Porous polymer metal complex, gas adsorbent, and gas separation device and gas storage device using same

Patent metadata

Field	Value
Publication number	US-9630164-B2
Application number	US-201314440014-A
Country	US
Kind code	B2
Filing date	Oct 31, 2013
Priority date	Nov 2, 2012
Publication date	Apr 25, 2017
Grant date	Apr 25, 2017

Abstract

An object of the present invention is to provide a porous polymer metal complex which can be used as a gas adsorbent and contains two or more types of similar ligands. A porous polymer metal complex is provided expressed by [CuX] n (1) (in the Formula, X represents two or more types of isophthalic acid ions selected from the group consisting of isophthalic acid ions and isophthalic acid ions having a substituent at position 5, at least an amount of one type of X is 5 mol % to 95 mol % of the total number of moles of X, and n represents an assembly number of constituent units expressed by CuX and is not particularly limited).

First claim

The invention claimed is:

1. A porous polymer metal complex expressed by Formula (1):
[CuX] n   (1)

wherein, in the Formula, X represents two or more types of isophthalic acid ions selected from the group consisting of isophthalic acid ions and isophthalic acid ions having a substituent at position 5, at least an amount of one type of X is 5 mol % to 95 mol % of the total number of moles of X, and n represents an assembly number of constituent units expressed by CuX and is not particularly limited.

2. The porous polymer metal complex according to claim 1 , expressed by Formula (2):
[CuX 1−m Y m ] n   (2)

wherein, in the Formula, each of X and Y represents isophthalic acid ions or isophthalic acid ions having a substituent at position 5, X and Y are different from each other, 0.05≦m≦0.95 is satisfied, and n represents an assembly number of constituent units expressed by CuX 1−m Y m and is not particularly limited.

3. The porous polymer metal complex according to claim 1 ,
wherein the porous polymer metal complex has a paddle-wheel structure having vertically coordinated two units in which a copper ion is coordinated to four carboxyl groups,
the paddle-wheel structure is connected by isophthalic acid derivatives to form a Kagome structure constituted by six-membered rings and three-membered rings, and
the Kagome structure has a stacked crystal structure.

4. The porous polymer metal complex according to claim 2 ,
wherein X in Formula (1), or X or Y in Formula (2) represents isophthalic acid ions having a substituent at position 5, and
the substituent at position 5 is a functional group selected from the group consisting of a methyl group, an ethyl group, a methoxy group, an ethoxy group, a tert-butyl group, a benzyloxy group, a nitro group, an azido group, a carboxyl group, an amino group, and a hydroxyl group.

5. The porous polymer metal complex according to claim 2 ,
wherein X and Y in Formula (2) represent isophthalic acid ions having a substituent at position 5,
the substituent at position 5 of X is a functional group selected from the group consisting of a methoxy group, a tert-butyl group, and a nitro group,
the substituent at position 5 of Y is a functional group selected from the group consisting of a methyl group, an ethyl group, a methoxy group, an ethoxy group, a tert-butyl group, a benzyloxy group, a nitro group, an azido group, a carboxyl group, an amino group, and a hydroxyl group, and
X and Y are different from each other.

6. A porous polymer metal complex expressed by Formula (21):
[CuX] n   (21)

wherein, in the Formula, X represents isophthalic acid ions having a substituted amino group at position 5, and n represents an assembly number of constituent units expressed by CuX and is not particularly limited.

7. The porous polymer metal complex according to claim 6 ,
wherein the porous polymer metal complex has a paddle-wheel structure having vertically coordinated two units in which a copper ion is coordinated to four carboxyl groups,
the paddle-wheel structure is connected by isophthalic acid derivatives to form a Kagome structure constituted by six-membered rings and three-membered rings, and
the Kagome structure has a stacked crystal structure.

8. The porous polymer metal complex according to claim 6 ,
wherein the substituted amino group is an amino group substituted with an alkyl group or an aryl group.

9. The porous polymer metal complex according to claim 6 ,
wherein the substituted amino group is a functional group selected from the group consisting of a methylamino group, a dimethylamino group, an ethylamino group, and a diethylamino group.

10. A porous polymer metal complex expressed by Formula (24):
[CuX] n   (24)

wherein, in the Formula, X represents two or more types of isophthalic acid ions selected from the group consisting of isophthalic acid ions and isophthalic acid ions having a substituent at position 5, an amount of the isophthalic acid ions having a substituted amino group at position 5 is 5 mol % or more of X, and n represents an assembly number of constituent units expressed by CuX and is not particularly limited.

11. The porous polymer metal complex according to claim 10 ,
wherein X in Formula (24) represents two or more types of ions selected from the group consisting of isophthalic acid ions, isophthalic acid ions having an alkyl group at position 5, isophthalic acid ions having an alkoxy group at position 5, isophthalic acid ions having an amino group at position 5, and isophthalic acid ions having a substituted amino group at position 5, and
an amount of the isophthalic acid ions having a substituted amino group at position 5 is 5 mol % or more with respect to the total number of moles of X.

12. A porous polymer metal complex expressed by Formula (31):
[CuX] n   (31)

wherein, in the Formula, X represents isophthalic acid ions having a branched alkyl group at position 5 or isophthalic acid ions having a branched alkoxy group at position 5, and the branched alkyl group is a functional group selected from the group consisting of an isopropyl group, 2-pentyl, 3-pentyl, 2-hexyl, 3-hexyl, and an isobutyl group, and n represents an assembly number of constituent units expressed by CuX and is not particularly limited,
wherein the porous polymer metal complex has a paddle-wheel structure having vertically coordinated two units in which a copper ion is coordinated to four carboxyl groups,
the paddle-wheel structure is connected by isophthalic acid derivatives to form a Kagome structure constituted by six-membered rings and three-membered rings, and
the Kagome structure has a stacked crystal structure.

13. The porous polymer metal complex according to claim 12 ,
wherein the branched alkyl group is a functional group selected from the group consisting of an isopropyl group, and an isobutyl group, and
the branched alkoxy group is a functional group selected from the group consisting of an isopropyloxy group, a tert-butyloxy group, and an isobutyloxy group.

14. A porous polymer metal complex expressed by Formula (34):
[CuX] n   (34)

wherein, in the Formula, X represents two or more types of isophthalic acids selected from isophthalic acid ions and isophthalic acid ions having a substituent at position 5, an amount of isophthalic acid ions having a branched alkyl group or a branched alkoxy group at position 5 is 5 mol % or more with respect to the total number of moles of X, and n represents an assembly number of constituent units expressed by CuX and is not particularly limited.

15. The porous polymer metal complex according to claim 14 ,
wherein X in Formula (34) represents two or more types of ions selected from the group consisting of isophthalic acid ions, isophthalic acid ions having an alkyl group at position 5, isophthalic acid ions having an alkoxy group at position 5, isophthalic acid ions having a unsubstituted or substituted amino group at position 5.

16. A porous polymer metal complex expressed by Formula (41):
[CuX] n   (41)

wherein, in the Formula, X represents a functional group selected from the group consisting of isophthalic acid ions in which position 5 is substituted by a perfluoroalkyl group containing 3 to 21 fluorine atoms and isophthalic acid ions in which position 5 is substituted by a perfluoroalkoxy group selected from O-n-C 3 F 7 , O-n-C 4 F 9 ,—O-n-C 5 F 11 , O-n-C 6 F 13 , O-n-C 7 F 15 , and O-n-C 8 F 17 , and n represents an assembly number of constituent units expressed by CuX and is not particularly limited,
wherein the porous polymer metal complex has a paddle-whe

Assignees

• Nippon Steel & Sumitomo Metal Corp
• Univ Kyoto

Inventors

• Kajiro Hiroshi
• Nose Koichi
• Kitagawa Susumu
• Matsuda Ryotaro
• Sato Hiroshi

Classifications

• F17C11/00

  Use of gas-solvents or gas-sorbents in vessels {(absorbing compositions for acetylene C10L3/04; absorbing compositions for hydrogen C01B3/0005)} · CPC title

• B01D2253/202

  Polymeric adsorbents · CPC title

• C07F1/08 Primary

  Copper compounds · CPC title

• 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} · CPC title

• B01D53/047

  Pressure swing adsorption · CPC title