WO2011007932A1 - Structure de reseau polymere a coordination tridimensionnelle et procede de preparation associe - Google Patents

Structure de reseau polymere a coordination tridimensionnelle et procede de preparation associe Download PDF

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WO2011007932A1
WO2011007932A1 PCT/KR2009/005938 KR2009005938W WO2011007932A1 WO 2011007932 A1 WO2011007932 A1 WO 2011007932A1 KR 2009005938 W KR2009005938 W KR 2009005938W WO 2011007932 A1 WO2011007932 A1 WO 2011007932A1
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formula
network structure
ligand
bptc
dimensional
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Korean (ko)
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백명현
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서울대학교산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D259/00—Heterocyclic compounds containing rings having more than four nitrogen atoms as the only ring hetero atoms

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  • the present invention relates to a three-dimensional coordination polymer network structure and a method of manufacturing the same.
  • CPNs Coordination polymer networks with passages or cavities have been found to be applicable for gas storage, gas separation, ion exchange and selective adsorption of organic or inorganic molecules.
  • Metal-organic frameworks have been reported to adsorb even higher amounts of carbon dioxide, for example 114 wt% at 195 K, 1 bar, and 150 wt% at 298 K, 42 bar. It has been reported to adsorb 176 wt% at 303 K, 50 bar.
  • the present invention is to provide a three-dimensional coordination polymer network structure and a method of manufacturing the same to improve such a conventional problem and other required physical properties.
  • the invention is a three-dimensional network structure comprising a two-dimensional grid consisting of (1) a double macrocyclic compound linked by a flexible organic molecule and (2) a ligand comprising 2 to 4 carboxyl groups, wherein the two-dimensional
  • the grid discloses a three-dimensional network structure connected to each other between grids by the double macrocyclic compound.
  • the present invention discloses a three-dimensional coordination polymer network structure having a structure of the following formula.
  • the compound is a two-dimensional grid formed by the LIGAND is connected to each other between the grid by M x L y acting as a flexible pillar to form a three-dimensional network as a whole.
  • M is a metal selected from Ni, Cu, Fe, Co, Zn coordinated to the L y ligand
  • x is an integer selected from 2 to 6, preferably 2,
  • the LIGAND is a ligand including 2 to 4 carboxyl groups and constituting a two-dimensional grid, and examples thereof include BPTC, BTC, BDC, and TCBPDA, but are not limited thereto.
  • BPTC, BTC, BDC, TCBTDA are 1,1'-biphenyl-3,3 ', 5,5'-tetracarboxylate, benzene-1,3,5-tricarboxylate, benzene-, respectively.
  • L y is a bismacrocyclic ligand in which 2 to 6, preferably 2, macrocycles of the formula are linked by a linker.
  • the macrocyclic portion of the formula is a ligand of coordination number 4 consisting of methylene group and nitrogen, each macrocyclic ring is composed of a total of 12 to 16 carbon or nitrogen atoms, and is bonded to the carbon or nitrogen of the methylene group Hydrogen present may be substituted with NH 2 or OH.
  • the linker moiety is a linear or branched alkyl group substituted or unsubstituted with a substituent, and the substituent may be NH 2 or OH, but is not limited thereto.
  • specific examples of the linker moiety include-(CR 1 R 2 ) n-,-(CR 1 R 2 -CR 3 R 4 -CR 5 R 6 ) n-,-(CR 1 R 2 -CR 3 R 4 And an alkyl group such as -CR 5 R 6 -CR 7 R 8 ) n-, wherein n is an integer of 1 or more, and the R 1 , R 2 , R 3 , R 4 , R 5, R 6 , R 7 And R 8 are each independently (i) H, NH 2 , OH or (ii) an alkyl group substituted by NH 2 or OH, wherein the alkyl group may be a C1-C20, or C1-C10 alkyl group, or C1 Or an alkyl group of -C
  • linker moiety examples include-(CH 2 ) n-,-(CH 2 -CHR-CH 2 ) n-,-(CS 1 -CH 2 -CHS 2 )-, and the S 1 and S 2 is NH 2 or OH, wherein R is — (CH 2 ) m —NH 2 or — (CH 2 ) m-OH.
  • M is an integer of 0 or more, and may be one of integers of 0 to 10, and may be one of integers of 0 to 5.
  • M x L y include a ligand having a form in which a bismacrocyclic macrocycle of the following formula is linked by a linker (a moiety represented by LINKER) and a metal coordinated by the moiety (part represented by M in the following general formula) Or a complex consisting of), but is not limited thereto.
  • the linker may be bonded to the nitrogen atom present in the relatively protruding portion of the macro ring, or may be bonded to the nitrogen atom relatively close to the metal.
  • LINKER and M are as described above for the linker and the metal, respectively.
  • X is C or N
  • Y is hydrogen or a substituent such as NH 2 or OH.
  • M x L y may include, but are not limited to, a complex in which a linker is connected to nitrogen, which is relatively external to the macrocycle, as shown in the following formula.
  • LINKER, M, X, Y are as described above.
  • M x L y may be a complex compound represented by the following formula.
  • M is a metal selected from Ni, Cu, Fe, Co, Zn, LINKER is as described above as a linker.
  • Preferred examples of the network structure of [Formula 1] include the network structure of the following [Formula 9] or [Formula 10], in which the Ni 2 L 2 and Ni 2 L 4 of the formula [8] Having the structure, wherein R is ethyl or butyl in the Ni 2 L 2 and Ni 2 L 4 , respectively.
  • the M x L y has the structure of [Formula 8], and in the formula, R is ethyl, preferably, the network structure is obtained by desolvating the solvate of the following Formula [11].
  • the solvent included therein can be divided into a solvent as a ligand for coordinating a metal and a non ligand solvent having a solvation function. Participating non-ligand solvents are easily evaporated in air so that the number of solvent molecules can vary over time, so p is a number from 1 to 20 and is not necessarily an integer.
  • the LBP-SOLVENT is a non-ligand solvent having a solvation effect, and the number p thereof is a number between 1 and 20, and is not necessarily an integer.
  • the LIGAND may be selected from BPTC, BTC, BDC, and TCBPDA, but is not limited thereto.
  • the LBP-SOLVENT is selected from MeCN, H 2 O, MeOH, EtOH, CHCl 3 , MeCN, DMSO, DMF, acetone, and toluene. It means a boiling point solvent.
  • the network structure wherein M x L y has the structure of [Formula 8], wherein R is ethyl and LIGAND is BPTC is obtained by desolvating a solvate having the structure of [Formula 12]. It is desirable to.
  • the low boiling solvents present in the solvates are readily evaporated in air so that the number of solvated solvent molecules can vary over time, where x is a number between 1 and 20, not necessarily an integer.
  • the M x L y has the structure of [Formula 8], and the network structure in which R is butyl in the formula is preferably obtained by desolvating the solvate of [Formula 13].
  • LIGAND may be selected from BPTC, BTC, BDC, TCBPDA, but is not limited thereto, SOLVENT is H 2 O, DMF, DEF, dimethylacet Solvent selected from amide, MeCH, MeOH.
  • M x L y has the structure of [Formula 8], wherein R is butyl and the LIGAND is BPTC, and the network structure desolvates a solvate having the structure of [Formula 14]. It is preferable.
  • x is a number between 1 and 20 and need not necessarily be an integer.
  • the present invention also discloses a three-dimensional coordination polymer network structure of the structure [Formula 15].
  • x and y are numbers between 1 and 20 and need not necessarily be integers.
  • Ni 2 L 2 has the structure of [Formula 8], in the following formula R is ethyl, the LIGAND may be selected from BPTC, BTC, BDC, TCBPDA, but is not limited to these SOL1 and silver H 2 O, DMF, DEF, dimethylacetamide, MeCH, MeOH is a solvent selected from, SOL2 is a solvent selected from DEF, ROH, DMF, DMSO, MeCN, MeOH, H 2 O, wherein x and y are each 1 to 10 Is selected from.
  • the Ni 2 L 2 portion and the BPTC portion has a structure that is connected to form a network structure in three dimensions with each other.
  • Preferred examples of the network structure of the above [Formula 15] include a network structure of the following [Formula 16].
  • x and y are each a number between 1 and 20.
  • the present invention also discloses a three-dimensional coordination polymer network structure having the structure of [Formula 13].
  • q is a number between 1 and 20 and need not necessarily be an integer.
  • Ni 2 L 4 has the structure of [Formula 8], wherein R is butyl, the LIGAND LIGAND may be selected from BPTC, BTC, BDC, TCBPDA, but is not limited to this, q is 1 Number between 20 and 20, wherein SOLVENT is a solvent selected from H 2 O, DMF, DEF, dimethylacetamide, MeCH, MeOH. Similarly, the Ni 2 L 4 portion and the BPTC portion are bonded to each other to form a network structure in three dimensions.
  • Preferred examples of the network structure of [Formula 13] include a three-dimensional coordination polymer network structure having a structure of the following [Formula 2].
  • x is a number between 1 and 20 and need not necessarily be an integer.
  • the present invention also discloses a method for producing a three-dimensional coordination polymer network structure having the structure of [Formula 15], the network structure in the mixture of SOL1 / SOL2 / SOL3 [Formula 17] and H 4 BPTC Or a salt thereof self-assembled, wherein SOL1 and SOL2 are as described above, and SOL3 is used to dehydrogenate a carboxyl group, including but not limited to TEA, TMA, pyridine.
  • the salt of H 4 BPTC include, but are not limited to, Na 4 BPTC or K 4 BPTC.
  • the network structure has the structure of [Formula 16], it is preferable to use a H 2 O / DEF / TEA mixture as the mixture of SOL1 / SOL2 / SOL3.
  • x and y are each independently a number between 1 and 20, and are not necessarily integers.
  • the present invention also discloses a method for producing a three-dimensional coordination polymer network structure having the structure of [Formula 13], the network structure in the mixture of SOLVENT / SOLVENT1 and [Formula 18] and H 4 BPTC or Na Self-assembling a salt thereof, such as 4 BPTC or K 4 BPTC, wherein SOLVENT1 is a solvent selected from DEF, DEF, pyridine (?).
  • the network structure has the structure of [Formula 14], it is preferable to use the DEF / H 2 O mixture as a mixture of SOLVENT / SOLVENT 1 .
  • the present invention also discloses a method for preparing a three-dimensional coordination polymer network structure of the following [Formula 19], the preparation method includes the following steps.
  • the present invention also discloses a method for producing a three-dimensional coordination polymer network structure of the following [Formula 20], the preparation method includes the following steps.
  • the network structures having the structures of [Formula 15] and [Formula 13] have a non-interpenetrating or non-penetrating three-dimensional network structure, each macrocyclic unit is coordinated with two ligands in the trans position and each ligand Combines with four metal ions belonging to four different bismacrocyclic complexes to form a two-dimensional grid extending parallel to the ab plane.
  • the two-dimensional grid forms rhombic cavities, each cavity comprising four macrocyclic units and four ligand units. That is, the alkyl crosslinking group of the bismacrocyclic complex acts as a pillar connecting the secondary layer formed by the ligand and the macrocyclic species of the metal.
  • the bismacrocyclic complex is intersected between two two-dimensional grids, and the alkyl bridging group of the bismacrocyclic complex acts as a column connecting the grid, whereby one embodiment of the present invention is implemented.
  • the network structure according to the example has the structure of a pillared-multilayer 3D network.
  • the interlayer distance between the two-dimensional grid of the network structure having the structures of [Formula 15] and [Formula 13] may vary depending on the length and structure of the bridging alkyl group, especially when the bridging alkyl group is ethyl
  • the interlayer distance of the grid is 5 to 15 mm 3, preferably 7 to 10 mm 3, most preferably 8 to 9 mm 3.
  • the distance between grid layers is 5 to 13 mm 3, preferably 5 to 9 mm 3, and most preferably 6 to 8 mm 3.
  • the network structure having the structure of [Formula 15] forms a three-dimensional channel along the [001], [010], and [100] directions, and the above direction is arbitrarily expressed in space. It is apparent that by setting different criteria for viewing the direction in the direction, the above-described directions may be changed to form three-dimensional channels of the same shape.
  • the network structure preferably has a void volume of 40 to 70%, more preferably 50 to 60% of the crystal volume measured by PLATON.
  • the network structure having the structure of [Formula 13] forms a one-dimensional rhombic channel along the [101] direction, and the effective hole size of the channel is 0.5-3 x 5-8 8 2 Is preferable, More preferably, it is 1-2x6-7 ⁇ 2> .
  • the network structure has a solvent-accessible free volume of 20 to 50% of the total crystal volume, more preferably 30 to 40%, as measured by PLATON.
  • the network structure having the structure of [Formula 19] or [Formula 20] is Langmuir surface area measured from carbon dioxide isotherm is preferably 450 ⁇ 4500 m 2 g -1 , 480 ⁇ 4000 m 2 g -1 More preferably.
  • the network structure preferably has a pore volume of 0.1 to 1.3 cm 3 g -1 and more preferably 0.15 to 1 cm 3 g -1 measured by applying the Dubinin-Radushkevich equation.
  • the network structure having the structure of [Formula 19] or [Formula 20] exhibits hysteresis desorption and gate opening behavior, and accordingly not only gas type but also control of opening and closing of channels according to temperature and pressure This is possible.
  • the present invention also provides a gas collecting device, a gas storage device, a gas separation device, a gas detection device, and an ion exchange device including the network structure.
  • a capture, storage, separation, and sensing device relating to carbon dioxide is preferable.
  • a device for separating CO 2 in a CO 2 / H 2 mixture is preferred.
  • the network structure of the present invention is excellent in gas collection, gas storage, gas separation, ion exchange and selective adsorption of organic or inorganic molecules, and also excellent in heat, water, and air, and is excellent in temperature and pressure as well as hysteresis desorption. Its excellent gate opening and closing phenomenon allows for efficient gas capture, storage and detection.
  • 1 shows the X-ray crystal structure of 1 .
  • a) Show the lozenge channel as seen from ab plane.
  • b) Show the inclined ethyl column as seen on the ac plane.
  • Color classification: BPTC 4- light meal; Ni II bismacrocyclic complexes intersected on a two-dimensional planar grid, brown and green; Hydrogen atom is omitted.
  • FIG. 2 shows the X-ray crystal structure of 2.
  • a) View on (101) plane.
  • b) Viewed from the ac plane, showing a beveled butyl column.
  • Color classification: BPTC 4- pale gray; Ni II bismacrocyclic complexes, intersected, blue and purple; Hydrogen atom omitted
  • Figure 4 shows the carbon dioxide adsorption and desorption isotherm of SNU-M11 .
  • Figure 6 shows the gas circulating data measured in TG equipment against SNU-M10 at 298 K using the method to shedding of carbon dioxide flow rate of N 2 in 15% (v / v) then flowing pure N 2 gaseous.
  • FIG. 7A shows 3D-vs. Self-assembly of organic building blocks and Ni (II) bismacrocyclic complexes.
  • FIG. 7B shows the ORTEP diagram of 1 , the coordination environment around BPTC 4 ⁇ (thermal ellipsoid at 30% probability). Symmetry operation: a, -x + 1, y, -z + 3/2; b, x-1 / 2, y + 1/2, z; c, -x + 3/2, y + 1/2, -z + 3/2; d, -x + 3/2, -y + 1/2, -z + 1; e, x, -y + 1, z-1 / 2.
  • 10 is a PXRD pattern of 1 and guest exchange samples measured at room temperature.
  • (a) 1 1, (b) one of the as-synthesized as prepared immersed for 4 hours in MeCN 1MeCN, (c) the preparation and release immersed in a 1 EtOH 1EtOH, (d) the one prepared immersed in hexane 1hexane.
  • 11 is a PXRD pattern measured at room temperature. a) the processed pattern based on the X-ray single crystal diffraction data of 1 , b) 1 in the synthesized state, c) 1 , d) 1 prepared by drying 1 for 18 hours under vacuum for 4 hours in MeCN. E) 1 MeCN prepared by dipping , e) 1 MeCN prepared under vacuum and dried for 6 hours, SNU-M10 prepared by drying for 6 hours, f) SNU-M10 soaked in MeCN for 6 hours, and then separated solid, g) SNU-M10 in MeCN steam, Solids separated after exposure, h) SNU-M10 after exposure for 30 days in air
  • FIG. 12 is an ORTEP diagram of 2 , showing the coordination environment around BPTC 4- (thermal ellipsoid at 30% probability). Symmetry operation: a, -x + 1, y, -z + 3/2; b, x + 1/2, y + 1/2, z; c, -x + 1/2, y + 1/2, -z + 3/2; d, x-3 / 2, -y + 1/2, z-1 / 2.
  • FIG. 13 shows CPK of 1 and 2.
  • FIG. (a) Planar and side views of 1 .
  • Figure 14 is a TGA / DSC trace of the second.
  • FIG. 17 shows gas adsorption and desorption isotherms for CO 2 (diamond), CH 4 (triangle), N 2 (square), and H 2 (circle) gases.
  • 19 is SNU-M10 Adsorption isotherm of carbon dioxide, showing temperature-dependent gate opening phenomenon. a) Measured from 195 K (square), 273 K (circle), and 298 K (triangle) to 1 atm. Filled Figures: Adsorption. Empty shapes: Desorption.
  • One of the objects of the present invention is a highly flexible three-dimensional coordination polymer network, in which channels and pores are opened and closed depending on the type of gas, particularly preferably a porous and three-dimensional coordination polymer useful for selectively capturing carbon dioxide. To provide a network structure.
  • a) is [Ni 2 L 2 ] (ClO 4 ) 4 ( A) And [Ni 2 L 4 ] (ClO 4 ) 4 xH 2 O ( B (X is a number between 1 and 20), which binds ethyl and butyl bridging units, respectively.
  • B (X is a number between 1 and 20), which binds ethyl and butyl bridging units, respectively.
  • b) is alkyl-bridged Ni II
  • Porous coordination polymer networks are formed from suitable metal and organic building blocks. If a square-planar macrycyclic complex is used as the metal building block, the complex has only two vacant coordination sites at the trans site and thus simply a linear linkage to the organic ligand.
  • the network design is simple and easy because it acts as a linear linker. In this type of self-assembly, the pore shape and size of the network structure is largely determined by the organic ligands that must be located at the nodes of the polygons.
  • Design strategy of a flexible three-dimensional solid network is 1,1'-biphenyl-3,3 ', 5,5'-tetracarboxylate (BPTC) as a rectangular organic building block 4- ) And square plane Ni as linear linkage II 2D grids are formed from macrocyclic complexes, [Ni 2 L 2 ] (ClO 4 ) 4 ( A) And [Ni 2 L 4 ] (ClO 4 ) 4 8H 2 O ( B Alkyl-crosslinked Ni such as II Bismacrocyclic complexes are used to connect the two-dimensional grid with highly flexible alkyl pillars.
  • BPTC 1,1'-biphenyl-3,3 ', 5,5'-tetracarboxylate
  • BPTC 1,1'-biphenyl-3,3 ', 5,5'-tetracarboxylate
  • BPTC 1,1'-biphenyl-3,3 ', 5,5'-tetracarboxylate
  • BPTC 1,
  • two soft three-dimensional solid-state coordination polymer network structures are representative of [(Ni 2 L 2 ) (BPTC)].
  • XH 2 OyDEF One
  • X, y, z is a number between 1 and 20). They not only show thermal stability up to 300 ° C, but also air and water stability, as well as N 2 , H 2 And CH 4 Highly selective carbon dioxide compared to gas Adsorption is shown.
  • One and 2 Ni II It is the first three-dimensional columnar network structure combined from the bismacrocyclic complex.
  • 1 and 2 are insoluble in water and common organic solvents such as MeOH, EtOH, MeCN, chloroform, acetone, toluene, dimethylformamide and dimethylsulfoxide (where x, y, z, p are 1 to Number between 20).
  • common organic solvents such as MeOH, EtOH, MeCN, chloroform, acetone, toluene, dimethylformamide and dimethylsulfoxide (where x, y, z, p are 1 to Number between 20).
  • the X-ray crystal structure of 1 shows a three-dimensional network of non-phase osmosis (see FIG. 1 and Ref. 1).
  • each Ni II macrocyclic unit of A is coordinated with two BPTC 4- ligands in the trans position and each B PTC 4 binds with four Ni II ions belonging to four different bismacrocyclic complexes To form a two-dimensional grid extending parallel to the ab plane.
  • the bismacrocyclic complex is intersected between two two-dimensional grids, and the ethyl bridging group of the bismacrocyclic complex acts as a column connecting the grid, whereby the columnar-multilayer three-dimensional network Create a pil lared-multilayer 3D network.
  • the interlayer distance is 8.72 mm 3
  • the ethyl column is inclined 40.5 o with respect to the straight line connecting the two-dimensional planes (see FIG. 1).
  • the network produces three-dimensional channels along the [001], [010], and [100] directions.
  • the void volume of 1 is 50-60% of the crystal volume.
  • the channel is filled with guest solvent molecules but cannot be identified in the X-ray structure because it is severely anxious thermally. Therefore, identification and identification of the number of guest molecules were determined by IR spectra, elemental analysis, and thermogravimetric analysis (TGA) data.
  • TGA data of 1 measured under N 2 are ca. It shows a 29.7% weight loss when heated to 90 ° C (see Figure 8).
  • the TGA data as well as the temperature dependent powder X-ray diffraction (PXRD) pattern shows that 1 is thermally stable up to 300 ° C. (see FIG. 9).
  • PXRD temperature dependent powder X-ray diffraction
  • the PXRD pattern differs from the pattern of 1 . This indicates that the host network was flexible enough to change its structure depending on the type of guest molecule (see FIG. 10).
  • 1 is immersed in MeCN to exchange 1 guest molecule with MeCN to obtain [(Ni 2 L 2 ) (BPTC)] ⁇ nMeCN ( 1MeCN ) (n is a number between 1 and 10). Thereafter, 1 MeCN was heated at 100 ° C. under vacuum for 6 hours to remove MeCN guest molecules, thereby preparing [(Ni 2 L 2 ) (BPTC)] ( SNU-M10) .
  • the PXRD patterns of 1 , 1 desolvated sample ( 1 ′ ), 1MeCN, and SNU-M10 show that the network structure changes by exchange and removal of guest solvent molecules (see FIG. 11). SNU-M10 has been demonstrated by the PXRD pattern that its network structure is stable even after exposure to air for 30 days.
  • X- ray crystal structure is similar to the crystal structure of 1 (see Fig. 2 and reference material 2).
  • the butyl crosslinking group of bismacrocyclic complex B acts as a column connecting the two-dimensional layer formed by BPTC 4- and Ni II macrocyclic species.
  • the interlayer distance (6.80 ⁇ ) is considerably shorter than the interlayer distance of 1 (8.72 ⁇ ) because the butyl column (68.4 o ) is much more inclined than the ethyl column (40.5 o ) of 1 (See FIG. 2).
  • solid 2 Is Creates a one-dimensional diamond, which creates a three-dimensional channel One The opposite is true. As measured by PLATON, 2 The solvent-accessible free volume of is 35% of the total crystal volume.
  • SNU-M11 was heated at 100 ° C. under vacuum for 12 hours to obtain a desolvated solid [(Ni 2 L 4 ) (BPTC)] ( SNU-M11 ).
  • the PXRD pattern of SNU-M11 is different from that of 2 (see FIG. 16), indicating that the network structure changes as the guest water molecules are removed (see FIG. 3).
  • SNU-M10 Adsorbs carbon dioxide gas at 195 K and shows type-I isotherm (FIG. 3).
  • CO2 adsorption capacity is 24.3 wt% (123.5 cm 3 g -One at STP, 5.5 mmolg -One ).
  • Langmuir surface area measured from carbon dioxide isotherm is 505 m 2 g -One to be.
  • the pore volume measured using the Dubinin-Radushkevich equation is 0.20 cm 3 g -One to be.
  • the carbon dioxide adsorption isotherm shows an S-shaped curve, which represents an uptake of 14.6 wt% of carbon dioxide at 1 atm (74.6 cm).
  • SNU-M11 also adsorbs carbon dioxide gas at 195 K but does not adsorb carbon dioxide gas at 273 K and 298 K (FIG. 4A).
  • 195 K almost no adsorption of carbon dioxide gas to 0.18 atm (point A, P go ), then suddenly starts to adsorb the gas at 0.18 atm and reaches a plateau at 0.41 atm (point B).
  • the carbon dioxide adsorption capacity at 1 atm is 24.4 wt% (124.0 cm 3 g ⁇ 1 at STP, 5.54 mmol g ⁇ 1 ).
  • SNU-M11 maintains the amount of adsorbed carbon dioxide until the pressure drops to 0.039 atm (point C, gate-closing pressure, P gc, ). And then rapidly desorbs carbon dioxide at 0.039 atm.
  • SNU-M11 Does not adsorb carbon dioxide gas up to 1 atm at 273 K and 298 K, but adsorbs carbon dioxide gas at a pressure higher than 1 atm (FIG. 4B).
  • CO2 at 298 K, 20.0 bar Start adsorption (point A, P go ), The carbon dioxide absorption reaches 20.6 wt% at 23 bar (point B).
  • Desorption isotherms show very large hysteresis and adsorbed carbon dioxide is 10.0 bar (point C, P gc Cannot be released until).
  • the synchrotron PXRD pattern of SNU-M10 measured under vacuum shows that the network structure is temperature independent at 195 K, 273 K and 298 K (see FIG. 21). However, at 1 atm CO 2 and 298 K, some of the peaks of the PXRD shift to a lower angular region than the peak measured under vacuum, which shows that the expansion of the network occurs by CO 2 adsorption (see FIG. 5). .
  • the inventors first produced highly flexible 3D pillared coordination networks using Ni II bismacrocyclic complexes.
  • the network structure can open and close channels according to gas type, temperature and pressure.
  • the alkyl column connecting the 2D square-grids is inclined considerably, and the channel size is adjusted according to the slope of the column.
  • the 1 and 2 desolvated solids, SNU-M10 and SNU-M11 exhibit thermal stability up to 300 ° C., stability to air and water, as well as higher selective adsorption to carbon dioxide than N 2 , H 2 and CH 4 . see.
  • the CO 2 : N 2 selectivity in SNU-M10 is 98: 1 (v / v) at 298 K, 1 atm.
  • the carbon dioxide adsorption isotherms of both networks show gate opening and large hysteresis desorption.
  • the gate opening pressure of the SNU-M10 is lower than that of the SNU-M11 , which shows that the ethyl column has more flexibility than the butyl column.
  • the gate opening energy for carbon dioxide absorption of SNU-M10 is 27.6 kJmol ⁇ 1 .
  • Selective and reversible carbon dioxide adsorption was also confirmed by gas cycle experiments.
  • This three-dimensional coordination polymer network with flexible columns can be applied to the selective capture, storage and detection of carbon dioxide gas as well as to the separation of the CO 2 / H 2 mixture due to a water gas shift reaction.
  • Ni (II) bismacrocyclic complexes A and B were prepared by modifying the one pot template condensation reactions developed by the present inventors.
  • H 4 BPTC (3,3 ', 5,5'-biphenyltetracarboxylic acid) was prepared by modifying the previously reported method.
  • Infrared spectra were recorded using a Perkin-Elmer Spectrum One FT-IR spectrophotometer. Elemental analysis was performed using a Perkin-Elmer 2400 Series II CHN analyzer. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were performed at a scanning rate of 5 ° C./min under N 2 using a TGA Q50 and DSC Q10 of TA apparatus, respectively.
  • TGA Thermogravimetric analysis
  • DSC differential scanning calorimetry
  • Synchrotron X-ray diffraction data were collected using a Korean Pohang Radiation Accelerator, Beamline 11A.
  • N, N-bis (2-aminoethyl) -1,3-propane diamine 8.33 g, 50.0 mmol
  • para Ethylenediamine 1.67 mL, 25.0 mmol
  • formaldehyde 4.35 g, 15.0 mmol
  • 1,4-diaminobutane 2.52 mL, 25.0 mmol
  • the mixture was heated to reflux for 2 days, during which time the solution gradually turned brown.
  • the solution was filtered while hot and the filtrate was concentrated to half volume.
  • the solution was left in a refrigerator until a purple precipitate of [Ni 2 L 2 Cl 4 ] or [Ni 2 L 4 Cl 4 ] was formed, filtered to remove the precipitate, washed with methanol and dried in air. .
  • the precipitate was dissolved in a minimum amount of water to form a yellow solution, then excess LiClO 4 saturated methanol solution was added.
  • the solution was left at room temperature until orange crystals formed.
  • the solid was removed by filtration, washed with methanol and dried in air.
  • Example 2 Preparation of [(Ni 2 L 2 ) (BPTC)].
  • Example 7 Preparation of [(Ni 2 L 4 ) (BPTC)] ⁇ pH 2 O (2), where p is a number between 1 and 20
  • N 2 and H 2 gas adsorption and desorption isotherms were monitored at 77 K, 195 K and 298 K, and carbon dioxide gas adsorption and desorption isotherms were measured at 195 K, 273 K and 298 K. After each gas adsorption and desorption measurement, the sample weight was again measured accurately.
  • High pressure gas adsorption isotherms of SNU-M10 and SNU-M11 on carbon dioxide gas were measured by gravimetric method using Rubotherm MSB (magnetic suspension balance). All gases used a 99.999% purity grade and carbon dioxide adsorption and desorption isotherms were measured at 298 K.
  • the SN U-M10 and SNU-M11 solids were heated in a Schlenk tube for 12 hours under vacuum at 100 ° C., vacuum, precisely measured the amount of dried solids, then inserted into the gas adsorption and desorption equipment, and subjected to 100 ° C. evacuation. By reactivation.
  • the He isotherm (up to 90 bar) was measured at 298 K before the gas adsorption and desorption measurement. After measuring the excess adsorption isotherm, the volume of the structure was multiplied by the density of the gas at each pressure and temperature to correct for buoyancy.
  • Preliminary orientation matrixes and unit cell parameters were obtained from the peak of the first 10 frames and then refined using the entire data set. After integrating the frames, DENZO was used to correct for Lorentz and polarization effects. Scaling and global refinement of crystal parameters were performed by SCALEPACK.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

L'invention concerne une structure de réseau polymère à coordination tridimensionnelle, ainsi qu'un procédé de préparation associé. La structure de réseau selon l'invention présente d'excellentes propriétés de collecte de gaz, de stockage de gaz, de séparation de gaz, d'échange d'ions et d'adsorption sélective de molécules organiques ou inorganiques. Cette structure présente également d'excellentes propriétés de stabilité à la chaleur, à l'eau et à l'air, ainsi que des phénomènes d'ouverture et de fermeture de grille qui dépendent de la température et de la pression, ainsi que de désorption hystérétique du gaz, ce qui permet une collecte, un stockage et une détection efficaces de gaz.
PCT/KR2009/005938 2009-07-17 2009-10-15 Structure de reseau polymere a coordination tridimensionnelle et procede de preparation associe WO2011007932A1 (fr)

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