COMPOSITIONS CONTAINING BORANE OR CARBORANE CAGE COMPOUNDS AND RELATED APPLICATIONS

• US 20130072604A1
• Filed: 10/31/2012
• Published: 03/21/2013
• Est. Priority Date: 06/16/2009
• Status: Active Grant

• Current Assignee: Honeywell Federal Manufacturing & Technologies, LLC (Honeywell International Inc.)
• Original Assignee: Honeywell Federal Manufacturing & Technologies, LLC (Honeywell International Inc.)
• Inventors: Bowen, Daniel E. III, Eastwood, Eric A.
• Granted Patent: US 8,883,895 B2
• Time in Patent Office: Days
• US Class Current: 524/183
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C08K 5/55 Boron-containing compounds C08K5/0091 takes precedence
• CPC Class Codes: Y10S 977/734 Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
• CPC Class Codes: Y10S 977/742 Carbon nanotubes, CNTs
• CPC Class Codes: Y10S 977/762 Nanowire or quantum wire, i.e. axially elongated structure having two dimensions of 100 nm or less

Abstract

Compositions comprising a polymer-containing matrix and a filler comprising a cage compound selected from borane cage compounds, carborane cage compounds, metal complexes thereof, residues thereof, mixtures thereof, and/or agglomerations thereof, where the cage compound is not covalently bound to the matrix polymer. Methods of making and applications for using such compositions are also disclosed.

Claims

1. A composition comprising:

a matrix comprising a polymer, wherein said polymer comprises less than 90 weight percent of a poly(conjugated diene), wherein said polymer comprises less than 90 weight percent of a polysiloxane; and

a filler comprising a mixture of cage compounds selected from the group consisting of a borane cage compound, a carborane cage compound, a metal complex thereof, a residue thereof, and agglomerations thereof, wherein said cage compounds comprise at least 7 cage atoms,

wherein said cage compounds are not covalently bound to said polymer.

2. The composition of claim 1, wherein said polymer comprises less than 10 weight percent of a poly(conjugated diene), wherein said polymer comprises less than 10 weight percent of a polysiloxane.

3. The composition of claim 1, wherein one of said cage compounds comprises a borane cage compound and/or a carborane cage compound having 12 cage atoms, wherein said cage compound has an icosahedral structure.

4. The composition of claim 1, wherein one of said cage compounds comprises one or more pendant groups selected from the group consisting of a C₁ to C₂₀ n-alkyl, a hydroxy, a carboxy, an epoxy, an isocyanate, a primary amine, a silyl, and an alkoxy silyl.

5. The composition of claim 1, wherein one of said cage compounds is selected from the group consisting of:

(a) a closo-carborane having the general formula C₂B_nH_n+2, wherein n is in the range of from 5 to 10;

(b) a closo-carborane having the general formula R_x[C₂B_nH<sub>n+2−

x</sub>], wherein n is in the range of from 5 to 10, x is in the range of from 1 to 2, and each R is independently selected from the group consisting of a C₁ to C₂₀ n-alkyl, a hydroxy, a carboxy, an epoxy, an isocyanate, a primary amine, a silyl, and an alkoxy silyl;

(c) a closo-carborane salt having the general formula [CB_nH_n+1]X, wherein n is in the range of from 6 to 11, and X is selected from the group consisting of Li⁺, Na⁺, K⁺, Cs⁺, and a quaternary ammonium;

(d) a closo-carborane salt having the general formula R[CB_nH_n]X, wherein n is in the range of from 6 to 11, R is selected from the group consisting of a C₁ to C₂₀ n-alkyl, a hydroxy, a carboxy, an epoxy, an isocyanate, a primary amine, a silyl, and an alkoxy silyl, and X is selected from the group consisting of Li⁺, Na⁺, K⁺, Cs⁺, and a quaternary ammonium;

(e) a closo-borane salt having the general formula [B_nH_n]X₂, wherein n is in the range of from 7 to 12, and X is selected from the group consisting of Li⁺, Na⁺, K⁺, Cs⁺, and a quaternary ammonium;

(f) a closo-borane salt having the general formula [B_nH_m(OR)_p]X₂, wherein n is in the range of from 7 to 12, wherein m+p=n, with p being in the range of from 1 to 12, each R is independently selected from the group consisting of a hydrogen atom and an aliphatic group, and X is selected from the group consisting of Li⁺, Na⁺, Cs⁺, and a quaternary ammonium;

(g) a nido-carborane salt having the general formula R_x[C₂B_nH<sub>n+2−

x</sub>]X₂, wherein n is in the range of from 5 to 9, x is in the range of from 1 to 2, each R is independently selected from the group consisting of a C₁ to C₂₀ n-alkyl, a hydroxy, a carboxy, an epoxy, an isocyanate, a primary amine, a silyl, and an alkoxy silyl, and X is selected from the group consisting of Li⁺, Na⁺, K⁺, Cs⁺, and a quaternary ammonium;

(h) a nido-carborane salt having the general formula R_x[CB_nH<sub>n+1−

x</sub>]X₃ wherein n is in the range of from 6 to 10, x is in the range of from 0 to 1, R is selected from the group consisting of a C₁ to C₂₀ n-alkyl, a hydroxy, a carboxy, an epoxy, an isocyanate, a primary amine, a silyl, and an alkoxy silyl, and X is selected from the group consisting of Li⁺, Na⁺, K⁺, Cs⁺, and a quaternary ammonium; and

(i) mixtures of two or more thereof.

6. The composition of claim 1, wherein one of said cage compounds is selected from the group consisting of:

7. The composition of claim 1, wherein said matrix comprises a plurality of polymers.

8. The composition of claim 1, wherein said polymer is selected from the group consisting of an epoxy polymer, a polyurethane, poly(ethylene-co-vinyl acetate), poly(ethylene-co-vinyl acetate-co-vinyl alcohol), poly(ethylene-co-ethyl acrylate), poly(ethylene-co-octene), a polycyanurate, and mixtures of two or more thereof.

9. The composition of claim 1, wherein said polymer constitutes at least 50 weight percent of said matrix, wherein said cage compound constitutes at least 50 weight percent of said filler, wherein said filler is present in said composition in an amount in the range of from about 0.01 to about 75 weight percent based on the entire weight of said composition, wherein said polymer is present in said composition in an amount in the range of from about 25 to about 99.99 weight percent based on the entire weight of said composition.

10. The composition of claim 1, wherein said filler further comprises a material selected from the group consisting of carbon nanotubes, carbon fullerenes, polyhedral oligomeric silsesquioxane, boron nitride nanotubes, clay, and mixtures of two or more thereof.

11. The composition of claim 1, wherein said polymer is not a sacrificial binder.

12. An article of manufacture comprising the composition of claim 1.

13. A composition comprising:

a matrix comprising a polymer; and

a filler comprising a cage compound selected from the group consisting of a borane cage compound, a carborane cage compound, a metal complex thereof, a residue thereof, mixtures thereof, and agglomerations thereof, wherein said cage compound comprises at least 7 cage atoms, wherein said cage compound comprises less than 95 weight percent of each of ortho-[1,2-dicarbadodecaborane], meta-[1,7-dicarbadodecaborane], para-[1,12-dicarbadodecaborane], and a compound having the following structure;

14. The composition of claim 13, wherein said cage compound comprises less than 10 weight percent of each of ortho-[1,2-dicarbadodecaborane], meta-[1,7-dicarbadodecaborane], para-[1,12-dicarbadodecaborane], and a compound having the following structure:

15. The composition of claim 13, wherein said cage compound comprises a borane cage compound and/or a carborane cage compound having 12 cage atoms, wherein said cage compound has an icosahedral structure.

16. The composition of claim 13, wherein said cage compound comprises one or more pendant groups selected from the group consisting of a C₁ to C₂₀ n-alkyl, a hydroxy, a carboxy, an epoxy, an isocyanate, a primary amine, a silyl, and an alkoxy silyl.

17. The composition of claim 13, wherein said cage compound is selected from the group consisting of:

(a) a closo-carborane having the general formula C₂B_nH_n+2, wherein n is in the range of from 5 to 10;

(b) a closo-carborane having the general formula R_x[C₂B_nH<sub>n+2−

x</sub>], wherein n is in the range of from 5 to 10, x is in the range of from 1 to 2, and each R is independently selected from the group consisting of a C₁ to C₂₀ n-alkyl, a hydroxy, a carboxy, an epoxy, an isocyanate, a primary amine, a silyl, and an alkoxy silyl;

(c) a closo-carborane salt having the general formula [CB_nH_n+1]X, wherein n is in the range of from 6 to 11, and X is selected from the group consisting of Li⁺, Na⁺, K⁺, Cs⁺, and a quaternary ammonium;

(d) a closo-carborane salt having the general formula R[CB_nH_n]X, wherein n is in the range of from 6 to 11, R is selected from the group consisting of a C₁ to C₂₀ n-alkyl, a hydroxy, a carboxy, an epoxy, an isocyanate, a primary amine, a silyl, and an alkoxy silyl, and X is selected from the group consisting of Li⁺, Na⁺, K⁺, Cs⁺, and a quaternary ammonium;

(e) a closo-borane salt having the general formula [B_nH_n]X₂, wherein n is in the range of from 7 to 12, and X is selected from the group consisting of Li⁺, Na⁺, K⁺, Cs⁺, and a quaternary ammonium;

(f) a closo-borane salt having the general formula [B_nH_m(OR)_p]X₂, wherein n is in the range of from 7 to 12, wherein m+p=n, with p being in the range of from 1 to 12, each R is independently selected from the group consisting of a hydrogen atom and an aliphatic group, and X is selected from the group consisting of Li⁺, Na⁺, K⁺, Cs⁺, and a quaternary ammonium;

(g) a nido-carborane salt having the general formula R_x[C₂B₂H<sub>n+2−

x</sub>]X₂, wherein n is in the range of from 5 to 9, x is in the range of from 1 to 2, each R is independently selected from the group consisting of a C₁ to C₂₀ n-alkyl, a hydroxy, a carboxy, an epoxy, an isocyanate, a primary amine, a silyl, and an alkoxy silyl, and X is selected from the group consisting of Li⁺, Na⁺, K⁺, Cs⁺, and a quaternary ammonium;

(h) a nido-carborane salt having the general formula R_x[CB_nH<sub>n+1−

x</sub>]X₃ wherein n is in the range of from 6 to 10, x is in the range of from 0 to 1, R is selected from the group consisting of a C₁ to C₂₀ n-alkyl, a hydroxy, a carboxy, an epoxy, an isocyanate, a primary amine, a silyl, and an alkoxy silyl, and X is selected from the group consisting of Li⁺, Na⁺, K⁺, Cs⁺, and a quaternary ammonium; and

(i) mixtures of two or more thereof.

18. The composition of claim 13, wherein said cage compound is selected from the group consisting of:

19. The composition of claim 13, wherein said matrix comprises a plurality of polymers.

20. The composition of claim 13, wherein said polymer is selected from the group consisting of an epoxy polymer, a polyurethane, a polysiloxane, poly(ethylene-co-vinyl acetate), poly(ethylene-co-vinyl acetate-co-vinyl alcohol), styrene-butadiene-styrene, polyethylene-co-ethyl acrylate), poly(ethylene-co-octene), a polycyanurate, and mixtures of two or more thereof.

21. The composition of claim 13, wherein said polymer constitutes at least 50 weight percent of said matrix, wherein said cage compound constitutes at least 50 weight percent of said filler, wherein said filler is present in said composition in an amount in the range of from about 0.01 to about 75 weight percent based on the entire weight of said composition, wherein said polymer is present in said composition in an amount in the range of from about 25 to about 99.99 weight percent based on the entire weight of said composition.

22. The composition of claim 13, wherein said filler further comprises a material selected from the group consisting of carbon nanotubes, carbon fullerenes, polyhedral oligomeric silsesquioxane, boron nitride nanotubes, clay, and mixtures of two or more thereof.

23. An article of manufacture comprising the composition of claim 13.

24. A method of making a nanocomposite, said method comprising:

combining and mixing a matrix and a filler,

wherein said matrix comprises a polymer, wherein said polymer comprises less than 90 weight percent of a poly(conjugated diene), wherein said polymer comprises less than 90 weight percent of a polysiloxane,

wherein said filler comprises a cage compound selected from the group consisting of a borane cage compound, a carborane cage compound, a metal complex thereof, a residue thereof, mixtures thereof, and agglomerations thereof, wherein said cage compound comprises at least 7 cage atoms,

wherein said cage compound does not covalently bond to said polymer during said mixing.

25. The method of claim 24, further comprising, after said mixing, curing said matrix and said filler at an elevated temperature, wherein said cage compound does not covalently bond to said polymer during said curing.

26. The method of claim 24, wherein said polymer comprises less than 10 weight percent of a poly(conjugated diene), wherein said polymer comprises less than 10 weight percent of a polysiloxane.

27. The method of claim 24, wherein said cage compound comprises less than 10 weight percent of each of ortho-[1,2-dicarbadodecaborane], meta-[1,7-dicarbadodecaborane], para-[1,12-dicarbadodecaborane], and a compound having the following structure:

28. The method of claim 24, wherein said polymer comprises one or more residues of a cage compound monomer selected from the group consisting of a borane cage compound monomer, a carborane cage compound monomer, and mixtures thereof.

29. The method of claim 24, wherein said cage compound comprises a borane cage compound and/or a carborane cage compound having 12 cage atoms, wherein said cage compound has an icosahedral structure.

30. The method of claim 24, wherein said cage compound comprises one or more pendant groups selected from the group consisting of a C₁ to C₂₀ n-alkyl, a hydroxy, a carboxy, an epoxy, an isocyanate, a primary amine, a silyl, and an alkoxy silyl.

31. The method of claim 24, wherein said cage compound is selected from the group consisting of:

(a) a closo-carborane having the general formula C₂B_nH_n+2, wherein n is in the range of from 5 to 10;

(b) a closo-carborane having the general formula R_x[C₂B_nH<sub>n+2−

x</sub>], wherein n is in the range of from 5 to 10, x is in the range of from 1 to 2, and each R is independently selected from the group consisting of a C₁ to C₂₀ n-alkyl, a hydroxy, a carboxy, an epoxy, an isocyanate, a primary amine, a silyl, and an alkoxy silyl;

(c) a closo-carborane salt having the general formula [CB_nH_n+1]X, wherein n is in the range of from 6 to 11, and X is selected from the group consisting of Li⁺, Na⁺, K⁺, Cs⁺, and a quaternary ammonium;

(d) a closo-carborane salt having the general formula R[CB_nH_n]X, wherein n is in the range of from 6 to 11, R is selected from the group consisting of a C₁ to C₂₀ n-alkyl, a hydroxy, a carboxy, an epoxy, an isocyanate, a primary amine, a silyl, and an alkoxy silyl, and X is selected from the group consisting of Li⁺, Na⁺, K⁺, Cs⁺, and a quaternary ammonium;

(e) a closo-borane salt having the general formula [B_nH_n]X₂, wherein n is in the range of from 7 to 12, and X is selected from the group consisting of Li⁺, Na⁺, K⁺, Cs⁺, and a quaternary ammonium;

(f) a closo-borane salt having the general formula [B_nH_m(OR)_p]X₂, wherein n is in the range of from 7 to 12, wherein m+p=n, with p being in the range of from 1 to 12, each R is independently selected from the group consisting of a hydrogen atom and an aliphatic group, and X is selected from the group consisting of Li⁺, Na⁺, K⁺, Cs⁺, and a quaternary ammonium;

(g) a nido-carborane salt having the general formula R_x[C₂B_nH<sub>n+2−

x</sub>]X₂, wherein n is in the range of from 5 to 9, x is in the range of from 1 to 2, each R is independently selected from the group consisting of a C₁ to C₂₀ n-alkyl, a hydroxy, a carboxy, an epoxy, an isocyanate, a primary amine, a silyl, and an alkoxy silyl, and X is selected from the group consisting of Li⁺, Na⁺, K⁺, Cs⁺, and a quaternary ammonium;

(h) a nido-carborane salt having the general formula R_x[CB_nH<sub>n+1−

x</sub>]X₃ wherein n is in the range of from 6 to 10, x is in the range of from 0 to 1, R is selected from the group consisting of a C₁ to C₂₀ n-alkyl, a hydroxy, a carboxy, an epoxy, an isocyanate, a primary amine, a silyl, and an alkoxy silyl, and X is selected from the group consisting of Li⁺, Na⁺, K⁺, Cs⁺, and a quaternary ammonium; and

(i) mixtures of two or more thereof.

32. The method of claim 24, wherein said cage compound is selected from the group consisting of: