IP Library Granted Patent US 7,763,665
Granted Patent B2
US 7,763,665 · App. 11/634,744 · Granted Jul 27, 2010

Block polymer processing for mesostructured inorganic oxide materials

Assignee: The Regents of the University of California
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 7,763,665
App. No.
11/634,744
Granted
Jul 27, 2010
Kind
B2
Abstract

Mesoscopically ordered, hydrothermally stable metal oxide-block copolymer composite or mesoporous materials are described herein that are formed by using amphiphilic block polymers which act as structure directing agents for the metal oxide in a self-assembling system.

Claims (54)

1. A method of forming a mesoscopically structured material comprising the step of combining an amphiphilic block copolymer with an inorganic species in a solvent, wherein the block copolymer and the inorganic species are assembled and then the assembled inorganic species are polymerized to form a mesoscopically structured inorganic-organic composite, wherein said inorganic species combined with said block copolymer is a precursor inorganic species and said assembled inorganic species are hydrolyzed inorganic species, and

wherein said inorganic species is a mixture comprising at least two of M(OR)s s-t-u-v-w-y R′ t R″ u R′″ v R″″ w R′″″ y , and/or MX S wherein:

M is at least one atom other than carbon, hydrogen, oxygen, or nitrogen;

S>=1;

R, R′, R″, R′″, R″″, and R′″″ are organic moieties;

while 0 >=s, t, u, v, w, y >=6;

s-t-u-v-w-y>=1; and

X is a halogen atom.

2. The method of claim 1 , wherein said inorganic species is selected from the group consisting of AlCl 3 /SiCl 4 , ZrCl 4 /TiCl 4 , AlCl 3 /TiCl 4 , SiCl 4 /TiCl 4 , ZrCl 4 /WCl 6 , SnCl 4 /InCl 3 .

3. The method of claim 1 , wherein said mesoscopically structured inorganic-organic composite has macroscopic orientational order.

4. The method of claim 1 , wherein said mesoscopically structured inorganic-organic composite has a framework in which there is located nanocrystallites.

5. The method of claim 1 , wherein said mesoscopically structured inorganic-organic composite is in the form of (a) a powder, (b) a film, (c) a fiber, or (d) a monolith.

6. The method of claim 1 , wherein said amphiphilic block copolymer and said inorganic species are combined under non-hydrolytic conditions.

7. The method of claim 1 , wherein said amphiphilic block copolymer and said inorganic species are combined under non-aqueous conditions.

8. The method of claim 1 , wherein said block copolymer and inorganic species are assembled and polymerized within an aligning field to form the mesoscopically structured inorganic-organic composite which has a macroscopic orientational order.

9. The method of claim 1 , wherein said combined block copolymer and inorganic species are processed to induce orientational ordering before the assembled inorganic species are polymerized to form the mesoscopically structured inorganic-organic composite.

10. The method of claim 1 , wherein said block copolymer and inorganic species are assembled and polymerized in the presence of electrically responsive molecules or optically responsive molecules to form the mesoscopically structured inorganic-organic composite.

11. The method of claim 1 , including the step, after assembly of the block copolymer and the inorganic species and polymerization of the assembled inorganic species, of calcining said mesoscopically structured inorganic-organic composite to form a mesoscopically structured material.

12. The method of claim 1 , including the step, after self-assembly of the block copolymer and the inorganic species and polymerization of the assembled inorganic species, of solvent extracting said mesoscopically structured inorganic-organic composite to form a mesoscopically structured material.

13. The method of claim 1 , including the step, after self-assembly of the block copolymer and the inorganic species and polymerization of the assembled inorganic species, of removing the block copolymer from said mesoscopically structured inorganic-organic composite to form a mesoscopically structured material.

14. The method of claim 1 , wherein said mesoscopically structured inorganic-organic composite is functionalized to impart responsiveness in at least one property including an optoelectronic property, a mechanical property, a thermal property, an optical property, a separation property, or a reaction property to form a multi-functional mesoscopically structured inorganic-organic composite.

15. A method of making any of(a) a fuel cell material, (b) an opto-electronic material, (c) a quantum-effect material, or (d) a medical implant, from a mesoscopically structured inorganic-organic composite or a mesoporous inorganic oxide material which are formed by combining an amphiphilic block copolymer with an inorganic species in a solvent, wherein the block copolymer and the inorganic species are assembled and then the assembled inorganic species are polymerized to form said mesoscopically structured inorganic-organic composite.

16. The method of claim 15 in which mesoscopically structured material is formed by the following steps:

placing the amphiphilic block copolymer in an aqueous solution of inorganic salt;

combining the aqueous solution containing the block copolymer with the inorganic species to form a multiphase medium that enables microphase separation of inorganic species and the block copolymer, thereby forming an inorganic-block copolymer composite, wherein the block copolymer enables macrophase separation of the inorganic-block copolymer composite and the aqueous solution of inorganic salt;

polymerizing the inorganic species to form a meso-macrostructured inorganic-organic composite;

removing the block copolymer and aqueous solution from said meso-macrostructured inorganic-organic composite to form said mesoscopically structured material.

17. A mesoscopically structured material that was formed by combining an amphiphilic block copolymer with an inorganic species in a solvent, wherein the block copolymer and the inorganic species are assembled and then the assembled inorganic species are polymerized to form a mesoscopically structured inorganic-organic composite, wherein said inorganic species combined with said block copolymer is a precursor inorganic species and said assembled inorganic species are hydrolyzed inorganic species, and

wherein said inorganic species is a mixture of M(OR) S , M(OR) s-t-u-v-w-y R′ t R″ u R′″ v R″″ w R′″″ y , and/or MX S whereby:

M is at least one atom other than carbon, hydrogen, oxygen, or nitrogen;

S>= 1

R, R′, R″, R′″, R″″, and R′″″ are organic moieties;

while 0>=s, t, u, v, w, y>=6

s-t-u-v-w-y>1; and

X is a halogen atom.

18. The mesoscopically structured material of claim 17 , wherein said inorganic species is selected from the group consisting of AlCl 3 /SiCl 4 , ZrCl 4 /TiCl 4 , AlCl 3 /TiCl 4 , SiCl 4 /TiCl 4 , ZrCl 4 /WCl 6 , SnCl 4 /InCl 3 .

19. The mesoscopically structured material of claim 17 wherein said inorganic species includes at least two inorganic compounds.

20. The mesoscopically structured material of claim 17 , wherein said mesoscopically structured inorganic-organic composite has macroscopic orientational order.

21. The mesoscopically structured material of claim 17 , wherein said mesoscopically structured inorganic-organic composite has a framework in which there is located nanocrystallites.

22. The mesoscopically structured material of claim 17 , wherein said mesoscopically structured inorganic-organic composite is in the form of(a) a powder, (b) a film, (c) a fiber, or (d) a monolith.

23. The mesoscopically structured material of claim 17 , wherein said amphiphilic block copolymer and said inorganic species are combined under non-hydrolytic conditions.

24. The mesoscopically structured material of claim 17 , wherein said amphiphilic block copolymer and said inorganic species are combined under non-aqueous conditions.

25. The mesoscopically structured material of claim 17 , wherein said block copolymer and inorganic species are assembled and polymerized within an aligning field to form the mesoscopically structured inorganic-organic composite which has a macroscopic orientational order.

26. The mesoscopically structured material of claim 17 , wherein said combined block copolymer and inorganic species are processed to induce orientational ordering before the assembled inorganic species are polymerized to form the mesoscopically structured inorganic-organic composite.

27. The mesoscopically structured material of claim 17 , wherein said block copolymer and inorganic species are assembled and polymerized in the presence of electrically responsive molecules or optically responsive molecules to form the mesoscopically structured inorganic-organic composite.

28. The mesoscopically structured material of claim 17 , wherein said mesoscopically structured inorganic-organic composite is subjected to a calcining step to form a mesoscopically structured material.

29. The mesoscopically structured material of claim 17 , wherein said mesoscopically structured inorganic-organic composite is subjected to a solvent extracting step to form a mesoscopically structured material.

30. The mesoscopically structured material of claim 17 , wherein said block copolymer is removed from said mesoscopically structured inorganic-organic composite to form a mesoscopically structured material.

31. A product comprising any one of(a) a catalyst, (b) a separation material, (c) a semi-permeable coating, (d) a material for sensing an agent in a mixture that contact the product, (e) a fuel cell material, (f) an opto-electronic material, (g) a quantum-effect material, or (h) a medical implant, the product including a mesoscopically structured inorganic-organic composite or a mesoporous inorganic oxide material which is formed by combining an amphiphilic block copolymer with an inorganic species in a solvent, wherein the block copolymer and the inorganic species are assembled and then the assembled inorganic species are polymerized to form said mesoscopically structured inorganic-organic composite.

32. The product of claim 31 formed by the following steps:

placing an amphiphilic block copolymer in an aqueous solution of inorganic salt;

combining the aqueous solution containing the block copolymer with an inorganic species in a solvent to form a multiphase medium that enables microphase separation of inorganic species and the block copolymer, thereby forming an inorganic-block copolymer composite, wherein the block copolymer enables macrophase separation of the inorganic-block copolymer composite and the aqueous solution of inorganic salt;

polymerizing the inorganic species to form a meso-macrostructured inorganic-organic composite;

removing the block copolymer and aqueous solution from said meso-macrostructured inorganic-organic composite to form said meso-macroscopically structured material.

Assignments (4)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 21, 2015
From: BOTTOMS, WILMER
To: SBA MATERIALS, INC.
Reel/Frame 037344/0459 →
CONFIRMATORY LICENSE Recorded Dec 27, 2010
From: UNIVERSITY OF CALIFORNIA
To: NATIONAL SCIENCE FOUNDATION
Reel/Frame 025568/0771 →
CONFIRMATORY LICENSE Recorded May 20, 2010
From: UNIVERSITY OF CALIFORNIA
To: NATIONAL SCIENCE FOUNDATION
Reel/Frame 024417/0147 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 11, 2010
From: STUCKY, GALEN E; CHMELKA, BRADLEY F; ZHAO, DONGYUAN; MELOSH, NICK; HUO, QISHENG; FENG, JIANGLIN; YANG, PEIDONG; PINE, DAVID; MARGOLESE, DAVID; LUKENS, WAYNE, JR.; FREDRICKSON, GLENN H; SCHMIDT-WINKEL, PATRICK
To: THE REGENTS OF THE UNIVERSITY OF CALIFORNIA
Reel/Frame 024065/0175 →
Continuity (5)
Division 1042644100 · Apr 30, 2003
Continuation 0955425900
Provisional Application 6006914300 · Dec 9, 1997
Provisional Application 6009701200 · Aug 18, 1998
Related Publication 20070256978A1 · Nov 8, 2007