Methods of surface treating porous particles

Patent metadata

Field	Value
Publication number	US-9078946-B2
Application number	US-201013504984-A
Country	US
Kind code	B2
Filing date	Nov 23, 2010
Priority date	Nov 23, 2009
Publication date	Jul 14, 2015
Grant date	Jul 14, 2015

Abstract

A method of treating porous particles, each porous particle having an external surface and a multiplicity of pores with interior pore surfaces, by contacting the external surface with a hydrophobic agent while causing the interior pore surfaces to remain substantially free of the hydrophobic agent. In certain illustrative embodiments, treating the external surfaces of the porous particles includes exposing the porous particles to at least one of water vapor, methanol vapor, or ethanol vapor; and subsequently exposing the porous particles to a second vapor comprising a reactive organosilane compound which reacts to form the hydrophobic agent. In some particular illustrative embodiments, at least a portion of the external surface of the treated porous particle includes hydrophobic groups, the hydrophobic groups selected from at least one of alkyl or aryl groups optionally substituted with fluorine, and siloxanes having alkyl groups, aryl groups, or combinations thereof.

First claim

The invention claimed is:

1. A method of treating a plurality of porous particles comprising:
providing a plurality of porous particles, each porous particle having an external surface and a plurality of pores with interior pore surfaces; and
treating the external surfaces of the porous particles by contacting and reacting the external surfaces with a hydrophobic agent formed from a vapor comprising a reactive organosilane compound having a hydrophobic group, while causing the interior pore surfaces to remain substantially free of the hydrophobic agent, wherein at least a portion of the treated external surfaces of the porous particles comprise the hydrophobic group.

2. The method of claim 1 , wherein treating the external surface of the porous particle comprises forming a layer comprising silicon, hydrogen, and carbon on at least a portion of the external surface of the porous particle by plasma deposition of the reactive organosilane compound.

3. The method of claim 2 , further comprising forming a layer comprising fluorine and carbon by plasma deposition of a fluorinated compound on at least the portion of the layer comprising silicon, hydrocarbon, and carbon.

4. The method of claim 1 , wherein treating the external surfaces of the porous particle comprises:
exposing the porous particles to at least one of water vapor, methanol vapor or ethanol vapor; and
exposing the porous particles to the vapor comprising the reactive organosilane compound, which reacts to form the hydrophobic agent.

5. The method of claim 4 , wherein exposing the porous particles to at least one of water vapor, methanol vapor or ethanol vapor takes place before exposing the porous particles to the vapor comprising the reactive organosilane compound.

6. The method of claim 5 , wherein at least a portion of the water vapor, methanol vapor or ethanol vapor condenses within at least a portion of the plurality of pores of the porous particles, thereby at least partially occluding the interior pore surfaces, before exposing the porous particles to the vapor comprising the reactive organosilane compound.

7. The method of claim 6 , further comprising substantially removing the condensed water vapor, methanol vapor, or ethanol vapor from the pores after exposing the porous particles to the vapor comprising the reactive organosilane compound, optionally wherein substantially removing the condensed water vapor, methanol vapor, or ethanol vapor from the pores is accomplished by heating the particles, exposing the particles to a vacuum, or a combination thereof.

8. The method of claim 4 , further comprising exposing the porous particles to a third vapor comprising a volatile compound non-reactive with the reactive organosilane before exposing the porous particles to the water vapor and the vapor comprising the reactive organosilane compound, wherein at least a portion of the volatile compound condenses within at least a portion of the plurality of pores of the porous particles, thereby at least partially occluding the interior pore surfaces.

9. The method of claim 8 , wherein the volatile compound is selected from the group consisting of molecular nitrogen, carbon dioxide, a C 1 -C 2 hydrocarbon, and combinations thereof.

10. The method of claim 8 , further comprising substantially removing the condensed volatile compound from the pores after exposing the porous particles to the vapor comprising the reactive organosilane compound, optionally wherein substantially removing the condensed volatile organic compound from the pores is accomplished by heating the particles, exposing the particles to a vacuum, or a combination thereof.

11. The method of claim 1 , wherein at least a portion of the water vapor reacts with at least a portion of the reactive organosilane compound in a vapor phase outside of the pores of the porous particles.

12. The method of claim 11 , wherein the reactive organosilane compound comprises at least two silane functional reactive groups.

13. The method of claim 12 , wherein the reactive organosilane compound is selected from dichlorodimethylsilane and dichlorodiethylsilane.

14. The method of claim 1 , wherein the reactive organosilane compound has a vapor pressure at 25° C. of from 133 Pa to 26,600 Pa.

15. The method of claim 1 , wherein treating the external surface of the porous particle takes place at a total vapor pressure of from 1,330 to 26,600 Pa.

16. The method of claim 15 , wherein the plurality of pores exhibit a median pore size of at least 1 nm and no more than 4 nm, and further wherein exposing the porous particle to the vapor comprising the reactive organosilane compound occurs at a total vapor pressure of from 1,330 to 19,950 Pa.

17. The method of claim 15 , wherein the plurality of pores exhibits a median pore size of at least 4 nm and no more than 10 nanometers, and further wherein exposing the porous particle to the vapor comprising the reactive organosilane compound occurs at a total vapor pressure of from 6,650 to 26,600 Pa.

18. The method of claim 1 , wherein the porous particles are selected from the group consisting of porous inorganic particles, porous organic particles, porous metal particles, porous (co)polymeric particles, porous carbon particles, porous clay particles, porous molecular sieve particles, porous zeolite particles, porous desiccant particles, and combinations thereof.

19. The method of claim 1 , wherein at least a portion of the external surface of the treated porous particle comprises hydrophobic groups, the hydrophobic groups comprising at least one of alkyl or aryl groups, further wherein the alkyl and aryl groups are each optionally substituted with fluorine, and additionally wherein the interior pore surfaces are at least partially hydrophilic.

20. The method of claim 19 , wherein the hydrophobic groups comprise siloxanes having alkyl groups, aryl groups, or combinations thereof.

Assignees

• Badri Brinda B
• David Moses M
• Rong Haoming
• Veeraraghavan Badri
• 3M Innovative Properties Co

Inventors

• Badri Brinda B
• David Moses M
• Rong Haoming
• Veeraraghavan Badri

Classifications

• B01J20/28078

  Pore diameter · CPC title

• B01J20/3208

  Polymeric carriers, supports or substrates · CPC title

• B01J20/267

  Cross-linked polymers · CPC title

• B01J2220/42

  Materials comprising a mixture of inorganic materials (materials coated or impregnated on a carrier B01J20/32) · CPC title

• B01J2220/49

  Materials comprising an indicator, e.g. colour indicator, pH-indicator · CPC title