Adjustable Colorimetric Moisture Indicators

• US 10,119,918 B2
• Filed: 11/14/2013
• Issued: 11/06/2018
• Est. Priority Date: 11/14/2012
• Status: Active Grant

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Kang, Myungchan, Hajime, Evan Koon Lun Yuuji
• Primary Examiner(s): Mui, Christine T
• Assistant Examiner(s): Berkeley, Emily R.
• Application Number:
  US14/441,478
• Publication Number:
  US 20150293028A1
• Time in Patent Office: 1,818 Days
• Field of Search: 436166
• CPC Class Codes: B01J 20/08 comprising aluminium oxide or hydroxide; comprising bauxite
• CPC Class Codes: B01J 20/103 comprising silica
• CPC Class Codes: B01J 20/223 containing metals, e.g. organo-metallic compounds, coordination complexes
• CPC Class Codes: B01J 20/28016 Particle form
• CPC Class Codes: B01J 20/28057 Surface area, e.g. B.E.T specific surface area
• CPC Class Codes: B01J 20/3204 Inorganic carriers, supports or substrates
• CPC Class Codes: B01J 20/3236 containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
• CPC Class Codes: B01J 20/3248 the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
• CPC Class Codes: B01J 2220/49 Materials comprising an indicator, e.g. colour indicator, pH-indicator
• CPC Class Codes: G01N 2021/7793 Sensor comprising plural indicators
• CPC Class Codes: G01N 21/81 Indicating humidity
• CPC Class Codes: G01N 31/222 for investigating moisture content

Abstract

Compositions are provided comprising: 1) a solid metal oxide support having surface hydroxyl groups; 2) a silyl-containing compound bound to the solid metal oxide support through a silanol bond with the surface hydroxyl groups; and 3) a bis(glyoxime)-transition metal complex bound to the solid metal oxide support. These compositions can be used to make a colorimetric relative humidity-indicating sensor. A method of adjusting the colorimetric response of a moisture-indicating composition and a method of detecting moisture are also provided.

Claims

1. A composition comprising:

a solid metal oxide support having surface hydroxyl groups;

a silyl-containing compound bound to the solid metal oxide support through a silanol bond with the surface hydroxyl groups; and

a bis(glyoxime)-transition metal complex bound to the solid metal oxide support;

wherein the composition is a reversible colorimetric moisture-indicating composition.

2. The composition of claim 1, wherein the silyl-containing compound is of Formula (I)

R¹—

Si(R²)_3-x(R³)_x 

 

(I)

wherein

R¹ is an alkyl, fluoroalkyl, alkyl substituted with an amino, aryl, aralkyl, or alkaryl group;

each R² is independently hydroxyl or a hydrolyzable group;

each R³ is independently a non-hydrolyzable group; and

x is an integer equal to 0, 1, or 2.

3. The composition of claim 1, wherein the silyl-containing compound is of Formula (II)

(R³)_x(R²)_3-xSi—

R⁴—

Si(R²)_3-x(R³)_x 

 

(II)

wherein

R⁴ is an alkylene, arylene, or a combination thereof;

each R² is independently hydroxyl or a hydrolyzable group;

each R³ is independently a non-hydrolyzable group; and

x is an integer equal to 0, 1, or 2.

4. The composition of claim 1, wherein the silyl-containing compound is selected from the group consisting of diethoxydimethylsilane, hexamethyldisilazane, n-octadecyltrichlorosilane, 1H,1H,2H,2H-perfluoroctyldimethylchlorosilane, and (3-aminopropyl)triethoxysilane.

5. The composition of claim 1, wherein no more than about 50% of surface hydroxyl groups of the support are bound to the silyl-containing compound.

6. The composition of claim 1, wherein the solid metal oxide support comprises an oxide of aluminum, silicon, or a combination thereof.

7. The composition of claim 1, wherein the transition metal in the bis(glyoxime)-transition metal complex comprises rhodium, iridium, platinum, palladium, gold, nickel, copper, or a combination thereof.

8. The composition of claim 1, wherein the bis(glyoxime)-transition metal complex comprises bis(dimethylglyoximato)-nickel(II).

9. The composition of claim 1, wherein the composition quantitatively changes optical spectrum at relative humidities ranging from about 50% to about 90% relative humidity at 25°

C.

10. A colorimetric relative humidity-indicating sensor comprising:

a reversible colorimetric moisture-indicating composition comprising

a solid metal oxide support having surface hydroxyl groups;

a silyl-containing compound bound to the solid metal oxide support through a silanol bond with the surface hydroxyl groups; and

a bis(glyoxime)-transition metal complex bound to the solid metal oxide support; and

wherein the optical spectrum of the sensor changes quantitatively according to the relative humidity within the environment within which the sensor is placed.

11. The sensor of claim 10, wherein the silyl-containing compound is of Formula (I)

R¹—

Si(R²)_3-x(R³)_x 

 

(I)

wherein

R¹ is an alkyl, fluoroalkyl, alkyl substituted with an amino, aryl, aralkyl, or alkaryl group;

each R² is independently hydroxyl or a hydrolyzable group;

each R³ is independently a non-hydrolyzable group; and

x is an integer equal to 0, 1, or 2.

12. The sensor of claim 10, wherein the silyl-containing compound is of Formula (II)

(R³)_x(R²)_3-xSi—

R⁴—

Si(R²)_3-x(R³)_x 

 

(II)

wherein

R⁴ is an alkylene, arylene, or a combination thereof;

each R² is independently hydroxyl or a hydrolyzable group;

each R³ is independently a non-hydrolyzable group; and

x is an integer equal to 0, 1, or 2.

13. The sensor of claim 10, wherein no more than about 50% of surface hydroxyl groups of the support are bound to the silyl-containing compound.

14. The sensor of claim 10, wherein the solid metal oxide support comprises an oxide of aluminum, silicon, or a combination thereof.

15. The sensor of claim 10, wherein the bis(glyoxime)-transition metal complex comprises bis(dimethylglyoximato)-nickel (II).

16. The sensor of claim 10, wherein the sensor quantitatively changes optical spectrum at relative humidities ranging from about 50% to about 90% relative humidity at 25°

C.

17. The sensor of claim 10, wherein the sensor quantitatively changes optical spectrum at relative humidities ranging from about 60% to about 80% relative humidity at 25°

C.

18. A method of adjusting the colorimetric response of a moisture-indicating composition comprising:

modifying the surface of a solid metal oxide support having surface hydroxyl groups by reacting the surface hydroxyl groups of the solid metal oxide support with a silyl-containing compound to create a modified solid metal oxide support; and

bonding a bis(glyoxime)-transition metal complex to the modified solid metal oxide support to create a reversible colorimetric moisture-indicating composition.

19. The method of claim 18, wherein the silyl-containing compound is of Formula (I)

R¹—

Si(R²)_3-x(R³)_x 

 

(I)

wherein

R¹ is an alkyl, fluoroalkyl, alkyl substituted with an amino, aryl, aralkyl, or alkaryl group;

each R² is independently hydroxyl or a hydrolyzable group;

each R³ is independently a non-hydrolyzable group; and

x is an integer equal to 0, 1, or 2.

20. The method of claim 18, wherein the silyl-containing compound is of Formula (II)

(R³)_x(R²)_3-xSi—

R⁴—

Si(R²)_3-x(R³)_x 

 

(II)

wherein

R⁴ is an alkylene, arylene, or a combination thereof;

each R² is independently hydroxyl or a hydrolyzable group;

each R³ is independently a non-hydrolyzable group; and

x is an integer equal to 0, 1, or 2.

21. The method of claim 18, wherein no more than about 50% of surface hydroxyl groups of the support are bound to the silyl-containing compound.

22. The method of claim 18, wherein the solid metal oxide support comprises an oxide of aluminum, silicon, or a combination thereof.

23. The method of claim 18, wherein the bis(glyoxime)-transition metal complex comprises bis(dimethylglyoximato)-nickel (II).

24. The method of claim 18, wherein the moisture-indicating composition quantitatively changes optical spectrum at relative humidities ranging from about 50% to about 90% relative humidity at 25°

C.

25. The method of claim 18, wherein the moisture-indicating composition quantitatively changes optical spectrum at relative humidities ranging from about 60% to about 80% relative humidity at 25°

C.