Organic/inorganic complex porous materials

• US 6,248,686 B1
• Filed: 07/02/1999
• Issued: 06/19/2001
• Est. Priority Date: 07/03/1998
• Status: Expired due to Term

• Current Assignee: Kabushiki Kaisha Toyota Chuo Kenkyusho (Toyota Motor Corporation)
• Original Assignee: Kabushiki Kaisha Toyota Chuo Kenkyusho (Toyota Motor Corporation)
• Inventors: Inagaki, Shinji, Guan, Shiyou, Fukushima, Yoshiaki
• Primary Examiner(s): Bell, Mark L.
• Assistant Examiner(s): DiVerdi, Michael J.
• Application Number:
  US09/347,005
• Time in Patent Office: 718 Days
• Field of Search: 423/210, 423/325, 423/335, 423/703, 502/62, 502/64, 502/65, 502/66, 502/71, 502/158, 502/232, 502/407, 502/415
• US Class Current: 502/158
• CPC Class Codes: B01J 20/103 comprising silica
• CPC Class Codes: B01J 20/262 obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds per se C08G
• CPC Class Codes: B01J 20/28083 being in the range 2-50 nm, i.e. mesopores
• CPC Class Codes: C08G 77/22 containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen C08G77/045 takes precedence
• CPC Class Codes: C08G 77/58 Metal-containing linkages C08G77/485 takes precedence
• CPC Class Codes: C08G 83/001 Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica

Abstract

Organic/inorganic complex porous materials are disclosed having a main skeletal chain containing metal atoms, oxygen atoms, and organic groups. Preferably, the metal atoms, oxygen atoms and organic groups are bound by ionic bonds and/or covalent bonds, and the organic group is bound to at least two metal atoms in the main chain of the skeleton of the porous material. More preferably, 60% or more of the total pore volume in the porous material has a pore diameter in a range of ±40% of the pore diameter, as determined from the maximum peak in a pore size distribution curve. Alternatively, at least one peak is present at a diffraction angle that preferably corresponds to a d value of at least 1 nm in an x-ray diffraction pattern. Method of making such organic/inorganic complex materials are also disclosed.

Claims

1. A porous material comprising:

a mesoporous material having pores, in which at least 60% total pore volume is within a range of ±

40% from a mean pore diameter or at least one peak is present in an x-ray diffraction pattern at a diffraction angle corresponding to a d value of at least 1 nm and comprising;

a skeleton comprising at least two metal atoms, at least one oxygen atom and at least one organic group bound to at least two metal atoms.

2. The porous material of claim 1, wherein the organic group is at least one group selected from an alkylene group, an alkenylene group, alkynylene group, phenylene group, hydrocarbons containing a phenylene group, organic groups derived from compounds having at least one carbon atom, an amido group, amino group, imino group, mercapto group, sulfone group, carboxyl group, ether group and acyl group.

3. The porous material of claim 1, wherein the organic group is selected from the group consisting of an alkyl group having a valency of at least two, an alkenyl group having a valency of at least two and an aromatic ring-containing a hydrocarbon group having a valency of at least two.

4. The porous material of claim 1, wherein the at least two metal atoms are selected from the group consisting of silicon, aluminum, zirconium, tantalum, niobium, tin, hafnium, magnesium, molybdenum, cobalt, nickel, gallium, beryllium, yttrium, lanthanum, lead and vanadium.

5. The porous material of claim 1, having a mean pore diameter of from about 1 nm to about 30 nm.

6. The porous material of claim 1, wherein the metal atoms are silicon.

7. The porous material of claim 1, wherein the porous material has a shape selected from the group consisting of a two-dimensional hexagonal structure, a three-dimensional hexagonal structure, a cubic structure, a lamella structure and an irregular structure.

8. The porous material of claim 1, wherein the porous material is a particle having a spherical shape or a hexagonal rod shape.

9. The porous material of claim 1, wherein the mesoporous material has a specific surface area of at least 700 m²/g.

10. The porous material of claim 1, wherein the organic group is selected from the group consisting of an alkyl group having a valency of at least two, an alkenyl group having a valency of at least two and an aromatic ring-containing a hydrocarbon group having a valency of at least two, the metal atom is silicon, the mean pore diameter is from about 1 nm to about 30 nm and the mesoporous material has a specific surface area that is at least 700 m²/g.

23. The porous material of claim 1, wherein the organic group is a polar organic group.

24. The porous material of claim 1, wherein the organic group is a nonpolar organic group.

11. A method for forming a porous material comprising:

polycondensing an organometallic compound in the presence of a surfactant, the organometallic compound comprising an organic group bound to at least two metal atoms, and a hydrolysis group bound to at least one of the at least two metal atoms.

12. The method of claim 11, wherein the organic group is at least one group selected from an alkylene group, an alkenylene group, alkynylene group, phenylene group, hydrocarbons containing a phenylene group, organic groups derived from compounds having at least one carbon atom, an amido group, amino group, imino group, mercapto group, sulfone group, carboxyl group, ether group and acyl group.

13. The method of claim 11, wherein the organometallic compound comprises at least one group consisting of an alkyl group which has a valency of at least two, an alkenyl group which has a valency of at least two and an aromatic ring-containing hydrocarbon group which has a valency of at least two.

14. The method of claim 11, wherein said at least two metal atoms are selected from the group consisting of silicon, aluminum, zirconium, tantalum, niobium, tin, hafnium, magnesium, molybdenum, cobalt, nickel, gallium, beryllium, yttrium, lanthanum, lead and vanadium.

15. The method of claim 11, wherein said metal atoms are silicon.

16. The method of claim 11, wherein said organometallic compound is selected from the group consisting of structures (1), (2), (3), (4), (5), and (6), wherein structure (1) is:

structure (2) is;

structure (3) is;

structure (4) is;

structure (5) is;

and structure (6) is;

and wherein

each respective M is a metal atom,

each respective R¹ is an organic group,

each respective R² is a hydrocarbon group,

each respective R³ is a hydrogen atom, hydroxyl group, or hydrocarbon group,

m is an integer of at least 1, and

n is an integer of 0 or more obtained by subtracting (m+1) from the valency of a metal atom M.

17. The method of claim 11, wherein said surfactant is an alkyltrimethylammonium compound having an alkyl chain of about 8 to 18 carbon atoms or a triblock copolymer having polyalkylene oxide chains.

18. The method of claim 11, wherein said polycondensation reaction is performed at a pH greater than 7.

19. The method of claim 11, wherein the hydrolysis group is an alkoxyl group or a halogen group.

20. The method of claim 19, wherein the organometallic compound comprises at least one of an alkyl group which has a valency of at least two, an alkenyl group which has a valency of at least two or an aromatic ring-containing hydrocarbon group which has a valency of at least two and the organometallic compound contains at least one of an amino group, an amido group, a mercapto group, a sulfone group or a carboxyl group, the metal atom is silicon, the surfactant is an alkyltrimethylammonium having an alkyl chain of about 8 to 18 carbon atoms or a triblock copolymer having polyalkylene oxide chains and the polycondensation reaction is performed at a pH greater than 7.

21. A method for forming a porous material comprising:

polycondensing at least a first compound and a second compound, wherein the first compound is an organometallic compound having an organic group bound to at least two metal atoms, and at least one hydrolysis group bound to each metal atom, and the second compound has at least one hydrolysis group bound to a metal atom.

22. The method of claim 21, wherein said hydrolysis group is an alkoxyl group or a halogen group.

25. A porous material formed by:

polycondensing an organometallic compound in the presence of a surfactant, the organometallic compound comprising an organic group bound to at least two metal atoms, and a hydrolysis group bound to at least one of the two metal atoms.

26. A porous material comprising

a mesoporous material having pores, in which at least 60% total pore volume is within a range of ±

40% from a mean pore diameter or at least one peak is present in an x-ray diffraction pattern at a diffraction angle corresponding to a d value of at least 1 nm and comprising;

a skeleton comprising at least two metal atoms, at least one oxygen atom and at least one organic group having a valency of at least two.