFs) prove to be the solids of choice for trapping molecules of the contaminating substances.

[0004] Metal-Organic Frameworks (MOFs), a type of hybrid organic-inorganic material, is a novel class of nanoporous crystalline materials that have received a lot of interest from the scientific community in the recent decade. Because of the nature of these materials, an a priori limitless number of structures with varying physicochemical characteristics may be designed. The high degree of versatility in terms of structure, pore size and shape, and internal surface chemistry allows a wide range of interesting applications in a variety of sectors such as adsorption and catalysis { 1 }. One of the most essential properties of these porous systems is the relatively weak nature of their interactions, which maintains structural cohesion. The structure of organic-inorganic hybrid materials is frequently more flexible than that of purely inorganic porous materials, such as zeolites, because it is based primarily on coordination chemistry and weak interactions between organic ligands (dispersion, hydrogen bonds).Attorney Docket No. CSP-0618PC(310316-02710) PATENT

[0005] The synthesis of MOFs is most often done using hydrothermal methods – or solvothermal methods, when the solvent is not water {2}. Several precursors are mixed in a liquid (aqueous, non-aqueous, ionic) and react within a confined medium (metal autoclave with Teflon reactor) at a temperature higher than the boiling temperature and, consequently, at a pressure higher than the atmospheric pressure (autogenous pressure). Alternative methods have been developed such as microwave irradiation assisted synthesis, ultrasonic, mechanical, electrochemical, and liquid ionic spray-drying methods which allow a reduction of the synthesis time and a better control of the crystallite size {3,4}.

[0006] MOFs are therefore composed of an inorganic and an organic part. The first part can come from 3p metals such as aluminum, transition metals, rare earths or alkaline earths such as magnesium. The chemical reactivity of the inorganic part can thus be very different according to the chosen element. Thus, the inorganic brick can assemble in different ways in the presence of ligands. Besides the inorganic part, the organic part is also very diverse. Since the sole requirement is the presence of groups that can complex with the metal, the rest of the ligand (spacer) can be chosen / modified almost infinitely. Thus, a very large number of ligands can be found in the listed MOFs, some of which are shown in FIGs. l(a)-l(g) and FIGs. 2(a)-2(b). So far, the metal anchoring groups used have mostly been carboxylic acids, phosphonic acids, imidazoles / triazoles / pyrazoles or other electron-donating groups such as pyridine or sulfonates. The number and position of these anchoring groups can also be very varied (typically between 2 and 4 complexing groups per spacer) with for example the ligands benzene- 1,3-dicarboxylic acid (isophthalic acid), benzene- 1,4-dicarboxylic acid (terephthalic acid; BDC), benzene- 1, 3, 5-tricarboxylic acid (trimesic acid, BTC), benzene- 1,2,4-tricarboxylic acid (trimellitic acid), benzene- 1,2, 4, 5-tetracarboxylic acid (pyromellitic acid, BTEC) etc. Most of these ligands are composed of aromatic rings, which confer rigidity and therefore stability to the structure.

[0007] Recently, MOFs have proven to be very interesting porous materials and alternatives to traditional materials (activated carbons, zeolites) for industrial applications, due to their higher pore volume than zeolites, their pore size, their structure and their adjustable chemical nature. Indeed, depending on the size and the chemical characteristics of the molecule to be adsorbed, MOFs with specific adsorption sites located on the organic ligands or on the metal atoms and with well-defined pore sizes can be produced almost " custom-made” by modifying the nature ofAttorney Docket No. CSP-0618PC(310316-02710) PATENTthe metal ion and / or the organic ligand that make up its hybrid framework. MOFs such as MIL-53(A1), MIL-53(Fe) {6,7}, MIL-47(V) {7}. MIL-101(Cr) {8} and ZIF-8(Zn) {9} have thus been used for the trapping of aromatic hydrocarbons. Indeed, the existence of π-π and cation-π type interactions between the framework of the MOF, with the phenyl groups or the accessible metal cations, and the aromatic pollutant promote the adsorption of VOCs such as BTEX. For benzene (B), the adsorption capacities measured in the case of MIL-101(Cr) (~13 mmol / g) are markedly higher than those of activated carbon (8 mmol / g) and HZSM-5 zeolite (1.9 mmol / g), making this MOF a good candidate for adsorption applications {10}. The carbonyl compounds are adsorbed by the MOFs thanks to van der Waals type interactions, cation-π (metal ion of the MOF and carbonyl group of the adsorbate), or polar-polar which make it possible to improve the capacities of MOF adsorption. In this family of compounds, the most studied molecule is formaldehyde (HCHO), known for its high toxicity. Jiang et al. thus showed that Cu-MOFs (copper-based MOFs) {11} exhibit excellent adsorption performance with respect to formaldehyde thanks to the presence of the metal ion and the amine groups of the organic ligand. Zheng et al. have shown that MOFs with ethylenediamine grafts improve the adsorption of formaldehyde under conditions of high relative humidity (5.49 mmolHCHO / gMOF) { 12} and that the adsorption of the carbonyl compound on this MOF is reversible, allowing regeneration of the adsorbent.

[0008] Water present in the form of vapor in the atmosphere, often expressed in terms of relative humidity, is an essential parameter to take into account in many industrial processes because it can be a major source of contamination by affecting the overall performance of equipment, instruments, drugs. Among the potential adsorbents of this humidity, mention may be made of anhydrous salts {13}, clays { 14, 15}, activated carbons { 16-18}, silica gels { 14, 19}, as well as aluminosilicon zeolites which are widely used industrially, due to their high water adsorption capacity of between 0.011 gH2O / gzeoliteand 0.33 gH2O / gzeolite{20-24} and their ability to trap water molecules present in trace amounts in the atmosphere {20-24}. On the other hand, their regeneration is very energy-intensive because of the strong interactions existing between the water molecules and the aluminosilicic framework of the zeolite, which require the application of high temperatures to desorb the water molecule. The use of MOFs for water trapping has shown the great potential of these materials for this type of application. Indeed, in addition to their high adsorption capacities (microcrystals of MOF-801: 22.5 wt.% at 25°C andAttorney Docket No. CSP-0618PC(310316-02710) PATENTp / p° = 0.1; MOF-841: 44 wt.% at 25°C and p / p° = 0.3), higher than that of the LTA type zeolite (24-25 wt.%). Furthermore, these Zr(IV)-MOFs are both stable in the presence of water and regenerable at room temperature {25}.

[0009] MOFs are also interesting porous materials for the separation and storage of gases {26,27}, in the same way as activated carbons and zeolites. Their advantage compared to activated carbons, whose pore size is heterogeneous, is the possibility of adjusting the geometry and the size of their porosity according to the molecule to be adsorbed by varying the nature of the organic ligand and that of the metal ion composing the frame. The study of oxygen storage, carried out on HKUST-1 and NU-125 showed that at pressures below 2 bar, these MOFs have oxygen adsorption capacities greater than NaX zeolite, which is very promising for the intended application, and that at p = 30 bar the storage capacities are respectively 6, 8.3 and 2 mol / kg at 25°C {28}.

[0010] Though some commercial products based on MOF materials have been launched recently {29}, there are still some challenging issues to be addressed for the application of MOFs in real implementation, including the shaping of bulk MOFs or composite based MOFs.Conventional syntheses of these MOFs generally result in powder form with crystals with dimensions smaller than tens to hundreds of microns. However, these powders cannot be used as such for the majority of industrial applications, due to certain disadvantages of powdery materials, such as difficulty in handing, ease in spilling, poor mass / heat transfer rate, high pressure drop across packed bed systems, unsatisfactory mechanical stability, and low volumetric efficiency in a container {30, 31 }. Practical applications can impose requirements for sspecific size, shape, hardness, mechanical strength and / or microscopic morphology. These requirements can be met with the use of polymers (to use form composite materials) or binders with MOFs in industrial applications.

[0011] Many preparation methods for the shaped bulks or composites of MOF crystals have been reported, and the representative ones include granulation {32-34}, extrusion {35-37}, spray drying {38-40}, pressing {41-43}, sol-gel method {44-46} and layer-by-layer deposition {47-49}.

[0012] There remains a need for materials and methods for adapting MOFs to commercial and industrial requirements. Also required are shaped forms of the materials, including but not limited to pellets, granules, thin films, foams, gels, and the like, which are advantageous forAttorney Docket No. CSP-0618PC(310316-02710) PATENTindustrial use, and related methods for manufacturing the shaped forms.SUMMARY

[0013] Accordingly, in one aspect, provided herein is an entrained polymer comprising a metal-organic framework (“MOF”). In addition to the MOF, the entrained polymer comprises a base polymer and, optionally, a channeling agent.

[0014] In another aspect, a package is provided for reducing contaminating substances in a closed container having a product located therein, the package comprising an entrained polymer as disclosed herein.

[0015] Also disclosed herein is a shaped form comprising an entrained polymer as disclosed herein. In some embodiments, the shaped form is chosen from a pellet, a granule, a thin film, a foam, and a gel.

[0016] Also disclosed herein, in another aspect, is a pellet comprising an entrained polymer as disclosed herein.

[0017] Also disclosed herein, in another aspect, is a method for manufacturing a pellet as disclosed herein, the method comprising the step of 3D printing.

[0018] Also provided herein is a film comprising an entrained polymer as disclosed herein.

[0019] Also provided herein is a method for removing one or more contaminating substances from the headspace of a package, the method comprising the step of placing an entrained polymer as disclosed herein in the package.

[0020] Also provided herein is a method for removing one or more contaminating substances from a product, the method comprising the step of placing the product in a package as disclosed herein. In some embodiments, at least one of the one or more contaminating substances is volatile.

[0021] Also provided herein is a method for reducing the amount of one or more volatile contaminating substances in a quantity of gas, the method comprising the step of enclosing the quantity of gas in a package as disclosed herein. Also provided herein is a method for preventing contamination of a product by one or more volatile contaminating substances, the method comprising the step of placing the product in a package as disclosed herein. In some embodiments, the one or more volatile contaminating substances is a hydrocarbon. In some embodiments, the hydrocarbon has 16 carbons or fewer, optionally 12 carbons or fewer, optionally 10 carbons or fewer, optionally 8 carbons or fewer.Attorney Docket No. CSP-0618PC(310316-02710) PATENT

[0022] Also provided herein is a method for reducing the amount of moisture in a quantity of gas, the method comprising the step of enclosing the quantity of gas in a package as disclosed herein. Also provided herein is a method for preventing contamination of a product by moisture, the method comprising the step of placing the product in a package as disclosed herein.

[0023] Also provided herein is the use of a package as disclosed herein for the removal of one or more contaminating substances from the headspace of the package.

[0024] Also provided herein is the use of a package as disclosed herein for the removal of one or more contaminating substances from a product contained within the package. In some embodiments, at least one of the one or more contaminating substances is volatile.

[0025] Also provided herein is the use of a package as disclosed herein for the prevention of contamination of a product by one or more volatile contaminating substances in the package.BRIEF DESCRIPTION OF THE DRAWINGS

[0026] The disclosure will be described in conjunction with the following drawings in which like reference numerals designate like elements and, wherein:

[0027] FIG. 1(a) depicts fumaric acid as an organic compound optionally used in MOFs.

[0028] FIG. 1(b) depicts 1 H-imidazole-4,5-dicarboxylic acid as an organic compound optionally used in MOFs.

[0029] FIG. 1(c) depicts terephthalic acid as an organic compound optionally used in MOFs.

[0030] FIG. 1(d) depicts 2,4,6-trihydroxybenzene-l,3,5-trisulfonic acid as an organic compound optionally used in MOFs.

[0031] FIG. 1(e) depicts 1,3,5-benzenetricarboxylic acid as an organic compound optionally used in MOFs.

[0032] FIG. 1(f) depicts l,4-bis(phosphomethyl)piperazine as an organic compound optionally used in MOFs.

[0033] FIG. 1(g) depicts isophthalic acid as an organic compound optionally used in MOFs.

[0034] FIG. 2(a) depicts l,3,5-tris(4-carboxyphenyl)benzene as an organic compound optionally used in MOFs.

[0035] FIG. 2(b) depicts 1,3,5-tri( lH-pyrazol-4-yl)benzene as an organic compound optionally used in MOFs.

[0036] FIG. 3 is a perspective view of a plug formed of an entrained polymer that may be deposited onto a substrate according to methods of the disclosed concept.Attorney Docket No. CSP-0618PC(310316-02710) PATENT

[0037] FIG. 4 is a cross section taken along line 2-2 of FIG. 3.

[0038] FIG. 5 is a cross section similar to that of FIG. 4, showing a plug formed of another embodiment of an entrained polymer according to an optional embodiment of the disclosed concept.

[0039] FIG. 6 is a schematic illustration of an entrained polymer according to an optional embodiment of the disclosed concept.

[0040] FIG. 7 is a cross sectional view of a sheet or film formed of an entrained polymer according to an optional embodiment of the disclosed concept, adhered to a barrier sheet substrate.

[0041] FIG. 8 is a cross section of a package that may be formed using an entrained polymer according to an optional embodiment of the disclosed concept.

[0042] FIG. 9 is a perspective view of an exemplary package incorporating entrained polymer films according to an optional aspect of the disclosed concept.

[0043] FIG. 10 shows the X-ray diffractograms of (i) polycrystalline AIFu and (ii) the material of Example 2; horizontal axis: 2-theta; vertical axis: intensity (au).

[0044] FIG. 11(a) is an SEM image of the material of Example 2.

[0045] FIG. 11(b) is an SEM image of the material of Example 2 at a magnification 10X greater than that of the image in FIG. 11(a).

[0046] FIG. 12 shows an N2adsorption – desorption isotherm at 77 K of the material of Example 2; horizontal axis: relative pressure (p / p°); vertical axis: amount adsorbed (cm3 / g STP).

[0047] FIG. 13 shows a TGA curve of the material of Example 2; horizontal axis: temperature (°C); vertical axis: mass (%).

[0048] FIG. 14 shows a water adsorption isotherm at 25 °C of the material of Example 2; horizontal axis: relative pressure (p / p°); vertical axis: amount adsorbed (cm3 / g STP).

[0049] FIG. 15 shows the kinetics of water adsorption isotherm at 22 °C and 80% RH of the material of Example 2; horizontal axis: time (hours); vertical axis: moisture uptake (mg / g).

[0050] FIG. 16 shows an n-hexane adsorption isotherm at 25 °C of the material of Example 2; horizontal axis: relative pressure (p / p°); vertical axis: amount adsorbed (mg / g STP).

[0051] FIG. 17(a) depicts the A520-2P-59-PP material in extruded form.

[0052] FIG. 17(b) depicts the A520-2P-59-PP material in the form of granules.Attorney Docket No. CSP-0618PC(310316-02710) PATENT

[0053] FIG. 18(a) is an SEM image of the A520-2P-59-PP material at a first magnification.

[0054] FIG. 18(b) is an SEM image of the A520-2P-59-PP material at a second magnification.

[0055] FIG. 18(c) is an SEM image of the A520-2P-59-PP material at a third magnification.

[0056] FIG. 19 shows the kinetics of water adsorption isotherm at 22 °C and 80% RH of the obtained granulates of 2-phase PP material; horizontal axis: time (days); vertical axis: moisture uptake (mg / g); (i) A520-2P-39-PP (ii) A520-2P-49-PP (iii) A520-2P-59-PP (iv) A520-2P-68-PP.

[0057] FIG. 20 shows the kinetics of water adsorption isotherm at 22 °C and 80% RH of the obtained granulates of 2-phase Exact™ 3040 material; horizontal axis: time (days); vertical axis: moisture uptake (mg / g) (i) A520-2P-36-Exact (ii) A520-2P-43-Exact (iii) A520-2P-48-Exact.

[0058] FIG. 21(a) is an SEM image of the A520-3P-54-PP material.

[0059] FIG. 21(b) is an EDX image of the A520-3P-54-PP material for carbon.

[0060] FIG. 21(c) is an EDS image of the A520-3P-54-PP material for oxygen.

[0061] FIG. 21(d) is an EDS image of the A520-3P-54-PP material for aluminum.

[0062] FIG. 22 shows the kinetics of water adsorption isotherm at 22 °C and 80 % RH of the obtained granulates of 3-phase material with PP; horizontal axis: time (days); vertical axis: moisture uptake (mg / g) (i) A520-3P-36-PP (ii) A520-3P-44-PP (iii) A520-3P-54-PP (iv) A520-3P-62-PP.

[0063] FIG. 23 shows the kinetics of water adsorption isotherm at 22 °C and 80 % RH of the obtained granulates of 3-phase material with Exact™ 3040; horizontal axis: time (days); vertical axis: moisture uptake (mg / g) (i) A520-3P-36-Exact (ii) A520-3P-44-Exact (iii) A520-3P-54-Exact (iv) A520-3P-62-Exact.

[0064] FIG. 24(a) provides a first view of a 3D printed pellet using A520-3P-54-PP.

[0065] FIG. 24(b) provides a second view of the 3D printed pellet of FIG. 24(a).

[0066] FIG. 25 shows the kinetics of water adsorption isotherm at 22 °C and 80 % RH of 3D printed pellets using A520-3P-54-PP up to 450 days; horizontal axis: time (days); vertical axis: moisture uptake (mg / g).

[0067] FIG. 26 shows the kinetics of water adsorption isotherm at 22 °C and 80 % RH of 3D printed pellets using A520-3P-54-PP up to 200 days; horizontal axis: time (days); vertical axis: moisture uptake (mg / g).Attorney Docket No. CSP-0618PC(310316-02710) PATENT

[0068] FIG. 27 provides a photo of the obtained MOF A520 films of A520-3P-32-Exact.

[0069] FIG. 28(a) depicts an SEM image coupled with EDX analysis for carbon of the MOF A520 (44 wt. %) films of 3-phase material (with Exact™ 3040 as main polymer and EVA as channeling agent).

[0070] FIG. 28(b) depicts an SEM image coupled with EDX analysis for aluminum of the MOF A520 (44 wt. %) films of 3-phase material (with Exact™ 3040 as main polymer and EVA as channeling agent).

[0071] FIG. 29 shows the kinetics of water adsorption at 22 °C and 80 % RH of the obtained films of 3-phase Exact™ 3040 material; horizontal axis: time (days); vertical axis: moisture uptake (mg / g) (i) A520-3P-32-Exact (ii) A520-3P-44-Exact (iii) A520-3P-52-Exact.

[0072] FIG. 30(a) shows an adsorption-desorption isotherm of oxygen at 20 °C of the MOF A520 powder; horizontal axis: O2pressure; vertical axis: O2uptake (mmol / g).

[0073] FIG. 30(b) shows an adsorption-desorption isotherm of oxygen at 20 °C of the entrained polymer films comprising MOF A520 powder in the following formulation: A520-3P-44-Exact.

[0074] FIG. 30(c) shows an adsorption-desorption isotherm of oxygen at 20 °C of the entrained polymer films comprising MOF A520 powder in the following formulation: A520-3P-52-Exact.

[0075] FIG. 31(a) shows a first view of a monoinjected part of 3-phase PP material containing 55 wt.% of MOF A520, which is optionally shaped and configured to adsorb humidity in an inhaler.

[0076] FIG. 31(b) shows a second view of the monoinjected part of FIG. 31(b).

[0077] FIG. 32 shows the kinetics of water adsorption at 22 °C and 80 % RH of the obtained monoinjected part of 2 and 3-phase PP material; horizontal axis: time (days); vertical axis: moisture uptake (mg / g) (i) A520-3P-31-PP (ii) A520-2P-55-PP (iii) A520-3P-55-PP.

[0078] FIG. 33 shows the mechanical properties (deformation) of the obtained monoinjected part of 2 and 3-phase PP material; horizontal axis: deformation (mm); vertical axis: applied compression force (N) (i) 4A-3P-55-PP (ii) A520-3P-31-PP (iii) A520-3P-55-PP (iv) A520-2P-55-PP.

[0079] FIG. 34 shows MOF CAU-10-H (aluminum isophthalate MOF) structure{Al(OH)(C8H4O4)}, in accordance with the prior art.Attorney Docket No. CSP-0618PC(310316-02710) PATENT

[0080] FIG. 35 shows SEM image of MOF CAU-10-H crystals in powder form.

[0081] FIG. 36 shows the kinetics of water adsorption at 22 °C and 80 % RH of MOF CAU- 10-H in powder form; horizontal axis: time (days); vertical axis: moisture uptake (mg / g).

[0082] FIG. 37 depicts SEM images coupled with EDX analysis of the MOF CAU-10-H granulates (CAU-3P-64-PP).

[0083] FIG. 38 shows the kinetics of water adsorption at 22 °C and 80 % RH of obtained MOF CAU-10-H granulates of 2-phase material with PP; horizontal axis: time (days); vertical axis: moisture uptake (mg / g) (i) CAU-2P-33-PP (ii) CAU-2P-48-PP (iii) CAU-2P-51-PP (iv) CAU-2P-59-PP (v) CAU-2P-68-PP.

[0084] FIG. 39 shows the kinetics of water adsorption at 22 °C and 80 % RH of obtained MOF CAU-10-H granulates of 3-phase material with PP; horizontal axis: time (days); vertical axis: moisture uptake (mg / g) (i) CAU-3P-47-PP (ii) CAU-3P-49-PP (iii) CAU-3P-61-PP (iv) CAU-3P-64-PP (v) CAU-3P-66-PP.

[0085] FIG. 40 shows MOF 801 (zirconium fumarate MOF) structure {Zr6C24H16O32}, in accordance with the prior art.

[0086] FIG. 41 shows SEM image of MOF 801 crystals in powder form.

[0087] FIG. 42 shows the kinetics of water adsorption at 22 °C and 80 % RH of MOF 801 in powder form; horizontal axis: time (days); vertical axis: moisture uptake (mg / g).

[0088] FIG. 43 depicts SEM images coupled with EDX analysis of the MOF 801 granulates (801-2P-49-PP).

[0089] FIG. 44 shows the kinetics of water adsorption at 22 °C and 80 % RH of obtained MOF 801 granulates of 2-phase material with PP; horizontal axis: time (days); vertical axis: moisture uptake (mg / g) (i) 801-2P-36-PP (ii) 801-2P-49-PP.

[0090] FIG. 45 shows the kinetics of water adsorption at 22 °C and 80 % RH of obtained MOF 801 granulates of 3-phase material with PP; horizontal axis: time (days); vertical axis: moisture uptake (mg / g) (i) 801-3P-45-PP (ii) 801-3P-52-PP.

[0091] FIG. 46 shows the kinetics of water adsorption at 22 °C and 80 % RH of obtained MOF 801 granulates of 2-phase material with PP; horizontal axis: time (days); vertical axis: moisture uptake (mg / g) (i) 801-2P-36-PP (ii) 801-2P-49-PP.

[0092] FIG. 47 shows the kinetics of water adsorption at 22 °C and 80 % RH of obtained MOF 801 granulates of 3-phase material with PP; horizontal axis: time (days); vertical axis:Attorney Docket No. CSP-0618PC(310316-02710) PATENTmoisture uptake (mg / g) (i) 801-3P-45-PP (ii) 801-3P-52-PP.

[0093] FIG. 48 shows MOF MIL- 160 structure {AlCeHsOe}.

[0094] FIG. 49 shows SEM image of MIL- 160 crystals in powder form.

[0095] FIG. 50 shows the kinetics of water adsorption of MIL- 160 in powder form (i) 30 °C and 65 % RH (ii) 25 °C and 60 % RH (iii) 22 °C and 80 % RH (iv) 30 °C and 80 % RH (v) 40 °C and 75 % RH; horizontal axis: time (days); vertical axis: moisture uptake (mg / g).

[0096] FIG. 51 shows the kinetics of water adsorption of MIL- 160 in powder form (i) 30 °C and 65 % RH (ii) 25 °C and 60 % RH (iii) 22 °C and 80 % RH (iv) 30 °C and 80 % RH (v) 40 °C and 75 % RH; horizontal axis: time (days); vertical axis: moisture uptake (mg I g)

[0097] FIG. 52 shows TGA analysis of MIL-160 powder; horizontal axis: temperature ( °C); vertical axis: weight loss (%).

[0098] FIG. 53 shows the kinetics of water adsorption at 22 °C and 80 % RH of obtained MIL-160 granulates of 3-phase material with PP; horizontal axis: time (days); vertical axis: moisture uptake (mg / g) (i) 160-3P-16-PP (ii) 160-3P-43-PP (iii) 160-3P-50-PP: horizontal axis: time (h); vertical axis: mg water I g MOF.

[0099] FIG. 54 shows RH monitoring in 48 mL vial at 30°C, 65% RH for MOF A520 powder and 3 phase MOF A520 film; horizontal axis: water loading in MOF material (wt.%); vertical axis: relative humidity at equilibrium in the closed vial (i) MOF A520 powder (ii) MOF A520-3P-50-PP; horizontal axis = saturation rate (%); vertical axis = RH.DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0100] While systems, devices and methods are described herein by way of examples and embodiments, those skilled in the art recognize that the systems, devices and methods of the presently disclosed technology are not limited to the embodiments or drawings described.Rather, the presently disclosed technology covers all modifications, equivalents and alternatives falling within the spirit and scope of the appended claims. Any headings used herein are for organizational purposes only and are not meant to limit the scope of the description or the claims.

[0101] Disclosed herein is an entrained polymer comprising a metal-organic framework (“MOF”). In addition to the MOF, the entrained polymer comprises a base polymer and, optionally, a channeling agent.

[0102] In some embodiments, the MOF is substantially in the form of nanocrystals. In someAttorney Docket No. CSP-0618PC(310316-02710) PATENTembodiments, the average nanocrystal size is below 125 nm, optionally below 100 nm, optionally below 75 mm. In some embodiments, the average nanocrystal size is about 60 nm.

[0103] In some embodiments, the BET surface area is 500 m2 / g or larger, optionally 600 m2 / g or larger, optionally 700 m2 / g or larger, optionally 800 m2 / g or larger, optionally 900 m2 / g or larger, optionally 1000 m2 / g or larger.

[0104] In some embodiments, the entrained polymer further comprises a porous material. The porous material can target one or more volatile organic compounds (“VOCs”) and I or moisture.

[0105] In some embodiments, the entrained polymer further comprises a zeolite. In some embodiments, the entrained polymer further comprises a silica gel. In some embodiments, the entrained polymer further comprises a porous carbon material.

[0106] In certain embodiments, the entrained polymer includes a combination or mixture of more than MOF. In other embodiments, the entrained polymer includes a combination or mixture of one or more MOFs with one or more of zeolite, silica gel. and carbon.

[0107] In certain embodiments, the base polymer of the entrained polymer ranges from 10% to 70%, optionally from 20% to 60%, optionally from 20% to 50%, optionally from 20% to 40%. optionally from 30% to 70%, optionally from 30% to 60%, from 30% to 50%, optionally from 40% to 70%, optionally from 40% to 60%, optionally from 40% to 50% by weight of the entrained polymer.

[0108] In certain embodiments, the entrained polymer includes from 30% to 80%, optionally 35% to 75%, optionally 40% to 70%, optionally about 60% by weight of MOF.

[0109] In certain embodiments, the entrained polymer comprises a channeling agent.

[0110] In certain embodiments, the channeling agent is in a range of 1% to 16%, optionally 1% to 14%, optionally from 1% to 12%, optionally from 1% to 10%, optionally from 1% to 8%, optionally from 1% to 6%, optionally from 1% to 5%, optionally from 1% to 4%, optionally from 2% to 16%, optionally from 2% to 14%, optionally from 2% to 12%, optionally from 2% to 10%, optionally from 2% to 8%, optionally from 2% to 6%, optionally from 2% to 5%, optionally from 2% to 4%, optionally from 4% to 12%, optionally from 4% to 10%, optionally from 4% to 8%, optionally from 4% to 6%, optionally from 4% to 5%, optionally from 6% to 12%, optionally from 6% to 10%, optionally from 6% to 8%, optionally from 8% to 12%, optionally from 8% to 10% by weight of the entrained polymer.Attorney Docket No. CSP-0618PC(310316-02710) PATENT

[0111] In certain embodiments, the metal-organic framework comprises Al(TIT) or Zr(IV). In certain embodiments, the metal-organic framework comprises an organic polycarboxylic acid, or a salt thereof. In certain embodiments, the organic polycarboxylic acid is chosen from an organic dicarboxylic acid and an organic tercarboxylic acid. In certain embodiments, the organic dicarboxylic acid is chosen from succinic acid, maleic acid, fumaric acid, malic acid, and phthalic acid, or a mixture thereof.

[0112] In some embodiments, the entrained polymer absorbs moisture from a humid environment. In some embodiments, the entrained polymer absorbs moisture from exposure to 80% relative humidity at 22 °C.

[0113] In some embodiments, the entrained polymer absorbs at least 50 mg I g, optionally at least 100 mg I g, optionally at least 150 mg / g, optionally at least 200 mg / g, optionally at least 250 mg / g water within 10 days of exposure to 80% relative humidity at 22 °C.

[0114] In some embodiments, the entrained polymer absorbs at least 100 mg / g, optionally at least 150 mg / g, optionally at least 200 mg / g, optionally at least 250 mg / g water within 20 days of exposure to 80% relative humidity at 22 °C.

[0115] In some embodiments, the entrained polymer absorbs at least 100 mg / g, optionally at least 150 mg / g, optionally at least 200 mg / g, optionally at least 250 mg / g, optionally at least 300 mg / g water within 50 days of exposure to 80% relative humidity at 22 °C.

[0116] In some embodiments, the entrained polymer absorbs at least 100 mg / g, optionally at least 150 mg / g, optionally at least 200 mg / g, optionally at least 250 mg / g, optionally at least 300 mg / g water within 100 days of exposure to 80% relative humidity at 22 °C.

[0117] Also provided herein is a shaped form comprising an entrained polymer as disclosed herein. In some embodiments, the shaped form is chosen from a pellet, a granule, a thin film, a foam, and a gel.

[0118] Also provided herein is a pellet comprising an entrained polymer as disclosed herein. In some embodiments, the entrained polymer comprises a metal-organic framework (“MOF”). In some embodiments, the MOF comprises an organic polycarboxylic acid, or a salt thereof. In some embodiments, the organic dicarboxylic acid is chosen from succinic acid, maleic acid, fumaric acid, malic acid, and phthalic acid, or a mixture thereof. In some embodiments, the MOF comprises fumaric acid. In some embodiments, the MOF is aluminum fumarate.

[0119] In some embodiments, the entrained polymer of the pellet consists of 30% to 80%,Attorney Docket No. CSP-0618PC(310316-02710) PATENToptionally 35% to 75%, optionally 40% to 70% by weight of MOF.

[0120] In some embodiments, the entrained polymer of the pellet consists of 10% to 70%, optionally from 20% to 60%, optionally from 20% to 50%, optionally from 20% to 40%, optionally from 30% to 50%, optionally from 40% to 50% by weight of base polymer.

[0121] In some embodiments, the base polymer is chosen from ethylene vinyl acetate, thermoplastic elastomers, thermoplastic polymers, e.g.. polyolefins such as polypropylene and polyethylene, polyisoprene, polybutadiene, polybutene, polysiloxane, polycarbonates, polyamides, ethylene / alpha olefin copolymers, ethylene / 1-butene copolymers, ethylene / 1-hexene copolymers, ethylene-vinyl acetate copolymers, ethylene- methacrylate copolymer, poly(vinyl chloride), polystyrene, polyesters including polylactic acid, poly anhydrides, polyacrylonitrile, polysulfones, polyacrylic ester, acrylic, polyurethane and polyacetal, or copolymers or mixtures thereof. In some embodiments, the base polymer is polypropylene.

[0122] In some embodiments, the base polymer is an Exact™ ethylene / alpha-olefin copolymer. In some embodiments, the base polymer is Exact™ 3040.

[0123] Other ethylene / alpha olefin copolymers can include copolymers of ethylene with an alpha olefin chosen from 1-butene, 1 -pentene, 1-hexene, 1-heptene, 1-octene, 1 -nonene, any one of which can include one or more more methyl, ethyl, or propyl substituents, ethyl, methyl, or dimethyl- substituted 1-decene; 1-dodecene, and styrene.

[0124] In some embodiments, the entrained polymer of the pellet contains a channeling agent. In some embodiments, the channeling agent is chosen from a polyglycol such as polyethylene glycol (PEG), ethylene-vinyl acetate (EVA), ethylene-vinyl alcohol (EVOH), polyvinyl alcohol (PVOH), glycerin polyamine, polyurethane and polycarboxylic acid including polyacrylic acid or polymethacrylic acid. In some embodiments, the entrained polymer of the pellet does not contain a channeling agent.

[0125] In some embodiments, the pellet is cylindrical in shape.

[0126] In some embodiments, the height of the cylindrical pellet is 2 mm or larger, optionally 3 mm or larger, optionally 5 mm or larger, optionally 10 mm or larger, optionally 20 mm or larger. In some embodiments, the height of the cylindrical pellet is 30 mm or smaller, optionally 20 mm or smaller, optionally 15 mm or smaller, optionally 10 mm or smaller, optionally 5 mm or smaller. In some embodiments, the height of the cylindrical pellet is about 5 mm.Attorney Docket No. CSP-0618PC(310316-02710) PATENT

[0127] In some embodiments, the diameter of the cylindrical pellet is 6 mm or larger, optionally 8 mm or larger, optionally 10 mm or larger, optionally 15 mm or larger, optionally 20 mm or larger. In some embodiments, the diameter of the cylindrical pellet is 40 mm or smaller, optionally 30 mm or smaller, optionally 25 mm or smaller, optionally 20 mm or smaller, optionally 16 mm or smaller, optionally 12 mm or smaller. In some embodiments, the diameter of the cylindrical pellet is about 5 mm.

[0128] In some embodiments, the pellet absorbs moisture from a humid environment. In some embodiments, the pellet absorbs moisture from exposure to 80% relative humidity at 22 °C.

[0129] In some embodiments, the pellet absorbs at least 20 mg / g, optionally at least 40 mg / g, optionally at least 60 mg I g, optionally at least 80 mg / g water within 5 days of exposure to 80% relative humidity at 22 °C.

[0130] In some embodiments, the pellet absorbs at least 40 mg / g, optionally at least 60 mg / g, optionally at least 80 mg I g, optionally at least 100 mg / g water within 10 days of exposure to 80% relative humidity at 22 °C.

[0131] In some embodiments, the pellet absorbs at least 60 mg / g, optionally at least 80 mg / g, optionally at least 100 mg / g, optionally at least 120 mg / g water within 25 days of exposure to 80% relative humidity at 22 °C.

[0132] In some embodiments, the pellet absorbs at least 80 mg / g, optionally at least 120 mg / g, optionally at least 160 mg / g, optionally at least 200 mg / g water within 100 days of exposure to 80% relative humidity at 22 °C.

[0133] Also provided herein is a method for manufacturing a shaped form as disclosed herein, the method comprising the step of 3D printing. In some embodiments, the shaped form is a pellet. In some embodiments, the 3D printing uses fused deposition modeling.

[0134] Also provided herein is a film comprising an entrained polymer as disclosed herein. In some embodiments, the entrained polymer comprises a metal-organic framework (“MOF”). In some embodiments, the MOF comprises an organic polycarboxylic acid, or a salt thereof. In some embodiments, the organic dicarboxylic acid is chosen from succinic acid, maleic acid, fumaric acid, malic acid, and phthalic acid, or a mixture thereof. In some embodiments, the MOF comprises fumaric acid. In some embodiments, the MOF is aluminum fumarate.

[0135] In some embodiments, the entrained polymer of the film consists of 15% to 80%,Attorney Docket No. CSP-0618PC(310316-02710) PATENToptionally 20% to 70%, optionally 25% to 65%, optionally 30% to 60% by weight of MOF.

[0136] In some embodiments, the entrained polymer of the film consists of 10% to 70%, optionally from 20% to 60%, optionally from 20% to 50%, optionally from 20% to 40%, optionally from 30% to 50%, optionally from 40% to 50% by weight of base polymer.

[0137] In some embodiments, the entrained polymer of the film contains a channeling agent. In some embodiments, the channeling agent is chosen from a polyglycol such as polyethylene glycol (PEG), ethylene-vinyl acetate (EVA), ethylene- vinyl alcohol (EVOH), polyvinyl alcohol (PVOH), glycerin polyamine, polyurethane and polycarboxylic acid including polyacrylic acid or polymethacrylic acid. In some embodiments, the entrained polymer of the film does not contain a channeling agent.

[0138] In some embodiments, the thickness of the film is at or below 500 pm, optionally at or below 450 pm, optionally at or below 400 pm, optionally at or below 350 pm, optionally at or below 300 pm, optionally at or below 250 pm.

[0139] In some embodiments, the thickness of the film is at or above 50 pm, optionally at or above 100 pm, optionally at or above 150 pm, optionally at or above 200 pm, optionally at or above 250 pm, optionally at or above 300 pm, optionally at or above 350 pm.

[0140] In some embodiments, the thickness of the film is between 100 pm and 400 pm, inclusive, optionally between 125 pm and 350 pm, inclusive, optionally between 150 pm and 300 pm, inclusive. In some embodiments, the thickness of the film is about 300 pm.

[0141] In some embodiments, the film absorbs moisture from a humid environment. In some embodiments, the film absorbs moisture from exposure to 80% relative humidity at 22 °C.

[0142] In some embodiments, the film absorbs at least 25 mg I g, optionally at least 50 mg I g, optionally at least 100 mg / g, optionally at least 150 mg / g water within 1 day of exposure to 80% relative humidity at 22 °C.

[0143] In some embodiments, the film absorbs at least 50 mg I g, optionally at least 75 mg I g, optionally at least 100 mg I g, optionally at least 150 mg / g water, optionally at least 175 mg / g water, optionally at least 200 mg / g water within 2 days of exposure to 80% relative humidity at 22 °C.

[0144] In some embodiments, the film absorbs at least 50 mg I g, optionally at least 75 mg / g, optionally at least 100 mg I g, optionally at least 150 mg / g water, optionally at least 175 mg / g water, optionally at least 200 mg / g water within 5 days of exposure to 80% relative humidityAttorney Docket No. CSP-0618PC(310316-02710) PATENTat 22 °C.

[0145] Also provided herein is a injected part for an inhaler comprising an entrained polymer as disclosed herein. The skilled artisan would appreciate that other injection molded parts and structures may be made from the entrained polymer for other uses as well.

[0146] Also provided herein is a package for reducing contaminating substances in a closed container having a product located therein, the package comprising an entrained polymer as disclosed herein.

[0147] In some embodiments, the package includes a closed container defining an interior space therein. A product (optionally a food, cosmetic, or medicament product) is provided within the interior space. A headspace is formed within a volume of the interior space that is not occupied by the product. An entrained polymer as disclosed herein is disposed within the interior space.

[0148] Also provided herein is a method for removing contaminating substances from a product (optionally a food, cosmetic, or medicament product), the method comprising the step of placing the product in a package as disclosed herein.

[0149] Also provided herein is the use of a package as disclosed herein for the removal of contaminating substances from a product (optionally a food, cosmetic, or medicament product) contained within the package.

[0150] Also provided herein is a method for the removal of contaminating substances from an inhalable medicament, the method comprising the step of packaging the inhalable medicament in an inhaler as disclosed herein.

[0151] Also provided herein is a method for the removal of moisture from an inhalable medicament, the method comprising the step of packaging the inhalable medicament in an inhaler as disclosed herein.

[0152] Also provided are embodiments, wherein any embodiment above may be combined with any one or more of these embodiments, provided the combination is not mutually exclusive.

[0153] As used herein, two embodiments are “mutually exclusive” when one is defined to be something which is different than the other.Definitions

[0154] As used herein, the terms below have the meanings indicated.Attorney Docket No. CSP-0618PC(310316-02710) PATENTAbbreviations

[0155] AIFu = aluminum fumarate; BET = Brunauer, Emmett and Teller; DSC = differential scanning calorimetry; LTA = Linde Type A; MOF = metal-organic framework; PXRD = XRD = powder X-ray diffractometry; RH = relative humidity; SEM = scanning electron microscopy; STP = standard temperature and pressure; TGA = thermogravimetric analysis.

[0156] As used herein, the term “active” is defined as capable of acting on, interacting with or reacting with a selected material (e.g., moisture or oxygen) according to an aspect of the disclosure. Examples of such actions or interactions may include absorption, adsorption or release of the selected material. Another example of “active”, which is pertinent to a primary focus of the present disclosure is an agent capable of acting on, interacting with or reacting with a selected material (e.g., moisture) in order to cause release of a released material (e.g., chlorine dioxide).

[0157] As used herein, the term “active agent,” in the context of an entrained polymer, is defined as a material that (1) is preferably immiscible with a base polymer and when mixed and heated with the base polymer and the channeling agent, will not melt, i.e., has a melting point that is higher than the melting point for either the base polymer or the channeling agent, and (2) acts on, interacts or reacts with a selected material. The term “active agent” may include but is not limited to materials that absorb, adsorb or release the selected material(s). The active agents of primary focus in this specification are metal-organic frameworks (MOFs), and mixtures and combinations thereof, that can adsorb contaminating substances.

[0158] As used herein, the term “base polymer” is a polymer optionally having a gas transmission rate of a selected material that is substantially lower than, lower than or substantially equivalent to, that of a channeling agent mixed into the base polymer. The primary function of the base polymer is to provide structure for the entrained polymer.

[0159] Suitable base polymers for use in optional embodiments of the disclosure include ethylene vinyl acetate, thermoplastic elastomers, thermoplastic polymers, e.g., polyolefins such as polypropylene and polyethylene, polyisoprene, polybutadiene, polybutene, polysiloxane, polycarbonates, polyamides, ethylene- vinyl acetate copolymers, ethylene- methacrylate copolymer, poly(vinyl chloride), polystyrene, polyesters including polylactic acid, polyanhydrides, polyacrylonitrile, polysulfones, polyacrylic ester, acrylic, polyurethane andAttorney Docket No. CSP-0618PC(310316-02710) PATENTpolyacetal, or copolymers or mixtures thereof.

[0160] In certain embodiments, the channeling agent has a water vapor transmission rate of at least two times that of the base polymer. In other embodiments, the channeling agent has a water vapor transmission rate of at least five times that of the base polymer. In other embodiments, the channeling agent has a water vapor transmission rate of at least ten times that of the base polymer. In still other embodiments, the channeling agent has a water vapor transmission rate of at least twenty times that of the base polymer. In still another embodiment, the channeling agent has a water vapor transmission rate of at least fifty times that of the base polymer. In still other embodiments, the channeling agent has a water vapor transmission rate of at least one hundred times that of the base polymer.

[0161] As used herein, the term “channeling agent” or “channeling agents” is defined as a material that is immiscible with the base polymer and has an affinity to transport a gas phase substance at a faster rate than the base polymer. Optionally, a channeling agent is capable of forming channels through the entrained polymer when formed by mixing the channeling agent with the base polymer. Optionally, such channels are capable of transmitting a selected material through the entrained polymer at a faster rate than in solely the base polymer.

[0162] As used herein, the term “channels” or “interconnecting channels” is defined as passages formed of the channeling agent that penetrate through the base polymer and may be interconnected with each other.

[0163] As used herein, the term “entrained polymer” is defined as a monolithic material formed of at least a base polymer, an active agent and optionally also a channeling agent entrained or distributed throughout. An entrained polymer thus comprises at least two phases (base polymer and active agent without a channeling agent) or at least three phases (base polymer and active agent with a channeling agent).

[0164] As used herein, the term “monolithic,” “monolithic structure” or “monolithic composition” is defined as a composition or material that does not consist of two or more discrete macroscopic layers or portions. Accordingly, a multi-layer composite is not itself a “monolithic composition,” although it could potentially have a layer that is a monolithic composition.

[0165] As used herein, the term “phase” is defined as a portion or component of a monolithic structure or composition that is uniformly distributed throughout, to give the structure orAttorney Docket No. CSP-0618PC(310316-02710) PATENTcomposition its monolithic characteristics.

[0166] As used herein, the term “selected material” is defined as a material that is acted upon, by, or interacts or reacts with an active agent and is capable of being transmitted through the channels of an entrained polymer.

[0167] As used herein, the term “three phase” is defined as a monolithic composition or structure comprising three or more phases. An example of a three phase composition according to the disclosure is an entrained polymer formed of a base polymer, active agent, and channeling agent. Optionally, a three phase composition or structure may include an additional phase, e.g., a colorant, but is nonetheless still considered “three phase” on account of the presence of the three primary functional components.

[0168] Furthermore, the terms “package,” “packaging” and “container” may be used interchangeably herein to indicate an object that holds, contains or is configured to hold or contain a good, e.g., a food, cosmetic and medicament product, and foodstuffs. Optionally, a package may include a container with a product stored therein. Non-limiting examples of a package, packaging and container include a tray, box, carton, bottle receptacle, vessel, pouch and flexible bag. A pouch or flexible bag may be made from, e.g., polypropylene or polyethylene. The package or container may be closed, covered and / or sealed using a variety of mechanisms including a cover, a lid, lidding sealant, an adhesive and a heat seal, for example. The package or container may be composed or constructed of various materials, such as plastic (e.g., polypropylene or polyethylene), paper, Styrofoam, glass, metal and combinations thereof. In one optional embodiment, the package or container is composed of a rigid or semi-rigid polymer, optionally polypropylene or polyethylene, and preferably has sufficient rigidity to retain its shape under gravity.Exemplary Entrained Polymers

[0169] Conventionally, desiccants, oxygen absorbers and other active agents have been used in raw form, e.g., as loose particulates housed in sachets or canisters within packaging, to control the internal environment of the package. For many applications, it is not desired to have such loosely stored active substances. Thus, the present application provides active entrained polymers comprising active agents, wherein such polymers can be extruded and / or molded into a variety of desired forms, e.g., container liners, plugs, film sheets, pellets and other such structures.Attorney Docket No. CSP-0618PC(310316-02710) PATENT

[0170] Optionally, such active entrained polymers may include channeling agents, such as polyethylene glycol (PEG), ethylene vinyl acetate copolymer (EVA) and vinylpyrrolidone- vinyl acetate copolymer (PVPVA), which form channels between the surface of the entrained polymer and its interior to transmit a selected material (e.g., moisture) to the entrained active agent (e.g., desiccant to absorb the moisture). As explained above, entrained polymers may be two phase formulations (i.e., comprising a base polymer and active agent, without a channeling agent) or three phase formulations (i.e., comprising a base polymer, active agent and channeling agent). Entrained polymers are described, for example, in U. S. Pat. Nos. 5,911.937, 6,080,350, 6,124,006, 6,130,263, 6,194,079, 6,214,255, 6,486,231, 7,005,459, and U. S. Pat. Pub. No.2016 / 0039955, each of which is incorporated herein by reference as if fully set forth.

[0171] Suitable active agents for use in the disclosure include MOFs. In certain embodiments, a mixture or combination of MOFs is used. In certain other embodiments, a mixture or combination of one or more MOFs with one or more of zeolite, silica gel, and carbon, is used. Suitable MOFs include, but are not limited to, MOF A520, MOF CAU-10-H, MOF 810, MIL- 160, and mixtures or combinations thereof. Suitable zeolites include, but are not limited to, MFI, *BEA, and FAU-type zeolites. In certain embodiments, zeolite 4A is used.

[0172] Suitable base polymers for use in the disclosure optionally include one or more of ethylene vinyl acetate, thermoplastic elastomers, thermoplastic polymers, e.g., polyolefins such as polypropylene and polyethylene, polyisoprene, polybutadiene, polybutene, polysiloxane, polycarbonates, polyamides, ethylene / alpha olefin copolymers, ethylene / 1-butene copolymers, ethylene / 1-hexene copolymers, Exact™, ethylene-vinyl acetate copolymers, ethylene-methacrylate copolymer, poly(vinyl chloride), polystyrene, polyesters including polylactic acid, polyanhydrides, poly(methyl methacrylate), polyacrylonitrile, polysulfones, polyacrylic ester, acrylic, polyurethane and polyacetal, or copolymers or mixtures thereof.

[0173] Suitable channeling agents in the disclosure optionally include one or more of polyglycol such as polyethylene glycol (PEG), ethylene-vinyl acetate (EVA), ethylene- vinyl alcohol (EVOH), polyvinyl alcohol (PVOH), glycerin polyamine, polyurethane and polycarboxylic acid including polyacrylic acid or polymethacrylic acid. Alternatively, the channeling agent can be, for example, a water insoluble polymer, such as a polypropylene oxide monobutyl ether, which is commercially available under the trade name Polyglykol B01 / 240, produced by CLARIANT. In other embodiments, the channeling agent could be a polypropyleneAttorney Docket No. CSP-0618PC(310316-02710) PATENToxide monobutyl ether, which is commercially available under the trade name Polyglykol B01 / 20, produced by CLARIANT, polypropylene oxide, which is commercially available under the trade name Polyglykol D01 / 240, produced by CLARIANT, ethylene vinyl acetate, nylon 6. nylon 66, or any combination of the foregoing.

[0174] FIGS. 3 – 8 illustrate entrained polymers 10 and various packaging assemblies formed of entrained polymers according to the disclosure. The entrained polymers 10 each include a base polymer material 25, a channeling agent 35 and an active agent 30. As shown, the channeling agent 35 forms interconnecting channels 45 through the entrained polymer 10. At least some of the active agent 30 is contained within these channels 45, such that the channels 45 communicate between the active agent 30 and the exterior of the entrained polymer 10 via channel openings 48 formed at outer surfaces of the entrained polymer 10. The active agent 30 can be, for example, any one of a variety of absorbing, adsorbing or releasing materials. The term “an active agent” may be understood as “an metal-organic framework(MOF)” according to the context. While a channeling agent, e.g., 35, is preferred, the disclosed concept broadly includes entrained polymers that optionally do not include channeling agents.

[0175] FIG. 3 shows a plug 55 constructed of an entrained polymer 20, in accordance with certain embodiments of the disclosure. The plug 55 may be placed inside of a container. As aforementioned, the entrained polymer 20 includes a base polymer 25, a channeling agent 35 and an active agent 30.

[0176] FIG. 4 shows a cross-sectional view of the plug 55 shown in FIG. 3. In addition, FIG.4 shows that the entrained polymer 20 has been solidified such that the channeling agent 35 forms interconnecting channels 45 to establish passages throughout the solidified plug 55. At least some of the active agent 30 is contained within the channels 45, such that the channels 45 communicate between the active agent 30 and the exterior of the entrained polymer 20 via channel openings 48 formed at outer surfaces of the entrained polymer 25.

[0177] FIG. 5 illustrates an embodiment of a plug 55 having similar construction and makeup to the plug 55 of FIG. 4, where interconnecting channels 45 are finer as compared to those shown in FIG. 4. This can result from the use of a dimer agent (i.e., a plasticizer) together with a channeling agent 35. The dimer agent may enhance the compatibility between the base polymer 25 and the channeling agent 35. This enhanced compatibility is facilitated by a lower viscosity of the blend, which may promote a more thorough blending of the base polymer 25 andAttorney Docket No. CSP-0618PC(310316-02710) PATENTchanneling agent 35, which under normal conditions can resist combination into a uniform solution. Upon solidification of the entrained polymer 20 having a dimer agent added thereto, the interconnecting channels 45 which are formed there through have a greater dispersion and a smaller porosity, thereby establishing a greater density of interconnecting channels throughout the plug 55.

[0178] Interconnecting channels 45, such as those disclosed herein, facilitate transmission of a desired material, such as moisture, gas or odor, through the base polymer 25, which generally acts as a barrier to resist permeation of these materials. For this reason, the base polymer 25 itself acts as a barrier substance within which an active agent 30 may be entrained. The interconnecting channels 45 formed of the channeling agent 35 provide pathways for the desired material to move through the entrained polymer 10. Without these interconnecting channels 45, it is believed that relatively small quantities of the desired material would be transmitted through the base polymer 25 to or from the active agent 30. Additionally, wherein the desired material is transmitted from the active agent 30. it may be released from the active agent 30, for example in embodiments in which the active agent 30 is a releasing material.

[0179] FIG. 6 illustrates an embodiment of an entrained polymer 10 according to the disclosed concept, in which the active agent 30 is an absorbing or adsorbing material. The arrows indicate the path of the selected material, for example moisture or gas, from an exterior of the entrained polymer 10, through the channels 45, to the particles of active agent 30, which absorb or adsorb the selected material.

[0180] FIG. 7 illustrates an active sheet or film 75 formed of the entrained polymer 20 used in combination with a barrier sheet 80 to form a composite, according to an aspect of the disclosure. The characteristics of the active sheet or film 75 are similar to those described with respect to the plug 55. The barrier sheet 80 may be a substrate such as foil and / or a polymer with low moisture or oxygen permeability. The barrier sheet 80 is compatible with the entrained polymer structure 75 and is thus configured to thermally bond to the active sheet or film 75, when the active sheet or film 75 solidifies after dispensing.

[0181] FIG. 8 illustrates an embodiment in which the active sheet or film 75 and the barrier sheet 80 are combined to form a packaging wrap having active characteristics at an interior surface formed by the entrained polymer 10 in the active sheet or film 75, and vapor resistant characteristics at an exterior surface formed by the barrier sheet 80. In this embodiment, theAttorney Docket No. CSP-0618PC(310316-02710) PATENTactive sheet or film 75 occupies a portion of the barrier sheet 80. The methods according to the disclosure for making the active sheet or film 75 and adhering it to the barrier sheet 80 are not particularly limited.

[0182] In one embodiment, the sheets of FIG. 7 are joined together to form an active package 85, as shown in FIG. 8. As shown, two laminates or composites are provided, each formed of an active sheet or film 75 joined with a barrier sheet 80. The sheet laminates are stacked, with the active sheet or film 75 facing one another, so as to be disposed on an interior of the package, and are joined at a sealing region 90, formed about a perimeter of the sealed region of the package interior.

[0183] Optionally, in any of the foregoing embodiments, the entrained polymer is in the form of a film that is disposed within a sealed package. Optionally, the film may be adhered, e.g., using an adhesive, to an inner surface of the package. Alternatively, the film may be heat staked (without an adhesive) to the inner surface of the package. The process of heat staking film onto a substrate is known in the art and described in detail in U. S. Pat. No. 8,142,603. which is incorporated by reference herein in its entirety. Alternatively, the film may be deposited and adhered to the inner surface of the package via a direct in-line melt process. The size and thickness of the film can vary. In certain embodiments, the film has a thickness of approximately 0.2 mm or 0.3 mm. Optionally, the film may range from 0.1 mm to 1.0 mm, more preferably from 0.2 mm to 0.6 mm.

[0184] FIG. 9 shows a package 100 for storing product, e.g., produce or meat, in accordance with certain embodiments of the disclosure. However, it is understood and contemplated that, in accordance with certain other embodiments of the disclosure, the package 100 is configured to store a cosmetic or medicament product. The package 100 is shown in the form of a plastic tray 102. Although, other forms and materials are also contemplated as being within the scope of the disclosure. The tray 102 comprises a base 104, and sidewalls 106 extending vertically from the base 104 leading to a tray opening 108. The base 104 and sidewalls 106 together define an interior 110, e.g. for holding and storing fresh produce. The package 100 also includes a flexible plastic lidding film 112, which is disposed over and seals the opening 108. It is contemplated and understood that a wide variety of covers or lids may be used to close and seal the opening 108.Optionally, the cover or lid is transparent, such that the interior can be viewed. When a product (e.g., sliced tomatoes) is stored within the interior 110, empty space surrounding and above theAttorney Docket No. CSP-0618PC(310316-02710) PATENTproduct is herein referred to as “headspace” (not shown).

[0185] The package 100 can further include sections of entrained polymer film 114 disposed on the sidewalls 106. In the embodiment shown, there are four sections of such film 114, one section of film 114 per sidewall 106. Midline 116 associated with sidewall 106 can be identified, midline 116 being centrally located between the base 104 and the opening 108. Depending on the characteristics of the contaminating substances associated with the product, the film sections 114 may be located variously above the midline 116, at approximately the same height as midline 116, or below midline 116. of the sidewall 106.

[0186] In certain embodiments, the antimicrobial entrained polymer film 114 may be connected to the surface of the lidding film 112 (or a lid) that is inside of the container, in place of the film sections 114 on the sidewall(s) 106, or in addition thereto. Alternatively, the antimicrobial entrained polymer film 114 may be incorporated into the composition of the lidding film 112 (or a lid). Optionally, the lidding film itself may include a lid barrier layer and an antimicrobial entrained polymer film layer beneath it.Exemplary Embodiments

[0187] The following exemplary embodiments further describe optional aspects of the presently disclosed technology and are part of this Detailed Description. These exemplary embodiments are set forth in a format substantially akin to claims (each with numerical designations), although they are not technically claims of the present application. The following exemplary embodiments refer to each other in dependent relationships as “embodiments” instead of “claims.”

[0188] Embodiment 1A: An entrained polymer comprising:a base polymer;a metal-organic framework (MOF); andoptionally, a channeling agent.

[0189] Embodiment 2A: The entrained polymer of Embodiment 1A, wherein the metalorganic framework comprises a metal ion chosen from Al(III) and Zr(IV).

[0190] Embodiment 3A: The entrained polymer of either one of Embodiments 1 A and 2A, wherein the metal-organic framework comprises an organic polycarboxylic acid, or a salt thereof.Attorney Docket No. CSP-0618PC(310316-02710) PATENT

[0191] Embodiment 4A: The entrained polymer of any one of Embodiments 1 A and 2A and OA, wherein the organic polycarboxylic acid is an organic dicarboxylic acid.

[0192] Embodiment 5A: The entrained polymer of Embodiment 4A, wherein the organic dicarboxylic acid is chosen from 1,3-benzenedicarboxylic acid, 2,5-furandicarboxylic acid, succinic acid, maleic acid, fumaric acid, malic acid, and phthalic acid, or a mixture thereof.

[0193] Embodiment 6A: The entrained polymer of Embodiment 5A, wherein the organic dicarboxylic acid is chosen from 2,5-furandicarboxylic acid and fumaric acid.

[0194] Embodiment 7A: The entrained polymer of Embodiment 6A, wherein the organic dicarboxylic acid is 2,5-furandicarboxylic acid.

[0195] Embodiment 8A: The entrained polymer of Embodiment 6A, wherein the organic dicarboxylic acid is fumaric acid.

[0196] Embodiment 9A: The entrained polymer of Embodiment 8A, wherein the MOF has at least 3 XRD peaks, using CuKa radiation, chosen from about 10°, about 15°, about 21°, about 32°, about 42°, and about 43° 2-theta.

[0197] Embodiment 10A: The entrained polymer of Embodiment 9A, wherein the MOF has at least 4 XRD peaks, using CuKa radiation, chosen from about 10°, about 15°, about 21°, about 32°, about 42°, and about 43° 2-theta.

[0198] Embodiment 11A: The entrained polymer of Embodiment 10A, wherein the MOF has at least 5 XRD peaks, using CuKa radiation, chosen from about 10°, about 15°, about 21°, about 32°, about 42°, and about 43° 2-theta.

[0199] Embodiment 12A: The entrained polymer of Embodiment 8A, comprising nanocrystals of MOF having a mean size between 40 nm and 100 nm, optionally between 50 nm and 80 nm, optionally between 55 nm and 70 nm.

[0200] Embodiment 13A: The entrained polymer of Embodiment 12A, comprising nanocrystals of MOF having a mean size of about 60 nm.

[0201] Embodiment 14A: The entrained polymer of either one of Embodiments 8A and 13A, wherein the MOF has a BET surface area of 500 m2 / g or larger, optionally 600 m2 / g or larger, optionally 700 m2 / g or larger, optionally 800 m2 / g or larger, optionally 900 m2 / g or larger.

[0202] Embodiment 15A: The entrained polymer of Embodiment 14A, wherein the MOF has a BET surface area of 900 m2 / g or larger.

[0203] Embodiment 16A: The entrained polymer of Embodiment 14A, wherein the MOF hasAttorney Docket No. CSP-0618PC(310316-02710) PATENTa BET surface area of 900 m2 / g or larger.

[0204] Embodiment 17A: The entrained polymer of any one of Embodiments 1A - 16A, wherein the base polymer is chosen from ethylene vinyl acetate, thermoplastic elastomers, thermoplastic polymers, e.g., polyolefins such as polypropylene and polyethylene, polyisoprene, polybutadiene, polybutene, polysiloxane, polycarbonates, polyamides, ethylene / alpha olefin copolymers, ethylene 1 1-butene copolymers, ethylene 1 1-hexene copolymers, ethylene-vinyl acetate copolymers, ethylene- methacrylate copolymer, poly(vinyl chloride), polystyrene, polyesters including polylactic acid, poly anhydrides, poly(methyl methacrylate), polyacrylonitrile, polysulfones, polyacrylic ester, acrylic, polyurethane and polyacetal, or copolymers or mixtures thereof.

[0205] Embodiment 18A: The entrained polymer of Embodiment 17A, wherein the base polymer is chosen from polyethylene, polypropylene, ethylene vinyl acetate, polyisoprene, polybutadiene, polybutene, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene-methacrylate copolymer, poly(vinyl chloride), polystyrene, poly(methyl methacrylate), polyacrylonitrile, or mixtures thereof.

[0206] Embodiment 19A: The entrained polymer of Embodiment 17A, wherein the base polymer is chosen from a polyolefin and an ethylene / alpha olefin copolymer.

[0207] Embodiment 20A: The entrained polymer of Embodiment 19A, wherein the base polymer is chosen from polypropylene and Exact™ 3040.

[0208] Embodiment 21 A: The entrained polymer of any one of Embodiments 1A - 20 A, consisting of 10% to 70%, optionally from 20% to 60%, optionally from 20% to 50%, optionally from 20% to 40%, optionally from 30% to 50%, optionally from 40% to 50% by weight of base polymer.

[0209] Embodiment 22A: The entrained polymer of any one of Embodiments 1A - 21 A, consisting of 30% to 80%, optionally 35% to 75%, optionally 40% to 70% by weight of MOF.

[0210] Embodiment 23A: The entrained polymer of any one of Embodiment 22A, consisting of about 60% MOF.

[0211] Embodiment 24A: The entrained polymer of any one of Embodiments 1A - 23A, wherein the entrained polymer absorbs at least 100 mg / g, optionally at least 150 mg / g, optionally at least 200 mg / g, optionally at least 250 mg / g, optionally at least 300 mg / g water within 50 days of exposure to 80% relative humidity at 22 °C.Attorney Docket No. CSP-0618PC(310316-02710) PATENT

[0212] Embodiment 25 A: The entrained polymer of any one of Embodiments 1 A - 23 A, wherein the entrained polymer absorbs at least 50 mg / g, optionally at least 100 mg / g, optionally at least 150 mg / g, optionally at least 200 mg / g, optionally at least 250 mg / g water within 10 days of exposure to 80% relative humidity at 22 °C.

[0213] Embodiment 26A: The entrained polymer of any one of Embodiments 1A - 23A, wherein the entrained polymer absorbs at least 50 mg / g, optionally at least 100 mg / g, optionally at least 150 mg / g, optionally at least 200 mg / g, optionally at least 250 mg / g water within 20 days of exposure to 80% relative humidity at 22 °C.

[0214] Embodiment 27A: The entrained polymer of any one of Embodiments 1A - 23A, wherein the entrained polymer absorbs at least 100 mg / g, optionally at least 150 mg / g, optionally at least 200 mg / g, optionally at least 250 mg / g, optionally at least 300 mg / g water within 50 days of exposure to 80% relative humidity at 22 °C.

[0215] Embodiment 28A: The entrained polymer of any one of Embodiments 1A - 27A, wherein the entrained polymer does not comprise a channeling agent.

[0216] Embodiment 29A: The entrained polymer of any one of Embodiments 1A - 27A, further comprising a channeling agent.

[0217] Embodiment 30 A: The entrained polymer of Embodiment 29 A, wherein the channeling agent is chosen from a polyglycol such as polyethylene glycol (PEG), ethylene-vinyl acetate (EVA), ethylene- vinyl alcohol (EVOH), polyvinyl alcohol (PVOH), glycerin polyamine, polyurethane and polycarboxylic acid including polyacrylic acid or polymethacrylic acid.

[0218] Embodiment 31 A: The entrained polymer of Embodiment 29A, wherein the channeling agent is chosen from polyethylene oxide, polypropylene oxide, ethylene vinyl acetate, nylon 6, nylon 66, or a combination thereof.

[0219] Embodiment 32A: The entrained polymer of Embodiment 29A, wherein the channeling agent is polyethylene glycol (PEG).

[0220] Embodiment 33A: The entrained polymer of Embodiment 29A, wherein the channeling agent is ethylene vinyl acetate copolymer (EVA).

[0221] Embodiment 1B: A pellet comprising the entrained polymer of any one of Embodiments 1A - 33A.

[0222] Embodiment 2B: The pellet of Embodiment 1B, wherein the pellet is cylindrical in shape (i.e., is a cylindrical pellet).Attorney Docket No. CSP-0618PC(310316-02710) PATENT

[0223] Embodiment 3B: The pellet of Embodiment 2B, wherein the height of the cylindrical pellet is 2 mm or larger, optionally 3 mm or larger, optionally 5 mm or larger, optionally 10 mm or larger, optionally 20 mm or larger.

[0224] Embodiment 4B: The pellet of Embodiment 2B, wherein the height of the cylindrical pellet is the height of the cylindrical pellet is 30 mm or smaller, optionally 20 mm or smaller, optionally 15 mm or smaller, optionally 10 mm or smaller, optionally 5 mm or smaller.

[0225] Embodiment 5B: The pellet of Embodiment 2B, wherein the height of the cylindrical pellet is about 5 mm.

[0226] Embodiment 6B: The pellet of any one of Embodiments 2B - 5B, wherein the diameter of the cylindrical pellet is 6 mm or larger, optionally 8 mm or larger, optionally 10 mm or larger, optionally 15 mm or larger, optionally 20 mm or larger.

[0227] Embodiment 7B: The pellet of any one of Embodiments 2B - 5B, wherein the diameter of the cylindrical pellet is 40 mm or smaller, optionally 30 mm or smaller, optionally 25 mm or smaller, optionally 20 mm or smaller, optionally 16 mm or smaller, optionally 12 mm or smaller.

[0228] Embodiment 8B: The pellet of any one of Embodiments 2B - 5B, wherein the diameter of the cylindrical pellet is from 11 mm to 12 mm.

[0229] Embodiment 9B: The pellet of any one of Embodiments 1B - 8B, wherein the volume of the pellet is at least 250 mm3, optionally at least 500 mm3, optionally at least 750 mm3, optionally at least 1000 mm3, optionally at least 1500 mm3, optionally at least 2000 mm3, optionally at least 2500 mm3.

[0230] Embodiment 10B: The pellet of any one of Embodiments 1B - 8B, wherein the volume of the pellet is at most 4000 mm3, optionally at most 3000 mm3, optionally at most 2000 mm3, optionally at most 1000 mm3, optionally at most 750 mm3, optionally at most 600 mm3, optionally at most 500 mm3.

[0231] Embodiment 11B: The pellet of any one of Embodiments 1B - 10B, wherein the surface area of the pellet is at least 250 mm2, optionally at least 500 mm2, optionally at least 750 mm2, optionally at least 1000 mm2, optionally at least 1250 mm2, optionally at least 1500 mm2, optionally at least 2000 mm2.

[0232] Embodiment 12B: The pellet of any one of Embodiments 1B - 11B, wherein the surface area of the pellet is at most 3000 mm2, optionally at most 2500 mm2, optionally at mostAttorney Docket No. CSP-0618PC(310316-02710) PATENT2000 mm2, optionally at most 1500 mm2, optionally at most 100 mm2, optionally at most 800 mm2, optionally at most 600 mm2.

[0233] Embodiment 13B: The pellet of any one of Embodiments 1B - 12B, wherein the pellet absorbs at least 40 mg / g, optionally at least 60 mg / g, optionally at least 80 mg / g, optionally at least 100 mg / g water within 10 days of exposure to 80% relative humidity at 22 °C.

[0234] Embodiment 14B: The pellet of any one of Embodiments 1B - 13B, wherein the pellet absorbs at least 80 mg / g, optionally at least 120 mg / g, optionally at least 160 mg / g, optionally at least 200 mg / g water within 100 days of exposure to 80% relative humidity at 22 °C.

[0235] Embodiment 15B: The pellet of any one of Embodiments 1B - 14B, wherein the pellet absorbs at least 30 pg / mm3volume, optionally at least 60 pg / mm3volume, optionally at least 90 pg / mm3volume, optionally at least 120 pg / mm3volume water within 10 days of exposure to 80% relative humidity at 22 °C.

[0236] Embodiment 16B: The pellet of any one of Embodiments 1B - 15B, wherein the pellet absorbs at least 60 pg / mm3volume, optionally at least 120 pg / mm3volume, optionally at least 180 pg / mm3volume, optionally at least 240 pg / mm3volume water within 100 days of exposure to 80% relative humidity at 22 °C.

[0237] Embodiment 17B: The pellet of any one of Embodiments 1B - 16B, wherein the pellet absorbs at least 50 pg / mm2surface area, optionally at least 100 pg / mm2surface area, optionally at least 150 pg / mm2surface area, optionally at least 200 pg / mm2surface area water within 10 days of exposure to 80% relative humidity at 22 °C.

[0238] Embodiment 18B: The pellet of any one of Embodiments 1B - 17B, wherein the pellet absorbs at least 100 pg / mm surface area, optionally at least 200 pg / mm surface area, optionally at least 300 pg / mm surface area water, optionally at least 400 pg / mm surface area water within 100 days of exposure to 80% relative humidity at 22 °C.

[0239] Embodiment 1C: A method for manufacturing the pellet of any one of Embodiments IB - 18B, wherein the method comprises the step of 3D printing.

[0240] Embodiment 2C: A method for manufacturing the pellet of Embodiment 1B, wherein the method comprises the step of fused deposition modeling or extrusion.

[0241] Embodiment ID: A film comprising the entrained polymer of any one ofAttorney Docket No. CSP-0618PC(310316-02710) PATENTEmbodiments 1 A - 33 A.

[0242] Embodiment 2D: The film of any Embodiment ID, wherein the thickness of the film is at or below 500 pm, optionally at or below 450 pm, optionally at or below 400 pm, optionally at or below 350 pm, optionally at or below 300 pm, optionally at or below 250 pm.

[0243] Embodiment 3D: The film of either one of Embodiments ID and 2D, wherein the thickness of the film is at or above 50 pm, optionally at or above 100 pm, optionally at or above 150 pm, optionally at or above 200 pm, optionally at or above 250 pm, optionally at or above 300 pm, optionally at or above 350 pm.

[0244] Embodiment 4D: The film of Embodiment ID, wherein the thickness of the film is between 100 pm and 400 pm, inclusive, optionally between 125 pm and 350 pm, inclusive, optionally between 150 pm and 300 pm, inclusive.

[0245] Embodiment 5D: The film of any one of Embodiments ID - 4D, wherein the film absorbs at least 25 mg / g, optionally at least 50 mg / g, optionally at least 100 mg / g, optionally at least 150 mg / g water within 1 day of exposure to 80% relative humidity at 22 °C.

[0246] Embodiment 6D: The film of any one of Embodiments ID - 5D, wherein the film absorbs at least 50 mg / g, optionally at least 75 mg / g, optionally at least 100 mg / g, optionally at least 150 mg / g water, optionally at least 175 mg / g water, optionally at least 200 mg / g water within 2 days of exposure to 80% relative humidity at 22 °C.

[0247] Embodiment 7D: The film of any one of Embodiments ID - 6D, wherein the film absorbs at least 50 mg / g, optionally at least 75 mg / g, optionally at least 100 mg / g, optionally at least 150 mg / g water, optionally at least 175 mg / g water, optionally at least 200 mg / g water within 5 days of exposure to 80% relative humidity at 22 °C.

[0248] Embodiment IE: A package comprising the entrained polymer of any one of Embodiments 1A - 33A.

[0249] Embodiment 2E: A package comprising the pellet of any one of Embodiments IB -18B.

[0250] Embodiment 3E: A package comprising the film of any one of Embodiments ID -7D.

[0251] Embodiment IF: A method for removing one or more contaminating substances from a product, the method comprising the step of placing the product in the package of any one of Embodiments IE - 3E.Attorney Docket No. CSP-0618PC(310316-02710) PATENT

[0252] Embodiment 2F: A method for preventing contamination of a product by one or more volatile contaminating substances, the method comprising the step of placing the product in the package of any one of Embodiments IE - 3E.

[0253] Embodiment 3F: A method for reducing the amount of one or more volatile contaminating substances in a quantity of gas, the method comprising the step of enclosing the quantity of gas in the package of any one of Embodiments IE - 3E.

[0254] Embodiment 4F: The method of either one of Embodiments 2F and 3F, wherein the one or more volatile contaminating substances comprises a hydrocarbon.

[0255] Embodiment 5F: A method for preventing contamination of a product by moisture, the method comprising the step of placing the product in the package of any one of Embodiments IE - 3E.

[0256] Embodiment 6F: A method for reducing the amount of moisture in a quantity of gas, the method comprising the step of enclosing the quantity of gas in the package of any one of Embodiments IE - 3E.

[0257] Embodiment 7F: A method for protecting a product from oxidation, the method comprising the step of placing the product in the package of any one of Embodiments IE - 3E.

[0258] Embodiment 8F: The method of any one of Embodiments IF, 2F, 5F, and 7F, wherein the product is selected from food, cosmetic and medicament.Example 1: Methods of characterizationPowder X-ray (XRD)

[0259] X-ray diffraction patterns are collected on a PANalytical MPD X'Pert Pro diffractometer operating with Cu Karadiation (Ka=0.15418 nm) equipped with a PIXcel realtime multiple strip detector (active length=3.347° 2d). Powder patterns are collected at ambient temperature in the range 3°<2d<50°, step- 0.013° 2d, time / step-220 s and the total collecting time of about 90 minutes.

[0260] Experimental patterns are analyzed with X'Pert HighScore software. The crystallographic data for MOF A520 published by E. Alvarez et al. {52} are found in the Cambridge Crystallographic Data Centre (CCDC) with RefCode DOYBEA and CSD 1051975. Additional databases available include ICDD (International Center for Diffraction Data), COD (Crystallography Open Database), and a database specific to the laboratory.Attorney Docket No. CSP-0618PC(310316-02710) PATENTScanning electron microscopy (SEM)

[0261] SEM can provide information about the size and morphology of MOFs by the following steps: The sample is subjected to an electron beam and scanned in a raster scan pattern. The position of the beam is combined with the detected signal (the scattered and secondary electrons emitted by the sample) to produce an image. Since MOFs are generally not conductive, they can be coated with a thin carbon layer (15 nm) using the carbon braid evaporator (Balzer SCD004) to ensure good electrical conduction. During this work, a high resolution SEM JSM-7900F from JEOL with an accelerating voltage of 2 kV and a working distance of 10 mm was used.Nitrogen adsorption-desorption

[0262] Nitrogen adsorption-desorption allows determination of the textural properties of a porous material such as specific surface area and microporous volume.

[0263] Nitrogen adsorption-desorption isotherms are performed at 77 K using a Micromeritics ASAP 2420 apparatus. Prior to the adsorption measurements, the samples are outgassed at 200 °C for 12 h under secondary vacuum. The degassing step is necessary to activate the pores by desorbing gases and evaporating volatile molecules that may be trapped, thus making the pores accessible for the adsorption of N2 molecules. After the outgassing process, the samples (~ 100 mg of product) are subjected to a definite pressure (pi) of N2 in gas phase at 77 K. This pressure decreases due to the adsorption of a quantity of nitrogen inside the porosity of the material until an equilibrium value (p) is reached. The difference p -p allows determination of the amount of adsorbed gas. Thus, a nitrogen adsorption-desorption isotherm is recorded as a function of the nitrogen relative pressure (p / p°. where p° is N2 saturation vapor pressure at 77 K) and it represents the gas adsorbed volume per gram of MOF (V) under standard temperature and pressure conditions (cm3 / g STP). The BET and Langmuir specific surface area and micropore volume (Vp) were calculated using the BET, Langmuir and t-plot methods, respectively, so the external surface area and VSP at p / p°=0.2 and was calculated using t-plot. MicroActive software is used to perform the N2 sorption measurements and to process the obtained adsorption-desorption isotherms.Attorney Docket No. CSP-0618PC(310316-02710) PATENTWater adsorption

[0264] Water adsorption isotherms of raw MOF powder samples are performed at 25 °C using a Micromeritics ASAP 2020 instrument. Prior to the water adsorption measurements, water (analyte) is flash frozen under liquid N2 and then evacuated under dynamic vacuum at least 5 times to remove any gases in the water reservoir. The samples (50-100 mg) are outgassed under vacuum at 90 °C for 1 h and 200 °C for 14 h to remove the physisorbed water.

[0265] Water adsorption kinetics of raw material and composite materials containing the raw MOF are performed by following the weight variation along the time at 22 °C at a relative humidity of 80% using a Memmert HCP 108 humidity chamber. Samples are taken from the sealed bags in which they were stored after being manufactured to avoid moisture intake and directly used for measurements.n-Hexane and oxygen adsorption

[0266] n-Hexane and oxygen adsorption isotherms of raw MOF powder and composite samples are performed at 25 °C for n-hexane and 20 °C for oxygen using a Micromeritics ASAP 2020 instrument. The samples (50-100 mg for n-hexane adsorption and 1 g for oxygen adsorption) are outgassed under vacuum at 90 °C for 1 h, followed by 200 °C for 12 h to remove the physisorbed water for raw MOF powder, and at 50 °C for 24 h for the composite materials.Thermogravimetric Analysis (TGA)

[0267] TGA allows measuring the changes in the mass of a sample that can occur while the latter is subjected to controlled increasing temperature. TGA is carried out in a controlled gaseous atmosphere that can be either static (gas at reduced pressure) or dynamic (inert or reactive gas). The mass of the sample employed is usually in the 1-100 mg range and the sensitivity of the technique is limited by that of the balance, which may be as high as 0.1 pg. During TGA, the studied sample undergoes changes that are mainly accompanied with one or several mass losses. Examples of mass loss processes include: degradation and / or decomposition, vaporization (of bulk liquids or liquids adsorbed by the solid surface or in the porosity), sublimation, desorption of gases, etc. The result of a TG measurement is a TG curve that represents the evolution of the mass of the sample (usually displayed in mass percentage) as a function of time, or more commonly, as a function of temperature.

[0268] The MOF material (20-35 mg) is inserted in a 150 pL alumina crucible and analyzed on a Mettler Toledo STARe apparatus using a 2 °C / min gradient from 30 to 900 °C under airAttorney Docket No. CSP-0618PC(310316-02710) PATENTflow. The STARe software is used to perform the experiments and, later, to exploit the data obtained. Usually, three mass losses have been to take into account and give an overview of physicochemical properties of the studied material:

[0269] Pi, mass loss (in %) calculated between room temperature and usually 200 °C and corresponding to the release of physisorbed or accommodated species.

[0270] Pz, mass loss (in %) calculated between room temperature and usually 600 °C and corresponding to the release of physisorbed or accommodated species in addition to framework degradation.

[0271] More generally, Pi, a given mass loss (in %) is defined by Pi = (mo-mi) / mo *100 where mo and mi stand for the sample mass (in mg) at room temperature and at the end of a supposed phenomenon, respectively.

[0272] P3, mass loss (in %) usually calculated between 200 and 600 °C, allowing determination of the framework composition, is expressed as a percentage and is calculated according to Equation 1:7,3 =2-^x 100(Eouationi)Example 2: Preparation of aluminum fumarate MOF (AIFu)

[0273] Synthesis conditions of MOF A520 employed in the protocol followed by Sankha Karmakar et al. {51 } were optimized: the quantities of reactants, additive and water have been increased (by a factor of 40).

[0274] In a 10 L polypropylene flask, 742.10g (2.17 mol) of aluminum sulfate octahydrate were dissolved in 3190 mL (176.67 mol) of water. The solution was mechanically stirred (300 rpm) at room temperature until dissolution (60 minutes) to give Solution 1. In a separate 10 L polypropylene flask were mixed 192.2 g (4.75 mol) of NaOH and 246.65 g (2.12 mol) of fumaric acid in 3820 mL (212.22 mol) of water to give Solution 2. Mechanical stirring (300 rpm) was maintained until dissolution (10 minutes) at room temperature. Solution 2 (ligand source) was then added to Solution 1 (metal source), and the reaction mixture was heated for 2 h with mechanical stirring, during which time a white precipitate of aluminum fumarate formed. The white pasty powder was recovered by centrifugation at 7000 rpm for 5 min (instead of 2000 rpm for 20 min) and washed 5-6 times with deionized water to remove the remaining reagents and additives. The white paste was then dried under vacuum at 100 °C for 24 h. The dehydratedAttorney Docket No. CSP-0618PC(310316-02710) PATENTsample obtained by this method was approximately 220 g.Example 3: Characterization of AIFuXRD characterization

[0275] The Example 2 material was characterized by powder X-ray diffraction. FIG. 10 shows (ii) the diffractogram of the synthesized AIFu material as well as (i) the pattern simulated from literature referenced in Cambridge Structural Database (number 1051975; code DOYBEA). Notably, the positions and relative intensities of the seven large diffraction peaks in the diffractogram for the AIFu material are consistent with the literature {42}. The relatively large full width at half maximum of the diffraction peaks is consistent with either small crystallite size or low crystallinity.SEM characterization

[0276] The Example 2 material was characterized by SEM. FIG. 11 shows particles of about several micrometers. Low resolution scans (FIG. 11(a)) show particles with dimensions on the order of several micrometers. Higher resolution scans (FIG. 11(b)) show that the micrometerscale particles are agglomerates of nanocrystals with an average size of 60 nm.N2adsorption / desorption characterization

[0277] The Example 2 material was characterized by N2 adsorption / desorption. FIG. 12 shows the N2 adsorption-desorption isotherms of this material performed at 77 K. These isotherms possess a type I profile characteristic of microporous materials, in addition a hysteresis at high relative pressure combined with the slope of the plateau probably revealing both interparticle mesoporosity and external surface due to nanoparticules.

[0278] The BET surfaces measured (in the range of relative pressure 0.00049-0.022021), and micropore volumes at p / p0= 0.2 are consistent with the values reported in the literature: BET surface areas of 1081 m2 / g and micropore volumes of 0.37 cm3 / g.

[0279] FIG. 13 shows a TGA curve of the Example 2 material. The TGA curve of the synthesized sample reveal a loss of mass between room temperature and 200 °C, which is attributed to the release of H2O molecules trapped in the porosity. This loss of mass (Pi = 28.13 %) indicates that the material is hydrophilic. This mass loss is probably correlated with hydration of the samples after drying and before analyzing (the mass loss would depend on the exposure time of the sample after drying). The TG curves show that the samples are thermallyAttorney Docket No. CSP-0618PC(310316-02710) PATENTstable up to around 410 °C. This is followed by a main decomposition step between 410-525 °C, which is attributed to the decomposition of the hybrid network into Al2O3. The experimental mass losses from 200 to 600°C (P3 = 65.9 %) is consistent with the theoretical value expected to 67.7 %. The slight difference could be explained by the presence of amorphous Al species with MOF A520.H2O adsorption

[0280] The water adsorption isotherm of the Example 2 material is displayed in FIG. 14. The isotherm shows low adsorption at relative pressure below 0.2 which increases sharply at relative pressure above 0.2 to reach at a relative pressure of 0.8 an adsorbed volume of 561.43 cm3 / g(STP) which correspond to 451.15 mg of water per g of MOF (45.1 wt.%) in agreement with the maximum adsorption capacities (47.3 wt.%) obtained from the adsorption kinetics studies performed on this MOF at 22 °C and a relative humidity of 80% (FIG. 15). This adsorption capacity is almost 2 times higher than the one observed for 4A and 3A zeolites usually used for humidity adsorption.n- Hexane adsorption

[0281] The / 7-hexane sorption capacity deduced from the n-hexane adsorption isotherm (see FIG. 16) realized at 25 °C on the Example 2 material is around 246 mg / g at p / p° = 0.2 and 375.7 mg / g in a pure 77-hexane atmosphere (p / p° = 1). This adsorption capacity is higher than those observed with «-hexane adsorption over zeolites (110 to 186.5 mg / g for conventional MFI, *BEA and FAU-type zeolite).Example 4, Polymer composites of AIFuManufacture

[0282] Manufacture of composite materials in form of granulates is performed with a Thermo Scientific Process 11 Parallel Twin-screw Extruder. This apparatus possesses segmented screw design allowing adjustment of the processing conditions to simulate various compounding applications. Due to the constant processing geometry within the Thermo Scientific™ extruder portfolio, knowledge obtained from the lab trials using the Process 11 Extruder can directly be transferred to pilot or production scale equipment. This scale-up transfer is based on the specific energy introduced into the material. The die of the extruder for these tests has a diameter of 2 mm. Seven heating zones along the screw are available with 8 temperature measurement points.Attorney Docket No. CSP-0618PC(310316-02710) PATENTScrew speed can be varied between 10 and 1000 rpm. Throughput rates of 20 g / h to 2.5 kg / h can be obtained.

[0283] The obtained composite material samples were denoted as follows: x-yP-z-w with x the name of the porous sample contained in the composite, y = the number of phases present in the composite, z = weight % of the porous material in the composite and w = abbreviation of the polymer(s) present in mixture. For example. A520-2P-40-PP refers to a 2 phase composite material composed of 40% by weight of MOF A520 and 60% by weight of polypropylene.

[0284] The granulates are then characterized to determine their MOF loading, the distribution of MOF crystals in their composite bodies, and their water adsorption capacities.

[0285] FIG. 17 shows the photos of one of the extruded materials (FIG. 17(a)) and the obtained granulates (FIG. 17(b)).Compositional analysis

[0286] The amount of raw and MOF samples contained in composite materials were determined using a Nabertherm Controller B170 oven or a TGA. Samples were taken from sealed aluminum bags in which the composite materials were directly stored and protected after being manufactured. To determine the MOF loading, a calcination program was carried out (up to 1000 °C with a heating rate of 2 °C / min). Heating the composite sample causes decomposition of the organic matter, wherein the inorganic part (metal) is oxidized to form oxides (for example with aluminum species that give rise to Al2O3). By determining the number of metal atoms in the formed oxide, the content corresponding to MOF in the formulation can be obtained.

[0287] The obtained formulations are listed in Table 1.Table 1. Formulations obtained for granulates.Formulation Channeling MOF amount in the name MOF used Polymers agent formulation A520-2P-39-PP A520 PP n / a 39 wt.%A520-2P-49-PP A520 PP n / a 49 wt.%A520-2P-59-PP A520 PP n / a 59 wt.%A520-2P-68-PP A520 PP n / a 68 wt.%A520-2P-36-Exact A520 Exact™ 3040 n / a 36 wt.%Attorney Docket No. CSP-0618PC(310316-02710) PATENTA520-2P-43 -Exact A520 Exact™ 3040 n / a 43 wt.%A520-2P-48-Exact A520 Exact™ 3040 n / a 48 wt.%A520-3P-36-PP A520 PP PEG 36 wt.%A520-3P-44-PP A520 PP PEG 44 wt.%A520-3P-54-PP A520 PP PEG 54 wt.%- A520-3P-62-PP A520 PP PEG 62 wt.%A520-3P-36-Exact A520 Exact™ 3040 PEG 36 wt.%A520-3P-44- Exact A520 Exact™ 3040 PEG 44 wt.%A520-3P-54- Exact A520 Exact™ 3040 PEG 54 wt.%A520-3P-62- Exact A520 Exact™ 3040 PEG 62 wt.%Characterization

[0288] FIG. 18 shows a homogeneous distribution of MOF A520 crystals within the polymer matrix at low, medium, and high magnification.

[0289] Water adsorption kinetics realized at 22 °C and a relative humidity of 80% on the obtained 2-phase granulates shows that porosity of the MOF is still accessible for the adsorption of humidity present in the air (see FIGS. 19 and 20). In general, water adsorption kinetics seems to be slower on granulates obtained with Exact™ 3040 as main polymer compared to the samples with the same composition containing PP as main polymer. However, those kinetics are much slower than the one observed with MOF A520 powder.

[0290] FIG. 21, representing the elemental mapping of the A520-3P-60-PP granulate, distinguishes clearly the polymer components composed of carbon from the inorganic part (Al) representing the MOF composed of carbon, oxygen, aluminum etc. In addition, the localization of the different Al atoms confirms the homogeneous distribution as well as the success of the extrusion process.

[0291] Water adsorption kinetics realized at 22 °C and a relative humidity of 80% on the obtained 3-phase granulates shows that porosity of the MOF is still accessible for the adsorption of humidity present in the air (see FIGS. 22 and 23). In general, water adsorption kinetics seems to be slower on granulates obtained with Exact™ 3040 as main polymer compared to the samples with the same composition containing PP as main polymer. However, those kinetics are much slower than the one observed with MOF A520 powder.Attorney Docket No. CSP-0618PC(310316-02710) PATENTExample 5. 3D printed materials

[0292] The following parameters were used for the 3D printing of pellets:3D Printer model: PAM Serie MC from Pollen AM supplier.Type of 3D 3D printing in FDM (Fused Deposition Modeling)printing: from compound pellets melted by an extrusion process(as described above).Type of nozzle brass nozzle diameter 0.6 mm.used:Part printed: Cylinder with height = 5 mm and diameter = 11.30 mmbased on M-3003-340 internal referenceProgram mainparameters:Layer height: 0.2 mm. Extrusion temperature: 180 °C Nozzle temperature: 200 °C Build plate temperature: 70 °C No coolingPrinting time for one part: around 8 min

[0293] FIG. 24 shows a representative 3D printed pellet. The obtained pellets are homogeneous and present good mechanical properties. Water adsorption kinetics experiments performed at 22 °C and a relative humidity of 80% on these pellets shows that porosity of the MOF is still accessible for the adsorption of humidity present in the air (see FIG. 26). Water adsorption kinetics seems to be slower than MOF A520 powder.Example 6. Thin composite films of AIFuManufacture

[0294] Manufacture of thin film composite materials was performed with a Thermo Scientific Process 11 Parallel Twin-screw Extruder equipped with a calender allowing the formation of thin film with a thickness between 150 and 300 pm.

[0295] The obtained composite material samples were denoted as follows: x-yP-z-w with xAttorney Docket No. CSP-0618PC(310316-02710) PATENTthe name of the porous sample contained in the composite, y = the number of phases present in the composite, z = weight % of the porous material in the composite and w = abbreviation of the polymer(s) present in mixture. For example. A520-2P-40-Exact refers to a 2 phase composite material composed of 40% by weight of MOF A520 and 60% by weight of Exact™ 3040. For this study, Exact™ 3040, comprising a copolymer of ethylene and 1-hexene, was used.

[0296] The films were then characterized to determine their MOF loading, the distribution of MOF crystals in their composite bodies, and their water adsorption capacities.

[0297] FIG. 27 shows the photos of one of the obtained thin composite films (A520-3P-32-Exact).Compositional analysis

[0298] The amount of raw and MOF samples contained in composite materials was determined using a Nabertherm Controller B170 oven or a TGA. Samples were taken from sealed aluminum bags in which the composite materials were directly stored and protected after being manufactured. To determine the MOF loading, a calcination program was carried out (up to 1000 °C with a heating rate of 2 °C / min). Heating the composite sample causes decomposition of the organic matter, wherein the inorganic part (metal) is oxidized to form oxides (for example with aluminum species that give rise to Al2O3). By determining the number of metal atoms in the formed oxide, the content corresponding to MOF in the formulation can be obtained.

[0299] The obtained formulations are listed in Table 2.Table 2, Formulations obtained for films.Film Formulation Channeling MOF amount in the thickness name MOF used Polymers agent formulation (pm) A520-3P-32-Exact A520 Exact™ 3040 EVA 32 wt.% 300 A520-3P-44-Exact A520 Exact™ 3040 EVA 44 wt.% 300 A520-3P-52-Exact A520 Exact™ 3040 EVA 52 wt.% 300Characterization

[0300] FIG. 28, representing the elemental mapping of the A520-3P-44-Exact film, distinguishes clearly the polymer components composed of carbon from the inorganic part (Al)Attorney Docket No. CSP-0618PC(310316-02710) PATENTrepresenting the MOF composed of carbon, oxygen, aluminum etc. In addition, the localization of the different Al atoms confirms the homogeneous distribution as well as the success of the extrusion process.

[0301] Water adsorption kinetics realized at 22 °C and a relative humidity of 80% on the obtained 3-phase films shows that porosity of the MOF is still accessible for the adsorption of humidity present in the air (see FIG. 29). In general, those kinetics are much slower than the one observed with MOF A520 powder but faster than the one observed on the granulates.

[0302] FIG. 30 shows the O2 adsorption-desorption isotherms of (a) MOF A520 powder, (b) A520-3P-44-Exact film and (c) A520-3P-52-Exact film performed at 20 °C. These isotherms confirm that the MOF A520 and the composite film are able to adsorb oxygen without the need of humidity or other triggers. Even when the MOF is incorporated in polymer(s) matrix oxygen is able to diffuse and to be adsorbed by the MOF particles incorporated in the thin film. To our knowledge this is the first time that MOF A520 is used for oxygen adsorption.Example 7. Molded parts containing AIFuManufacture

[0303] The granulates made from MOF A520 and zeolite 4A (for comparison), made with a Thermo Scientific Process 11 Parallel Twin-screw Extruder, were used to inject parts with an industrial press (mono-injection). An Allrounder 470 C 1500 press was used. It has a closing force of 1500 kN, a distance between columns of 470 x 470 mm and a sleeve diameter of 25 mm. The material was injected into a one-cavity prototype mold.

[0304] The injected composite material samples obtained by this process were denoted as follows: x-yP-z-w with x the name of the porous sample contained in the composite, y = the number of phases present in the composite, z = weight % of the porous material in the composite and w = abbreviation of the polymer(s) present in mixture. For example, A520-3P-55-PP refers to a 3 phase composite material composed of 55% by weight of MOF A520 and 40% by weight of polypropylene.

[0305] The injected parts were then characterized to determine their MOF loading, the distribution of MOF crystals in their composite bodies, and their water adsorption capacities.

[0306] FIG. 31 shows a schematic of a molded part (A520-3P-55-PP), fabricated having a curved shape, e.g., c-shaped, as depicted in this figure, with a typical height of 20 mm, outsideAttorney Docket No. CSP-0618PC(310316-02710) PATENTdiameter of 22 mm, total volume of 1856 mm3and a total surface of 1392 mm2.Compositional analysis

[0307] The amount of raw and MOF samples contained in composite materials was determined using a Nabertherm Controller B170 oven or a TGA. Samples were taken from sealed aluminum bags in which the composite materials were directly stored and protected after being manufactured. To determine the MOF loading, a calcination program was carried out (up to 1000 °C with a heating rate of 2 °C / min). Heating the composite sample causes decomposition of the organic matter, wherein the inorganic part (metal) is oxidized to form oxides (for example with aluminum species that give rise to Al2O3). By determining the number of metal atoms in the formed oxide, the content corresponding to MOF in the formulation can be obtained.

[0308] The obtained formulations are listed in Table 3.Table 3. Formulations obtained for molded parts.Formulation Channeling MOF or 4A amount name MOF used Polymers agent in the formulation 4A-3P-55-PP 4A PP PEG 55 wt.%A520-3P-31-PP A520 PP PEG 31 wt.%A520-3P-55- PP A520 PP PEG 55 wt.%A520-2P-55- PP A520 PP n / a 55 wt.%Characterization

[0309] Water adsorption kinetics realized at 22 °C and a relative humidity of 80% on the obtained injected parts shows that microporosity of the MOF is still accessible for the adsorption of humidity present in the air (see FIG. 32). It is believed that these kinetics are much slower than observed with MOF A520 powder and the granulates due to the higher thickness of molded parts are much higher, thereby increasing the diffusion length of the water molecule to be adsorbed. After 220 days, the molded parts containing MOF A520 are still adsorbing moisture (they did not reach their maximum adsorption properties).

[0310] FIG. 33 shows the mechanical resistance of the molded parts for (i) 4A-3P-55-PP (ii) A520-3P-31-PP (iii) A520-3P-55-PP (iv) A520-2P-55-PP determined by vertical compression (Zwick / Roell Zmart. Pro Dynamometer). The mechanical properties seem to be higher for theAttorney Docket No. CSP-0618PC(310316-02710) PATENTmolded part containing MOF compared to the one composed with 4A zeolite. 2 phase molded part containing MOF A520 showed higher mechanical properties than the 3 phase molded part containing the same MOF.Example 8. Polymer composites of CAU-10-HManufacture

[0311] Manufacture of composite materials in form of granulates is performed with a Thermo Scientific Process 11 Parallel Twin-screw Extruder. This apparatus possesses segmented screw design allowing adjustment of the processing conditions to simulate various compounding applications. Due to the constant processing geometry within the Thermo Scientific™ extruder portfolio, knowledge obtained from the lab trials using the Process 11 Extruder can directly be transferred to pilot or production scale equipment. This scale-up transfer is based on the specific energy introduced into the material. The die of the extruder for these tests has a diameter of 2 mm. Seven heating zones along the screw are available with 8 temperature measurement points. Screw speed can be varied between 10 and 1000 rpm. Throughput rates of 20 g / h to 2.5 kg / h can be obtained.

[0312] The obtained composite material samples were denoted as follows: x-yP-z-w with x the name of the porous sample contained in the composite, y = the number of phases present in the composite, z = weight % of the porous material in the composite and w = abbreviation of the polymer(s) present in mixture. For example, CAU-2P-33-PP refers to a 2 phase composite material composed of 33% by weight of MOF CAU-10-H and 67% by weight of polypropylene.

[0313] The granulates are then characterized to determine their MOF loading, the distribution of MOF crystals in their composite bodies, and their water adsorption capacities.

[0314] FIG. 34 shows the MOF CAU-10-H structure composed of aluminum species linked together with isophthalate organic linkers to form microporous material with the following chemical formula {AKOHjCsEEO^.

[0315] FIG. 35 shows SEM image of the MOF CAU-10-H crystals purchased from NovoMOF. This SEM image show crystal with cubic shape characteristic of MOF CAU-10-H with particle size ranging from 1 to 9 pm.

[0316] FIG. 36 shows water adsorption kinetics realized at 22 °C and a relative humidity of 80% on CAU-10-H over 185 days. CAU-10-H reaches in 24 h its maximum adsorption capacityAttorney Docket No. CSP-0618PC(310316-02710) PATENTof 344 mg of water / g of C AU- 10-H. No decrease in its adsorption capacity toward water is observed after 6 months of exposure to 80 % RH environment.Compositional analysis

[0317] The amount of raw and MOF samples contained in composite materials were determined using a Nabertherm Controller B170 oven or a TGA. Samples were taken from sealed aluminum bags in which the composite materials were directly stored and protected after being manufactured. To determine the MOF loading, a calcination program was carried out (up to 1000 °C with a heating rate of 2 °C / min). Heating the composite sample causes decomposition of the organic matter, wherein the inorganic part (metal) is oxidized to form oxides (for example with aluminum species that give rise to Al2O3). By determining the number of metal atoms in the formed oxide, the content corresponding to MOF in the formulation can be obtained. 75.5 % of weight loss is expected for well crystallized and dehydrated sample as shown from the formula below:Expected weight loss thCAU-10(Al)-H= (2 × M(Al(OH)(C8H4O4)) - M(Al2O3)) / (2 × M(Al(OH)(C8H4O4)))2 x 208.10 - 101.9675.5 %2 x 208.10

[0318] The obtained formulations are listed in Table 4.Table 4, Formulations obtained for granulates.Formulation Channeling MOF amount in the name MOF used Polymers agent formulationCAU-2P-33-PP CAU-10-H PP n / a 33 wt.%CAU-2P-48-PP CAU-10-H PP n / a 48 wt.%CAU-2P-51-PP CAU-10-H PP n / a 51 wt.%CAU-2P-59-PP CAU-10-H PP n / a 59 wt.%CAU-2P-68-PP CAU-10-H PP n / a 68 wt.%CAU-3P-47-PP CAU-10-H PP PEG 47 wt.%CAU-3P-49-PP CAU-10-H PP PEG 49 wt.%CAU-3P-61-PP CAU-10-H PP PEG 61 wt.%Attorney Docket No. CSP-0618PC(310316-02710) PATENTCAU-3P-64-PP CAU-10-H PP PEG 64 wt.%CAU-3P-66-PP CAU-10-H PP PEG 66 wt.%Characterization

[0319] FIG. 37 represents the elemental mapping of the CAU-3P-64-PP granulate, distinguishes clearly the polymer components composed of carbon from the inorganic part (Al) representing the MOF composed of carbon, oxygen, aluminum etc. In addition, the localization of the different Al atoms confirms the homogeneous distribution as well as the success of the extrusion process.

[0320] Water adsorption kinetics realized at 22 °C and a relative humidity of 80% on the obtained 2-phase granulates (see FIG. 38) and 3-phase granulates (see FIG. 39) shows that porosity of the MOF is still accessible for the adsorption of humidity present in the air. Those kinetics are much slower than the one observed with MOF CAU-10-H powder.Example 9. Polymer composites of MOF 801Manufacture

[0321] Manufacture of composite materials in form of granulates is performed with a Thermo Scientific Process 11 Parallel Twin-screw Extruder. This apparatus possesses segmented screw design allowing adjustment of the processing conditions to simulate various compounding applications. Due to the constant processing geometry within the Thermo Scientific™ extruder portfolio, knowledge obtained from the lab trials using the Process 11 Extruder can directly be transferred to pilot or production scale equipment. This scale-up transfer is based on the specific energy introduced into the material. The die of the extruder for these tests has a diameter of 2 mm. Seven heating zones along the screw are available with 8 temperature measurement points. Screw speed can be varied between 10 and 1000 rpm. Throughput rates of 20 g / h to 2.5 kg / h can be obtained.

[0322] The obtained composite material samples were denoted as follows: x-yP-z-w with x the name of the porous sample contained in the composite, y = the number of phases present in the composite, z = weight % of the porous material in the composite and w = abbreviation of the polymer(s) present in mixture. For example, 801-2P-36-PP refers to a 2 phase composite material composed of 36% by weight of MOF 801 and 64% by weight of polypropylene.

[0323] The granulates are then characterized to determine their MOF loading, theAttorney Docket No. CSP-0618PC(310316-02710) PATENTdistribution of MOF crystals in their composite bodies, and their water adsorption capacities.

[0324] FIG. 40 shows the MOF 801 structure composed of zirconium species linked together with fumaric acid organic linkers to form microporous material with the following chemical formula {Zr6C24H16O32}.

[0325] FIG. 41 shows SEM image of the MOF 801 crystals purchased from NovoMOF. This SEM image show crystal with truncated octahedral shape characteristic of MOF 801 with particle size of 0.16 + / - 0.031 pm.

[0326] FIG. 42 shows water adsorption kinetics realized at 22 °C and a relative humidity of 80% on MOF 801 over 2 days. MOF 801 reaches in 24 h its maximum adsorption capacity of 377 mg of water / g of MOF 801.Compositional analysis

[0327] The amount of raw and MOF samples contained in composite materials were determined using a Nabertherm Controller B170 oven or a TGA. Samples were taken from sealed aluminum bags in which the composite materials were directly stored and protected after being manufactured. To determine the MOF loading, a calcination program was carried out (up to 1000 °C with a heating rate of 2 °C / min). Heating the composite sample causes decomposition of the organic matter, wherein the inorganic part (metal) is oxidized to form oxides (for example with aluminum species that give rise to ZrO2). By determining the number of metal atoms in the formed oxide, the content corresponding to MOF in the formulation can be obtained. 45.8 % of weight loss is expected for well crystallized and dehydrated sample as shown from the formula below:Expected weight loss = M(Zr₆O₄(OH)₄(C₄H₂O₄)₆ - 6 × M(ZrO₂)) / M(Zr₆O₄(OH)₄(C₄H₂O₄)₆) = 1363.71 - 123.22 / 1363.71 = 45.8%4(0H\(C4H20jJ1363’71

[0328] The obtained formulations are listed in Table 5.Table 5. Formulations obtained for granulates.Formulation Channeling MOF amount in the name MOF used Polymers agent formulation801-2P-36-PP 801(Zr) PP n / a 36 wt.%801-2P-49-PP 801(Zr) PP n / a 49 wt.%Attorney Docket No. CSP-0618PC(310316-02710) PATENT801-3P-45-PP 801(Zr) PP PEG 45 wt.%801-3P-52-PP 801(Zr) PP PEG 52 wt.%Characterization

[0329] FIG. 43 represents the elemental mapping of the 801-2P-36-PP granulate, distinguishes clearly the polymer components composed of carbon from the inorganic part (Zr) representing the MOF composed of carbon, oxygen, zirconium etc. In addition, the localization of the different Zr atoms confirms the homogeneous distribution as well as the success of the extrusion process.

[0330] Water adsorption kinetics realized at 22 °C and a relative humidity of 80% on the obtained 2-phase granulates (see FIG. 44) and 3-phase granulates (see FIG. 45) shows that porosity of the MOF is still accessible for the adsorption of humidity present in the air. Those kinetics are much slower than the one observed with MOF 801 powder. After 298 days, these granulates did not their maximum adsorption capacity.Example 10. Polymer composites of MOF MIL- 160Manufacture

[0331] Manufacture of composite materials in form of granulates is performed with a Thermo Scientific Process 11 Parallel Twin-screw Extruder. This apparatus possesses segmented screw design allowing adjustment of the processing conditions to simulate various compounding applications. Due to the constant processing geometry within the Thermo Scientific™ extruder portfolio, knowledge obtained from the lab trials using the Process 11 Extruder can directly be transferred to pilot or production scale equipment. This scale-up transfer is based on the specific energy introduced into the material. The die of the extruder for these tests has a diameter of 2 mm. Seven heating zones along the screw are available with 8 temperature measurement points. Screw speed can be varied between 10 and 1000 rpm. Throughput rates of 20 g / h to 2.5 kg / h can be obtained.

[0332] The obtained composite material samples were denoted as follows: x-yP-z-w with x the name of the porous sample contained in the composite, y = the number of phases present in the composite, z = weight % of the porous material in the composite and w = abbreviation of the polymer(s) present in mixture. For example, 160-3P-16-PP refers to a 3 phase composite material composed of 16% by weight of MIL- 160 and 84% by weight of polymer mixture (ExactAttorney Docket No. CSP-0618PC(310316-02710) PATENT3040 (91%) & Elvax 250 (9%).

[0333] The granulates are then characterized to determine their MOF loading, the distribution of MOF crystals in their composite bodies, and their water adsorption capacities.

[0334] FIG. 48 shows the MIL- 160 structure composed of aluminum species linked together with organic linkers to form microporous material with the following chemical formula {AlC6H3O6}.

[0335] FIG. 49 shows SEM image of the MIL-160 crystals purchased from MOFApps. This SEM image show agglomerated crystals with sand rose format with particle size of 1.5 ± 0.5 pm.

[0336] FIG. 50 shows water adsorption kinetics realized at 5 different conditions of teamperature and relative humidity. MIL- 160 reaches in 3 h its maximum adsorption capacity of 368 to 387 mg of water / g of MIL-160 depending on conditions.Compositional analysis

[0337] The amount of raw and MOF samples contained in composite materials were determined using a Nabertherm Controller B170 oven or a TGA. Samples were taken from sealed aluminum bags in which the composite materials were directly stored and protected after being manufactured. To determine the MOF loading, a calcination program was carried out (up to 1000 °C with a heating rate of 2 °C / min). Heating the composite sample causes decomposition of the organic matter, wherein the inorganic part (metal) is oxidized to form oxides (for example with aluminum species that give rise to Al2O3). By determining the number of metal atoms in the formed oxide, the content corresponding to MOF in the formulation can be obtained. 25.8 % of weight loss is expected for well crystallized and dehydrated sample as shown from the formula below:Expected weight loss = (M(AlC6H3O6) - 0.5 × M(Al2O3)) / M(AlC6H3O6) = (198 - 51) / 198 = 25.8%

[0338] FIG. 51 shows TGA done on MIL- 160 powder which allow to obtain the real weight loss and then determine the exact amount of MOF MIL-160 present in the composite material.

[0339] The obtained formulations are listed in Table 6.Attorney Docket No. CSP-0618PC(310316-02710) PATENTTable 6. Formulations obtained for granulates.Formulation Channeling MOF amount in the name MOF used Polymers agent formulation160-3P-16-PP MIL- 160 Exact 3040 Elvax 250 16 wt.%160-3P-16-PP MIL- 160 Exact 3040 Elvax 250 43 wt.%160-3P-16-PP MIL- 160 Exact 3040 Elvax 250 50 wt.%Characterization

[0340] Water adsorption kinetics realized at 22 °C and a relative humidity of 80% on the obtained 3-phase granulates (see FIG. 52) shows that porosity of the MOF is still accessible for the adsorption of humidity present in the air. Those kinetics are much slower than the one observed with MIL-160 powder. After 250 h, these granulates have reached their maximum adsorption capacity.Example 11. RH monitoring in 48 mL vial in the presence MOF A520 powder or 3 phase A520 film

[0341] FIG. 53 shows RH monitoring in 48 mL vial at 30°C, 65% RH in the presence of MOF A520 powder or 3 phase MOF A520 film that have been pre- saturated at different rates at 22°C and 80 % RH. It can be seen that MOF A520 powder or film are able to maintain / monitor the RH between 20 and 30 % in the vial in a large domain of presaturation (up to 80 % of loading of water in the A520 MOF).References

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[0394] All references, patents or applications, U. S. or foreign, cited in the application are hereby incorporated by reference as if written herein in their entireties. Where any inconsistencies arise, material literally disclosed herein controls.

[0395] From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this disclosure, and without departing from the spirit and scope thereof, can make various changes and modifications of the disclosure to adapt it to various usages and conditions.

Claims

Attorney Docket No. CSP-0618PC(310316-02710) PATENTCLAIMSWhat is claimed is:

1. An entrained polymer comprising:a base polymer; anda metal-organic framework (MOF).

2. The entrained polymer of claim 1, wherein the metal-organic framework comprises a metal ion chosen from Al(III) and Zr(IV).

3. The entrained polymer of claim 2, wherein the metal-organic framework comprises an organic dicarboxylic acid, or a salt thereof.

4. The entrained polymer of claim 3, wherein the organic dicarboxylic acid is chosen from 1,3-benzenedicarboxylic acid, 2,5-furandicarboxylic acid, succinic acid, maleic acid, fumaric acid, malic acid, and phthalic acid, or a mixture thereof.

5. The entrained polymer of claim 4, wherein the organic dicarboxylic acid is fumaric acid.

6. The entrained polymer of claim 1, wherein the base polymer is chosen from ethylene vinyl acetate, thermoplastic elastomers, thermoplastic polymers, e.g., polyolefins such as polypropylene and polyethylene, polyisoprene, polybutadiene, polybutene, polysiloxane, polycarbonates, polyamides, ethylene / alpha olefin copolymers, ethylene 1 1 -butene copolymers, ethylene / 1 -hexene copolymers, ethylene-vinyl acetate copolymers, ethylene- methacrylate copolymer, poly(vinyl chloride), polystyrene, polyesters including polylactic acid, polyanhydrides, polyacrylonitrile, polysulfones, polyacrylic ester, acrylic, polyurethane and polyacetal, or copolymers or mixtures thereof.

7. The entrained polymer of any one of claims 1 - 6, wherein the base polymer is chosen from a polyolefin and an ethylene / alpha olefin copolymer.

8. The entrained polymer of claim 7, consisting of 10% to 70% by weight of base polymer.

9. The entrained polymer of claim 8, consisting of 30% to 80% by weight of MOF.

10. The entrained polymer of claim 1, further comprising a channeling agent.

11. The entrained polymer of claim 10, wherein the channeling agent is chosen from a polyglycol such as polyethylene glycol (PEG), ethylene-vinyl acetate (EVA), ethylene-Attorney Docket No. CSP-0618PC(310316-02710) PATENTvinyl alcohol (EVOH), polyvinyl alcohol (PVOH), glycerin polyamine, polyurethane and polycarboxylic acid including polyacrylic acid or polymethacrylic acid.

12. The entrained polymer of claim 11, wherein the channeling agent is chosen from polyethylene oxide, polypropylene oxide, ethylene vinyl acetate, nylon 6, nylon 66, or a combination thereof.

13. The entrained polymer of claim 12, wherein the channeling agent is polyethylene glycol (PEG).

14. The entrained polymer of claim 12, wherein the channeling agent is ethylene vinyl acetate copolymer (EVA).

15. The entrained polymer of claim 12, wherein the entrained polymer absorbs at least 50 mg I g, optionally at least 100 mg / g, optionally at least 150 mg / g, optionally at least 200 mg / g, optionally at least 250 mg / g water within 10 days of exposure to 80% relative humidity at 22 °C.

16. A pellet comprising the entrained polymer of any one of claims 1 -6.

17. The pellet of claim 16, wherein the base polymer is chosen from polypropylene and Exact™ 3040.

18. The pellet of claim 16, wherein the MOF is aluminum fumarate.

19. A method for manufacturing the pellet of claim 16, wherein the method comprises the step of 3D printing.

20. A film comprising the entrained polymer of any one of claims 1 -6.

21. The film of claim 20, wherein the MOF is aluminum fumarate.

22. A package comprising the entrained polymer of any one of claims 1 - 6.

23. A package comprising the pellet of claim 16.

24. A package comprising the film of claim 20.

25. A method for removing one or more contaminating substances from a product, the method comprising the step of placing the product in the package of claim 22.

26. A method for preventing contamination of a product by moisture, the method comprising the step of placing the product in the package of claim 22.Attorney Docket No. CSP-0618PC(310316-02710) PATENT27. A method for protecting a product from oxidation, the method comprising the step of placing the product in the package of claim 22.

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