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• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F301/00—Macromolecular compounds not provided for in groups C08F10/00 - C08F299/00

Definitions

• Known substance classes of porous solids are called metal organic frameworks (MOF) or coordination polymers.
• MOF metal organic frameworks
• Stable coordination polymers are obtained by adding organic molecules capable of complex formation, like diamines or diacids, to dissolved inorganic salts. The distances between the metal ions as coordination centers can be set in a wide range through the structure, in particular of the organic components, and result in micro- to mesoporous substances. Coordination polymers can thus be varied and are substantially documented [S. Kitagawa, et al. Angew. Chem. Int. Ed. 43 (2004) 2334].
• the ability to synthesize coordination polymers with porosity results in a new class of materials that are crystalline molecular sieves.
• the atomic structure of any coordination polymers can be determined by x-ray crystallography, the dimensions of the pores or channels can be determined with excellent certainty.
• the internal surface areas of some porous coordination polymers are significantly greater than other porous materials.
• the pore sizes/shapes are highly tunable and large pore sizes can be synthesized when compared to know zeolites. Functionalization of the backbones or frameworks in these materials can be achieved by starting the synthesis with organic linkers with functional groups already installed or by post synthesis modification.
• the present invention describes a new class of materials, coordination copolymers. Production of these materials involves sequential growth techniques such as the seed growth method, and the three dimensional propagation of the second or higher shells generates the layer features.
• the materials may be used in processes such as separation processes and as catalysts for reactions.
• the new material is a coordination copolymer comprising at least a first coordination polymer and a second coordination polymer wherein the first and second coordination polymers are not identical.
• the first coordination polymer and the second coordination polymer may be present in a first and second layered configuration.
• at least a third coordination polymer may be layered on the second layer.
• the third coordination polymer may be the same as the first layer.
• the third coordination polymer may have a different composition or a different structure from that of either the first or the second coordination polymer.
• the first and second layered configuration may form a core and shell configuration.
• At least a third coordination polymer may be layered on the shell.
• the third coordination polymer may be the same as the core.
• the third coordination polymer may have a different composition or a different structure from that of either the first or the second coordination polymer.
• One method of making a coordination copolymer involves adding at least one source of metal cations and at least one organic linking compound to a solvent to form a first solution or colloidal suspension; treating the first solution or colloidal suspension to form crystals of a first coordination polymer; adding at least one source of metal cations and at least one organic linking compound to a solvent to form a second solution or colloidal suspension wherein the second solution is not identical to the first solution or colloidal suspension; adding crystals of the first coordination polymer to the second solution or colloidal suspension; and treating the second solution or colloidal suspension to form crystals of a second coordination polymer as a layer over one or more crystals of the first coordination polymer forming a coordination copolymer wherein the first coordination polymer is not identical to the second coordination polymer.
• the crystals of the first coordination polymer may be of a size ranging from 10 nanometers to 1 micron.
• the coordination copolymers may be made by a "one-pot" method as well.
• a coordination copolymer may be made by adding at least one source of metal cations and at least one organic linking compound in a solvent to form a solution or colloidal suspension; treating the solution or colloidal suspension to form crystals of a first coordination polymer; adding at least one additional reagent selected from the group consisting of a second source of metal cations, a second organic linking compound, and a combination thereof, to the solution or colloidal suspension; and treating the solution to form crystals of a second coordination polymer as layer over one or more crystals of the first coordination polymer forming a coordination copolymer wherein the first coordination polymer is not identical to the second coordination polymer.
• the coordination copolymer may be used in a process for separating a first component from a second component of a mixture by contacting the mixture with a coordination copolymer comprising at least a first coordination polymer and a second coordination polymer wherein the first and second coordination polymers are not identical.
• the coordination copolymer may also be used as a catalyst in a chemical reaction.
• the coordination copolymer may be used for converting at least one reactant by contacting a feed comprising at least one reactant with a coordination copolymer comprising at least a first coordination polymer and a second coordination polymer wherein the first and second coordination polymers are not identical and wherein at least one coordination polymer comprises a catalytic function, to give a converted product.
• FIG. 1a and 1b are microscope images of two-layer core-shell coordination copolymers of the present invention.
• FIG. 2a and 2b are microscope images of multilayered coordination copolymers of the present invention
• FIG. 3 is a plot of the amount of adsorbed nile red into (1) a coordination copolymer wherein the two coordination polymers of the coordination copolymer are IRMOF-3 and MOF-5 and (2) a coordination copolymer wherein the two coordination polymers of the coordination copolymer is a cyclohexyl modified IRMOF-3 and MOF- 5, as a function of exposure time.
• the present invention provides a novel class of materials called block coordination copolymers, which comprise at least two different coordination polymers.
• the two different coordination polymers are spatially contiguous and the coordination copolymer exhibits regions or blocks of the first coordination polymer and of the second coordination polymer.
• the at least two different coordination polymers may be porous coordination polymers or non-porous coordination polymers or a combination thereof.
• Processes described herein demonstrate the formation of block coordination copolymers which comprise at least two non-identical coordination polymers.
• two coordination polymers may each have different pore sizes, and when used to form a single coordination copolymer the resulting multi- compositional coordination copolymer may have at least one portion having a first pore size and at least one other portion having a second pore size. More than two coordination polymers may be used to form the multicompositional coordination copolymer resulting in multiple portions of the composite having differing pore sizes.
• a novel class of materials with new properties can be produced.
• One benefit of the process is that the coordination polymers used to make the composite and hence the pore sizes can be selected depending upon the application within which the composite will be used.
• coordination copolymers may be formed for specific applications by selecting the starting coordination polymers and the process for making the coordination copolymer. It is envisioned that a coordination copolymer may be synthesized to have a high selectivity as well as a high capacity in applications such as size selective separations and size and or shape selective catalysis. [0014] Examples of suitable coordination polymers for use in synthesizing the composite coordination copolymer will be first described herein, and then the process for forming the composite coordination copolymer will be described.
• the coordination polymers used to form a coordination copolymer composite define a molecular framework.
• the coordination polymers contain a plurality of metal atoms or metal clusters linked together by a plurality of organic linking ligands.
• the linking ligand coordinates two or more metal atoms or metal clusters.
• the organic linking ligands may be the same or different.
• the organic linking ligands may be charge neutral, or each organic linking ligand is derived from a negatively charged multidentate ligand. Characteristically the linking ligands of a coordination copolymer include a first linking ligand having a first backbone, and a second linking ligand having a second backbone.
• the first and second backbones are identical, having, for example, the same aromatic ring or straight chain hydrocarbon structures. However, it is also understood that the first and second backbones may be different. For example, the first and second backbones may have different ring or straight chain structures; the first and second backbones may have the same ring or straight chain structures but be substituted with different functional groups; or the first and second backbones may be hydrocarbons, or may have one or more atoms replaced by a heteroatom such as N, O, or S.
• the coordination copolymers may be in crystal form such as in crystal clusters, they may be catalytically active, and the surface of the coordination polymer may be polar or non-polar.
• each metal cluster of the coordination copolymer includes one or more metal ions with the organic linking ligands partially or fully compensating for the charges of the metal ions.
• each metal cluster includes a metal ion or metalloid having a metal selected from the group consisting of Group 1 though 16 of the IUPAC Periodic Table of the Elements including actinides, lanthanides, and combinations thereof.
• useful metal ions include, but are not limited to, the metal ion selected from the group consisting of Mg 2 +, Ca 2+ , Sr 2 +, Ba 2+ , Sc3+, ⁇ 3+, Ti 4+ , Zr 4+ , Hf 4+ , V 4 +, V3+, V 2+ , Nb3+, Ta3+, Cr3+, Mo+3, ⁇ /3+, Mn3+, Mn 2 +, Re3+, Re 2+ , Fe3+, Fe 2 +, Ru3+, Ru 2+ , Os3+, Os 2+ , Co3+, Co 2+ , Rh+, Rh 2 +, Rh3+,
• the coordination copolymers comprise coordination polymers that have organic linking ligands.
• the organic linking ligand may be described by Formula I:
• X is a functional group
• n is an integer that is equal to or greater than 2
• Y is a hydrocarbon group or a hydrocarbon group having one or more carbon atoms replaced by a heteroatom.
• R 1 C(ZR 2 )C C(ZR 2 )R 1 ; E is O, S, Se, or Te; Z is N, P, or As; R R 1 R 2 are H, alkyl group, or aryl group; A is N, P, or As and G is O, S, Se, or Te. Suitable examples for
• X include, but are not limited to, CO2 " , CS2 “ , ROPO2 “ , PO3- 2 , ROPO3 “2 , PO4- 2 ,
• Y comprises a moiety selected from the group consisting of monocyclic aromatic ring, a polycyclic aromatic ring, a monocyclic heteroaromatic ring, a polycyclic heteroaromatic ring, alkyl groups having from 1 to 10 carbon atoms, and combinations thereof.
• Y is alkyl, alkyl amine, aryl amine, alkyl aryl amine, or phenyl.
• Y is a C-
• the coordination copolymers are characterized by having an average pore dimension from 2 to 40 angstroms, from 5 to 30 angstroms, or from 8 to 20 angstroms as determined by nitrogen adsorption. In another embodiment of the invention the coordination copolymers are characterized by having a surface area greater than 2000 m 2 /g as determined by the Langmuir method.
• the coordination copolymers are characterized by having a surface area of greater than 1000 to 40000 m ⁇ /g as determined by the Langmuir method. In yet another embodiment, the coordination polymer has a pore volume per grams of coordination polymer greater than 0.1 cm ⁇ /g as determined by nitrogen adsorption.
• bulk properties of the multicompositional coordination copolymer may be controlled by varying the concentration of the different linkers in solution during syntheses of at least one of the coordination polymers, see Example 2. Controlling the bulk properties of coordination copolymers allow for the coordination copolymers to be synthesized for specific purposes which require specific bulk properties. For example, controlling the surface area of the coordination copolymer composite could allow an end user to use less material to accomplish a given task because of the higher surface area provides a significantly larger number of active sites.
• Controlling the order of the addition of the linkers constitutes an approach to making the coordination copolymer and can be considered a seeded growth technique involving epitaxial growth of metal organic coordinated molecules with different components.
• the resultant composition of matter is a layered material derived from the nesting of the frameworks.
• techniques have relied on substitution of metal ions resulting in color contrast or magnetism changes.
• the technique herein allows for engineering of multi layered crystalline structure with different functionality.
• seeds of two different coordination polymers, A and B are separately prepared such as by the solvothermal process. Time and heat may be applied to allow seeds of the coordination polymers A and B to grow. Typical crystallization temperatures range from ambient to 25O 0 C, with reaction times from minutes to months.
• Suitable solvents include formamides, sulfoxides, nitriles, esters, amines, ethers, ketones, aromatics, aliphatics, water, and combinations thereof.
• solvents include, but are not limited to, ammonia, hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene, naphthalene, thipohene, pyridine, acetone, 1 ,2-dichloroethane, methylenechloride, tetrahydrofuran, ethanolamine, triethylamine, N.N-dimethyl formamide, N,N-diethyl formamide, methanol, ethanol, propanol, alcohols, dimethylsulfoxide, choloroform, bromoform, dibromomethane, iodoform, diiodomethane, halogenated organic solvents, N,N-dimethylacetamide, N, N- diethylacetamide, 1 -methyl-2-pyrrolidinone, amide solvents, methylpyridine, dimethylpyridine, and mixtures thereof.
• a portion of the respective reaction solutions are exchanged.
• a portion of the reaction solution containing seeds of coordination polymer A is added to the reaction solution for coordination polymer B; and a portion of the reaction solution containing seeds of coordination polymer B is added to the reaction solution for coordination polymer A.
• the seed-containing portions may be added to fresh reaction solutions instead of those used to generate the seeds.
• Time and heat may again be applied causing a new layer of coordination polymer to grow on top of the primary layer already present, see Example 3.
• the procedure may be stopped at this point with a coordination copolymer having two coordination polymers, one as a primary or core layer and the other as a layer over or surrounding the primary layer, such as a shell.
• the procedure may continue with one or more iterations causing additional layers of coordination polymers to grow.
• the original two coordination polymers may be used to form alternating layers, or additional different coordination polymers may be used to create layers of different compositions. It is also within the scope of the invention to grow the first layer on a substrate with the second layer grown over the first layer and so on.
• the coordination copolymer composition of matter may be engineered for a specific purpose.
• a coordination polymer in the primary or core layer may contain large pore sizes, while a coordination polymer in the first layer over the primary layer may contain smaller pore sizes. In this way, the material may be used as a high capacity selective adsorbent.
• the smaller pore coordination polymer layer would operate to provide the selectivity, while the larger pore coordination polymer in the primary layer would operate to provide a high capacity. Tuning of the kinetics of guest uptake and release may be possible. Other properties of the coordination copolymer may be controlled in the same manner. Furthermore, multistage catalysts in a single material may be formed. [0024] By selecting at least one coordination polymer that has a catalytic function, the coordination copolymer may be used as a catalyst to catalyze a reaction.
• the coordination copolymer may be used in a process for converting at least one reactant by contacting a feed comprising at least one reactant with the coordination copolymer comprising at least a first coordination polymer and a second coordination polymer wherein the first and second coordination polymers are not identical and wherein at least one coordination polymer comprises a catalytic function, to give a converted product.
• the reaction may be a hydrocarbon conversion reaction where a feed comprising hydrocarbons is contacted with a coordination copolymer comprising at least a first coordination polymer and a second coordination polymer wherein the first and second coordination polymers are not identical and wherein at least one coordination polymer comprises a catalytic function, to give a converted product.
• Hydrocarbon conversion process include reactions such as cracking, hydrocracking, aromatic alkylation, isoparaffin alkylation, isomerization, polymerization, reforming, dewaxing, hydrogenation, dehydrogenation, transalkylation, dealkylation, hydration, dehydration, hydrotreating, hydrodenitrogenation, hydrodesulfurization, methanation, ring opening, and syngas shift.
• the catalytic functionality may be added to the coordination copolymer after synthesis.
• Examples 5-7 further demonstrate that a coordination polymer with a particular crystal habit can be successfully layered on crystals of a coordination polymer with a different crystal habit.
• this is a difficult task to carry out successfully because crystals tend to grow most effectively on seeds of the same morphology and crystal habit.
• prisms grow best on prisms and cubes grow best on cubes.
• crystals can also be heterogeneously nucleated on nanoparticles present in reaction mixtures supersaturated with respect to the reagents necessary to the nucleation and growth of a given crystalline material.
• ice crystals are heterogeneously nucleated and then continue to grow as snowflakes on nano dust particles in the atmosphere.
• the nanocrystals can range from 10 to 100nm, although crystals approaching 500nm and even one micron in size can still be utilized as the core material. Often these nanocrystals are more irregular in habit and morphology than larger crystals of the same material. However, despite their nano size and often less- well pronounced crystal habit and morphology, the crystals can be easily identified by their characteristic powder XRD pattern. Likewise, when a second layer is grown on the surface of the first layer, the second material's characteristic XRD pattern will appear in the final product XRD pattern as a separate set of peaks.
• a key benefit of this process is that the crystals of the second material can be grown on crystals of the first or core layer in the same reaction solution used to grow the first material.
• Such in situ or "one-pot" syntheses are of significant practical importance because of such issues as waste minimization and elimination of costly intermediate processing steps such as isolation and purification of the first material before subjecting the first material to the layering chemistry of the second layer.
• the crystals of the first layer are isolated and re-suspend in a supersaturated solution of the second material in order to grow the second material on the first material. This processing might be required where the solution chemistries or other processing conditions of the two materials are incompatible.
• Another aspect of the "one-pot" Examples 5 through 7 is matching the chemistry of the material of the first or core layer with the chemistry of the second layer. This is important because, for example, the solvent for the first layer must be similar to, or the same as, the solvent for the second layer. This is because the reagents for the preparation of the second layer must be added to a suspension of the nanocrystals of the first layer. If the reagents for the preparation of the second material are insoluble in the solvent from the preparation of the first material, or if these reagents react with another soluble reagent left over in solution from the preparation of the first material, undesired by-products and/or precipitates may form.
• the chemistry of the preparation of the second material may be tailored in such a way as to react with, modify, and/or partially dissolve the crystals of the first material.
• the resultant second layer on a first material composite might then possess a highly desirable physical property such as enhanced porosity or crystal integrity.
• the selection of core and shell materials were based on the offset placement of XRD peaks for the two respective materials.
• the general design of these experiments involves reducing reactants for each product down to stoichiometric quantities, based on the molecular formula of the desired product.
• An equimolar amount of a base, such as triethylamine (TEA) was used per carboxylic acid function in order to facilitate coordination of linker to metal or metal clusters.
• the first or core material reaction is allowed to proceed for an appropriate period of time before the addition of pre-mixed reactants for the second material. Details are provided in Examples 5 - 7. Abbreviations as used in the examples include: H3BTC - 1 ,3,5-benzenetricarboxylic acid
• MOF formulas as used in the example include: HKUST-1 Cu 3 BTC2(H 2 O)3
• an abbreviation of a coordination copolymer is as follows: a first MOF formula is recited, followed by the symbol @ , followed by a second MOF formula. Multiple copolymers in a coordination copolymer are shown by reciting multiple MOF formulas, each separated from the others by the symbol @ .
• IRMOF-3@MOF-5 is used to describe the coordination copolymer containing both IRMOF-3 and MOF-5; and MOF-5@ IRMOF-3@MOF-508 is used to describe the coordination copolymer containing all three of MOF-5, MOF- 3, and MOF-508.
• the coordination copolymer has layers of MOFs, the order of the layers may be reflected in the abbreviation.
• the coordination copolymer derived from the ditopic linker benzene-1 ,4- dicarboxylate (BDC) and 2-amino benzene-1 , 4-dicarboxylate (ABDC) serves to illustrate the invention.
• FIG. 1 a shows IRMOF-3 as the shell layer and MOF-5 as the core layer
• FIG. 1 b shows MOF-5 as the shell layer and IRMOF-3 as the core layer.
• the scale bar in FIG. 1 a and 1 b is 200 ⁇ m. In both cases of MOF-5 and IRMOF-3 as seeds, core-shell-fashioned MOFs are successfully obtained.
• MOF-5@ IRMOF-3@ MOF-5 as shown in FIG. 2a
• IRMOF-3® MOF-5 @ IRMOF-3 as shown in FIG. 2b.
• the scale bar in FIG. 2a and 2b is 200 ⁇ m.
• H2ABDC 48 mg, 0.26 mmol
• H2BDC 44 mg, 0.26 mmol
• Zn(NO3)2-4H2O 0.208 g, 0.795 mmol
• 10 ml_ of DEF 10 ml_ of DEF
• MOFs were soaked in 5 ppm of nile red solution in chloroform. In prescribed time, the absorbance of solutions was measured by a UV-vis spectrometer. Using the calibration curve, the nile red concentration in solutions was calculated. From the decrease of the nile red concentrations, the adsorbed amounts of the nile red into MOFs were measured. FIG.
• FIG. 3 is a plot of the amount of adsorbed nile red into (1) a coordination copolymer wherein the two coordination polymers of the coordination copolymer are IRMOF-3 and MOF-5 and (2) a coordination copolymer wherein the two coordination polymers of the coordination copolymer is a cyclohexyl modified IRMOF-3 and MOF-5, as a function of exposure time.
• a suspension of nanoHKUST-1 was prepared by adding H3BTC (0.5g,
• a suspension of nanolRMOF-1 was prepared by adding H2BDC (0.85g, ⁇ mmol), DMF (10OmL), and zinc (II) nitrate (3.Og, l Ommol) to a glass jar with magnetic stirring at room temperature.
• TEA 1.mL, lOmmol
• a suspension of H2BDC (0.38g, 2.37mmol), EtOH (5OmL), bipy
• a suspension of nanoHKUST-1 was prepared by adding H3BTC (0.5g, 2.38mmol), DMF (8.3mL), EtOH (8.3mL), H2O (8.3mL), and copper (II) nitrate
• the blue suspension was centrifuged at 15,000 relative centrifugal force (rcf) for 1 hour, the mother liquor at pH 2-3 was decanted, and the solids were dried in a 50 0 C oven under nitrogen overnight.
• the XRD powder pattern for the solid material showed peaks for both MIL-53 and HKUST-1 , and elemental analysis on the mother liquor revealed 0.094 mass% Cu and 0.11 mass% Al in solution.

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