LIGAND EXCHANGE THERMOCHROMIC, (LETC), SYSTEMS

• US 20080100902A1
• Filed: 09/04/2007
• Published: 05/01/2008
• Est. Priority Date: 09/01/2006
• Status: Active Grant

• Current Assignee: Pleotint LLC
• Original Assignee: Pleotint LLC
• Inventors: Griend, Douglas, Ogburn, Paul, Winkle, Derick, Byker, Harlan, Veldkamp, Brad
• Granted Patent: US 7,542,196 B2
• Time in Patent Office: Days
• US Class Current: 359/288
• CPC Class Codes: B32B 17/10005 laminated safety glass or glazing
• CPC Class Codes: B32B 17/10036 comprising two outer glass sheets
• CPC Class Codes: B32B 17/10174 Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
• CPC Class Codes: B32B 17/10477 thermochromic
• CPC Class Codes: B32B 17/10651 comprising colorants, e.g. dyes or pigments
• CPC Class Codes: B32B 17/10678 comprising UV absorbers or stabilizers, e.g. antioxidants
• CPC Class Codes: B32B 17/10761 containing vinyl acetal
• CPC Class Codes: B32B 2367/00 Polyesters, e.g. PET, i.e. polyethylene terephthalate
• CPC Class Codes: B32B 2369/00 Polycarbonates
• CPC Class Codes: C09K 2211/187 of the iron group metals, i.e. Fe, Co or Ni
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02F 1/0147 based on thermo-optic effects G02F1/132 takes precedence

Abstract

Ligand exchange of thermochromic, LETC, systems exhibiting a reversible change in absorbance of electromagnetic radiation as the temperature of the system is reversibly changed are described. The described LETC systems include one or more than one transition metal ion, which experiences thermally induced changes in the nature of the complexation or coordination around the transition metal ion(s) and, thereby, the system changes its ability to absorb electromagnetic radiation as the temperature changes.

Claims

1. A thermochromic system comprising:

a) Ni(II);

b) a first ligand which forms a Lε

MLC with Ni(II);

c) a second ligand which forms a Hε

MLC with Ni(II); and

d) a polymer

wherein the system is in the form of a solid or semi-solid layer and the system exhibits a reversible net increase in light energy absorbance in the 400 nm to 1400 nm range as the temperature of the system is increased.

2. The thermochromic system of claim 1, wherein the system further comprises at least one of a UV absorber, a hindered amine light stabilizer, a thermal stabilizer, and a plasticizer.

3. The thermochromic system of claim 1, wherein the system includes a plasticizer wherein the plasticizer is cation with the following structure:

4. The thermochromic system of claim 1, wherein the haze level in the solid or semi-solid layer is below 5%.

5. The thermochromic system of claim 4, wherein the haze level in the solid layer is below 10% after 500 hours of exposure to 0.55 watts per square meter at 340 nm from a xenon arc lamp in a chamber with a black panel temperature of 80 C.

6. The thermochromic system of claim 1, wherein the first ligand comprises a Lε

L selected from the group consisting of the polymer, diols, triols, polyols and combinations thereof.

7. The thermochromic system of claim 1, wherein the first ligand comprises a hydroxyl group and the ratio of the concentration of the second ligand to the concentration of the Ni(II) ([Hε

L_T]/[Ni(II)_T]) is greater than four.

8. The thermochromic system of claim 1, wherein the absorption increase is due to the formation of a Hε

MLC of Ni(II) with an absorption peak with a λ

_max between 400 nm and 640 nm.

9. The thermochromic system of claim 1, wherein the total concentration of Ni(II) is between about 0.04 moles and 0.4 moles of Ni(II) per kilogram of polymer.

10. A thermochromic system which comprises Ni(II) in a polymer wherein the system has a reversible, net increase in its ability to absorb in the 400 nm to 1400 nm range due to a change in coordination of the Ni(II) in a coordination compound of Ni(II) as the temperature of the system is increased.

11. The thermochromic system of claim 10 wherein the system further comprises a diol, a triol or polyol and the coordination compound comprises a ligand which coordinates to the Ni(II) through a nitrogen, a phosphorous or a sulfur.

12. The thermochromic system of claim 10, wherein the absorbance of the system at 25°

C. is less than about 0.3 throughout in the 400 nm to 1400 nm range.

13. The thermochromic system of claim 10 wherein the system further comprises a phosphine ligand and the reversible, net increase in the ability of the system to absorb light energy in the visible and NIR range as the temperature of the system is increased is due to a reversible increase in concentration of a coordination compound between the phosphine ligand and the Ni(II) as the temperature is increased.

14. The thermochromic system of claim 10 wherein the system further comprises iodide ions and the reversible, net increase in the ability of the system to absorb light energy in the visible and NIR range as the temperature of the system is increased is due to a reversible increase in concentration of a coordination compound between the iodide ions and the Ni(II) as the temperature is increased.

15. The thermochromic system of claim 14 wherein the thermochromic system further comprises a phosphine compound at a concentration below the concentration of the Ni(II) ions.

16. The thermochromic system of claim 10 wherein the thermochromic system further comprises a phosphine ligand and iodide ions and the reversible, net increase in the ability of the system to absorb light energy in the 400 nm to 1400 nm range as the temperature of the system is increased is due to a reversible increase in concentration of a coordination compound between Ni(II) and both iodide and the phosphine ligand as the temperature is increased.

17. A thermochromic system comprising:

a) Ni(II)

b) a first ligand comprising a pseudohalide or a halide, wherein the halide is selected from the group consisting of Cl—

, Br—

, I— and

combinations thereof, and

c) a second ligand comprising a nitrogen-containing ligand, a phosphorous-containing ligand or a sulfur-containing ligand;

wherein the system has a reversible, net increase in its ability to absorb light energy in the 400 nm to 1400 nm range as the temperature of the system is increased.

18. The thermochromic system of claim 17 wherein the net increase in absorbance is due to an increase in concentration of a coordination compound between Ni(II), the first ligand and the second ligand.

19. A thermochromic system comprising:

a) Co(II)

b) a first ligand comprising a pseudohalide or a halide, wherein the halide is selected from the group consisting of Cl—

, Br—

, I— and

combinations thereof, and

c) a second ligand comprising an oxygen containing ligand, a phosphorous-containing ligand or a sulfur-containing ligand, wherein the second ligand is capable of coordinating to a transition metal ion through oxygen, phosphorus or sulfur;

wherein the system has a reversible, net increase in its ability to absorb light energy in the 400 nm to 1400 nm range as the temperature of the system is increased.

20. A thermochromic system comprising:

a) a Hε

MLC of Co(II);

b) a first ligand selected from the group consisting of diols, triols, polyols and combinations thereof, and

c) a second ligand which coordinates to the Co(II) through an oxygen atom or an oxygen anion;

wherein the system exhibits a reversible increase in concentration due to a change in coordination as the temperature is increased.

21. The thermochromic system of claim 20, wherein the second ligand comprises a phosphinate anion.

22. The thermochromic system of claim 21, wherein the phosphinate anion is selected from the group consisting of anions of the following structure and mixtures thereof:

23. The thermochromic system of claim 21, wherein the phosphinate anions are provided as salts of alkali metal cations, quaternary ammonium cations or quaternary phosphonium cations.

24. The thermochromic system of claim 21, wherein the phosphinate anion is selected from the group consisting of bis(hydroxymethyl)phosphinate, bis(4-Methoxyphenyl)phosphinate, methylphenylphosphinate, diphenylphosphinate, dimethylphosphinate and mixtures thereof.

25. The thermochromic system of claim 20, wherein the second ligand is part of a carboxylate anion.

26. The thermochromic system of claim 25, wherein the carboxylate anion is selected from the group consisting of acetate, trifluoroacetate, benzoate 2-methoxybenzoate, salicylate malonate, succinate, phthalate and mixtures thereof.

27. The thermochromic system of claim 20, wherein the second ligand is part of a phosphine oxide.

28. The thermochromic system of claim 27, wherein the phosphine oxide is selected from the group consisting of hexamethylphosphoramide, tributylphosphine oxide, triphenylphosphine oxide and mixtures thereof.

29. The thermochromic system of claim 20, wherein the second ligand is part of a nitrate anion, a pyridine-N-oxide or a phenolate anion.

30. The thermochromic system of claim 20, wherein the Hε

MLC of Co(II) comprises a heteroleptic complex comprising a halide anion.

31. A thermochromic system comprising

a) Co(II);

b) Iodide; and

c) either a first ligand, a second ligand or both wherein the first ligand is selected from the group consisting of a diol, a triol, a polyol, and mixtures thereof and the second ligand comprises one or more phosphine compounds,

wherein the system exhibits a reversible, net increase in its ability to absorb light energy in the 400 nm to 1400 nm range as the temperature of the system is increased.

32. The thermochromic system of claim 31, wherein the system comprises the second ligand, which comprises a phosphine compound having the structure:

33. A thermochromic system comprising Co(II) ions and a phosphine compound wherein the system exhibits a reversible, net increase in the system'"'"'s ability to absorb energy in the 400 nm to 1400 nm of the electromagnetic radiation from the sun, as the temperature of the system is increased, due to a reversible increase in concentration of a coordination compound of the phosphine compound with Co(II) ions.

34. The thermochromic system of claim 33 wherein the system further comprises iodide ions, and the reversible, net increase in the system'"'"'s ability to absorb energy in the 400 nm to 1400 nm of the electromagnetic radiation from the sun, as the temperature of the system is increased is due to a reversible increase in concentration of a heteroleptic coordination compound between the phosphine compound and iodide ions with Co(II) ions.

35. A thermochromic system comprising:

a) a polymer;

b) Co(II) ions;

c) a first ligand that forms a Hε

MLC with Co(II); and

d) a second ligand that forms a Lε

MLC with Co(II), wherein the second ligand is represented by the following structure;

wherein R is selected from the group consisting of H, alkyl, substituted alkyl, branched alkyl, aralkyl, aryl, amino, substituted amino, nitro and combinations thereof.

36. The thermochromic system of claim 35, wherein the second ligand is selected from the group consisting of trimetholmethane, trimethylolethane, trimethylpropane, trimethylolbutane, pentaerythritol, di-pentaerythritol, trimethylolnitromethane, trimethylolaminomethane and mixtures thereof.

37. The thermochromic system of claim 35, wherein the first ligand is selected from the group consisting of chloride, bromide, iodide and mixtures thereof.

38. A thermochromic system comprising a polymer layer and:

a) a transition metal ion;

b) a first ligand capable of forming a Hε

MLC with the transition metal ion; and

c) a second ligand represented by the following structure;

wherein R₁, R₂, R₃, R₄, R₅ and R₆ are independently selected from the group consisting of straight, branched, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl and combinations thereof, provided that optionally any combination of two or more of R₁, R₂, R₃, R₄, R₅ and/or R₆ may be joined together to form one or more optionally substituted ring systems.

39. The thermochromic system of claim 38 wherein the second ligand is a diol ligand selected from the group consisting of 1,3-Cyclohexanediol;

1,1-Bis(hydroxymethyl)cyclopropane;

2,2-Bis(hydroxymethyl)propionic acid;

2,2-Dibutyl-1,3-propanediol;

2,2-Diethyl-1,3-propanediol;

2,2,4-Trimethyl-1,3-pentanediol;

2,4-Dimethyl-2,4-pentanediol;

2,4-Pentanediol;

2-Bromo-2-nitro-1,3-propanediol;

Serinol;

2-Butyl-2-Ethyl-1,3-propanediol;

2-Ethyl-1,3-hexanediol;

2-Methyl-1,3-propanediol;

2-Methyl-2,4-pentanediol;

2-Methyl-2-propyl-1,3-propanediol;

2-Methylenepropane-1,3-diol;

2-Phenyl-1,3-propanediol;

Cyclohex-3-ene-1,1-diyldimethanol;

3-Methyl-1,3-butanediol;

3-Methyl-2,4-heptanediol;

[2-(2-phenylethyl)-1,3-dioxane-5,5-diyl]dimethanol;

Neopentyl Glycol;

Trimethylolpropane allyl ether and mixtures thereof.

40. The thermochromic system of claim 38 wherein the transition metal ion is selected from the group consisting of Fe(II), Co(II), Ni(II), Cu(II) and mixtures thereof.

41. The thermochromic system of claim 40 wherein the first ligand is iodide.

42. A thermochromic system which comprises a polymer layer which comprises:

a) a transition metal ion;

b) a first ligand capable of forming a Hε

MLC with the transition metal ion; and

c) a second ligand with the follow structure;

wherein R is selected from the group consisting of straight, branched, substituted or unsubstituted alkyl;

substituted or unsubstituted aryl;

substituted or unsubstituted aralkyl;

a nitro group, a substituted or unsubstituted amino group and combinations thereof.

43. The thermochromic system of claim 42 wherein the second ligand is selected from the group consisting of 2,2′

-(propane-1,3-diyldiimino)bis[2-(hydroxymethyl)propane-1,3-diol];

2-[bis(2-hydroxyethyl)amino]-2-(hydroxymethyl)propane-1,3-diol;

Dipentaerythritol;

Pentaerythritol;

2-(bromomethyl)-2-(hydroxymethyl)propane-1,3-diol;

2-(hydroxymethyl)-2-propylpropane-1,3-diol;

2-(hydroxymethyl)-2-methylpropane-1,3-diol;

2-(hydroxymethyl)propane-1,3-diol;

2-(hydroxymethyl)-2-nitropropane-1,3-diol;

Trimethylolpropane;

2-amino-2-(hydroxymethyl)propane-1,3-diol and mixtures thereof.

44. A thermochromic system comprising a polymer layer and

a) a transition metal ion;

b) a first ligand capable of forming a Hε

MLC with the transition metal ion; and

c) a second ligand capable of forming a Lε

MLC wherein the second ligand is selected from the group consisting of Di(Trimethylolpropane);

L-Fucose;

meso-Erythritol;

N-propyl-N-pyridin-2-ylpyridin-2-amine;

Poly(vinylbutyral);

Poly(vinylpyrrolidone);

Tetrahydrofurfuryl alcohol;

Tetrahydropyran-2-methanol;

Triethanolamine;

1,2,4-Butanetriol;

1,2-phenylenedimethanol;

1,2-Hexanediol;

1,2-Propanediol;

cis,cis-1,3,5-Cyclohexanetriol;

1,3,5-Pentanetriol;

2,5-bis(hydroxymethyl)-1,4-dioxane-2,5-diol;

1,4-Butanediol;

1,4-Cyclohexanediol;

18-Crown-6;

1-ethyl-1H-benzimidazole;

2,3-Dimethyl-2,3-butanediol;

2-Phenyl-1,2-Propanediol;

3-(Diethylamino)-1,2-propanediol;

2-ethyl-2-(hydroxymethyl)butane-1,4-diol;

3,3-Dimethyl-1,2-butanediol;

3-Hydroxypropionitrile;

3-Methyl-1,3,5-Pentanetriol;

3-Phenoxy-1,2-Propanediol;

4-Hydroxy-4-methyl-2-pentanone;

3-Phenyl-1-propanol;

(5-methyl-1,3-dioxan-5-yl)methanol;

Bis(methylsulfinyl)methane;

Butyl sulfoxide;

Diethylene glycol;

Diethylformamide;

Hexamethylphosphoramide;

3,3′

-oxydipropane-1,2-diol Dimethyl sulfoxide;

Ethanol;

Ethylene Glycol;

Glycerol;

Glycolic Acid;

3-(2-methoxyphenoxy)propane-1,2-diol;

Lithium Salicylate;

Lithium Trifluoroacetate;

N,N-Dimethylformamide;

1,1,3,3-Tetramethylurea;

2,2-dimethylpropan-1-ol;

Pentaethylene glycol;

Pentaerythritol ethoxylate;

tetrahydrothiophene 1-oxide;

Tributylphosphine oxide;

Trimethylolpropane ethoxylate;

Trimethylolpropane propoxylate;

Triphenylphosphine oxide and mixtures thereof.

45. The thermochromic system of claim 44, wherein the polymer comprises a poly(vinylacetal) or a poly(vinylacetal) copolymer.

46. The thermochromic system of claim 45, wherein the polymer comprises poly(vinylbutyral-co-vinylalcohol-co-vinylacetate).

47. A thermochromic system which comprises a polymer layer which comprises:

a) a transition metal ion; and

b) a ligand capable of forming a Hε

MLC with the transition metal ion;

wherein the polymer is selected from the group consisting of poly(hydroxyethyl methacrylate);

poly(1-glycerol methacrylate);

hydroxyalkylcelluloses;

urethanes;

poly(2-ethyl-2-oxazoline);

poly(N-vinylpyrrolidone);

poly(ethylene-co-vinylalcohol);

poly(vinyl methyl ether);

polyacrylamide;

poly(N,N-dimethylacrylamide);

polyvinylpyridines, copolymers thereof and mixtures thereof.

48. The thermochromic system of claim 47 wherein the transition metal ion is selected from the group consisting of Fe(II), Co(II), Ni(II), Cu(II) and mixtures thereof.

49. The thermochromic system of claim 48 wherein the ligand is iodide.

50. The thermochromic system of claim 49 wherein the system comprises a phosphine compound with the following structure:

51. The thermochromic system of claims 49 wherein the system as prepared comprises a phosphine compound with the following structure: