COMPOSITIONS OF SURFACE MODIFIED NANOPARTICLES

• US 20100215894A1
• Filed: 02/01/2010
• Published: 08/26/2010
• Est. Priority Date: 02/02/2009
• Status: Abandoned Application

• Current Assignee: Invista North America Sarl (Invista)
• Original Assignee: Invista North America Sarl (Invista)
• Inventors: RUDAT, Martin August, IVERSON, Isaac Keene
• Application Number:
  US12/697,911
• Publication Number:
  US 20100215894A1
• Time in Patent Office: Days
• US Class Current: 428/87
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C01P 2006/16 Pore diameter
• CPC Class Codes: C08K 3/22 of metals
• CPC Class Codes: C08K 3/346 Clay
• CPC Class Codes: C08K 3/36 Silica
• CPC Class Codes: C08K 9/06 with silicon-containing compounds
• CPC Class Codes: C09C 1/00 Treatment of specific inorganic materials other than fibrous fillers tenebrescent materials C09K9/00; luminescent materials C09K11/00; Preparation of carbon black
• CPC Class Codes: C09C 1/28 Compounds of silicon C09C1/0009, C09C1/0015, C09C1/0078 take precedence
• CPC Class Codes: C09C 1/3081 Treatment with organo-silicon compounds
• CPC Class Codes: C09C 1/3684 Treatment with organo-silicon compounds
• CPC Class Codes: C09C 1/405 containing combined silica, e.g. mica
• CPC Class Codes: C09C 1/42 Clays
• CPC Class Codes: C09D 5/1687 Use of special additives
• CPC Class Codes: C09D 7/62 modified by treatment with other compounds
• CPC Class Codes: D06M 23/08 Processes in which the treating agent is applied in powder or granular form adhesives for multi-layer textile fabrics D06M17/00
• CPC Class Codes: Y10T 428/23921 With particles
• CPC Class Codes: Y10T 428/249921 Web or sheet containing structurally defined element or component
• CPC Class Codes: Y10T 428/249987 With nonvoid component of specified composition
• CPC Class Codes: Y10T 428/2933 Coated or with bond, impregnation or core
• CPC Class Codes: Y10T 428/2964 : Artificial fiber or filament

Abstract

Disclosed is a composition comprising: an aqueous dispersion of fluoroalkylsilyl surface modified nanoparticles, wherein the nanoparticles comprise at least one member selected from the group consisting of silica, titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay and mixtures thereof, and wherein the fluoroalkylsilyl is: (F(CF₂)_nCH₂CH₂)_mSi(O—)_p, where n is 2, 3 or 4, p is 1, 2 or 3, and m is (4−p). Also disclosed are processes of making an aqueous dispersion of fluoroalkylsilyl surface modified nanoparticles, and treating a substrate with an aqueous dispersion of fluoroalkylsilyl surface modified nanoparticles. Articles and substrates comprising the fluoroalkylsilyl surface modified nanoparticles are also disclosed.

Claims

1. A composition comprising an aqueous dispersion of fluoroalkylsilyl surface modified nanoparticles, wherein the nanoparticles comprise at least one member selected from the group consisting of silica, titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay and mixtures thereof, and wherein the fluoroalkylsilyl is:

(F(CF₂)_nCH₂CH₂)_mSi(O—

)_p,

where n is 2, 3 or 4,

where p is 1, 2 or 3, and

where m is (4−

p).

2. The composition of claim 1 wherein n is 4.

3. The composition of claim 1 wherein p is 3 and m is 1.

4. The composition of claim 1 wherein the synthetic clay is hectorite clay.

5. The composition of claim 1 wherein the fluoroalkylsilyl is covalently bonded to the nanoparticle surface.

6. The composition of claim 1 wherein the fluoroalkylsilyl surface modified nanoparticle is present at a concentration in the range of from about 0.01% to about 50% by weight of the total composition.

7. The composition of claim 1 wherein the fluoroalkylsilyl surface modified nanoparticle is present at a concentration in the range of from about 1% to about 40% by weight of the total composition.

8. The composition of claim 1 wherein the fluoroalkylsilyl surface modified nanoparticle is present at a concentration in the range of from about 1% to about 8% by weight of the total composition.

9. The composition of any of claims 1-9 further comprising a fluorinated resin emulsion.

10. The composition of any of claims 1-9 further comprising an alkylated inorganic nanoparticle having no fluorine.

11. The composition of any of claims 1-9 further comprising at least one member selected from the group consisting of a wetting agent, anti-soil agent, anti-stain agent, fluorochemical resin, surfactant and mixtures thereof.

12. The composition of any of claims 1-8 further comprising a component moiety bonded to the surface of the nanoparticles having the formula:

[H(CH₂)_M]_nSi—

(O—

)_p.

where M is an integer between 1 and 12,

where p is 1, 2, or 3, and

where n is 4−

p.

13. A process for making fluoroaklysilyl surface modified nanoparticles, comprising:

(i) creating an aqueous dispersion of at least one member selected from the group consisting of silica, titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay and mixtures thereof;

(ii) adding a water immiscible fluoroalkylsilane reagent to the aqueous dispersion to form a heterogeneous mixture where the fluoroalkylsilane reagent is;

(F(CF₂)_nCH₂CH₂)_mSi(O—

R)_p,

where n is 2, 3 or 4,

where p is 1, 2 or 3,

where m is (4−

p), and

where R is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and —

C(O)CH₃; and

(iii) mixing the heterogeneous mixture until it becomes a homogeneous aqueous dispersion of fluoroaklysilyl surface modified nanoparticles.

14. The process of claim 13 wherein n is 4, p is 3, m is 1, R is selected from the group consisting of methyl and ethyl, and the synthetic clay is a hectorite clay.

15. The process of claim 13 or 14 wherein the fluoroalkylsilane molecules are covalently bonded to the nanoparticle surface, forming fluoroalkylsilyl moiety on the surface of the nanoparticle.

16. The process of claim 13 or 14 wherein the fluoroalkylsilyl surface modified nanoparticles are formed at a concentration in the range of from about 0.01% to about 50% by weight of the aqueous dispersion.

17. The process of claim 13 or 14 wherein the fluoroalkylsilyl surface modified nanoparticles are formed at a concentration in the range of from about 1% to about 40% by weight of the aqueous dispersion.

18. The process of claim 13 or 14 wherein the fluoroalkylsilane surface modified nanoparticles are formed at a concentration in the range of from about 1% to about 8% by weight of the aqueous dispersion.

19. The process of claim 13 or 14 further comprising adding a fluorinated resin emulsion.

20. The process of claim 13 or 14 further comprising adding an alkylated inorganic nanoparticle having no fluorine.

21. The process of claim 13 or 14 further comprising adding at least one member selected from the group consisting of a wetting agent, anti-soil agent, anti-stain agent, fluorochemical resin, surfactant and mixtures thereof.

22. The process of claim 13 or 14, further comprising adding a component prior to the addition of the fluoroalkylsilane, wherein said component has the formula:

[H(CH₂)_M]_n—

Si—

(X)_p.

where M is an integer between 1 and 12,

where p is 1, 2, or 3,

where n is 4−

p, and

where X is selected from the group consisting of methoxy, ethoxy, propoxy, butoxy, acetoxy, and chloride leaving groups.

23. The process of claim 22, wherein said mixing further comprises recirculating the fluoroalkylsilane and nanoparticles through a static mixer.

24. A modified substrate comprising:

a fluoroalkylsilyl surface modified nanoparticle on at least one surface of said substrate, wherein the nanoparticle comprises at least one member selected from the group consisting of titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay and mixtures thereof, and wherein the fluoroalkylsilyl is;

(F(CF₂)_nCH₂CH₂)_mSi(O—

)_p,

where n is 2, 3 or 4,

where p is 1, 2 or 3, and

where m is (4−

p)

25. The modified substrate of claim 24 wherein said substrate is selected from the group consisting of synthetic fiber, natural fiber, stone, ceramic, glass, plastic and composites.

26. The modified substrate of claim 24 wherein n is 4.

27. The modified substrate of claim 24 wherein p is 3 and m is 1.

28. The modified substrate of claim 27 wherein the synthetic clay is a hectorite clay.

29. The modified substrate of claim 27 wherein the fluoroalkylsilyl is covalently bonded to the nanoparticle surface.

30. The modified substrate of claim 24 or 25 wherein the substrate comprises pores having an average diameter in the range of from about 100 to about 100,000 nanometers.

31. The modified substrate of claim 24 or 25 wherein the fluoroalkylsilyl surface modified nanoparticle forms at least one layered structure on the substrate, wherein the layered structure has a thickness of about 10,000 nanometers or less, and a width and length of about 100,000 nanometers or more.

32. The modified substrate of claim 24, wherein the substrate further comprises a component moiety bonded to the surface of the nanoparticle having the formula:

[H(CH₂)_M]_n—

Si—

(O—

)_p.

where M is an integer between 1 and 12,

where p is 1, 2, or 3, and

where n is 4−

p; and

further wherein said nanoparticle comprises at least one member selected from the group consisting of silica, titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay and mixtures thereof.

33. An article made from the substrate of claim 24 or 32.

34. The article of claim 33 wherein the article is a fabric, carpet, or paper.

35. The article of claim 34 wherein the article is a fabric or a carpet, and further wherein said nanoparticle comprises at least one member selected from the group consisting of silica, titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay and mixtures thereof.

36. The article of claim 35 wherein the total concentration of fluorine on the external surface is in a range of from about 10 ppm to about 500 ppm w/w.

37. The article of claim 35 wherein the total concentration of fluorine on the external surface is in a range of from about 50 ppm to about 300 ppm w/w.

38. The article of claim 35 wherein the fluoroalkylsilyl surface modified nanoparticle is present from about 0.01% to about 2.0% by weight of the article.

39. The article of claim 35 wherein the fluoroalkylsilyl surface modified nanoparticle is present from about 0.1% to about 1.0% by weight of the article.

40. The article of claim 35 wherein elemental fluorine is present from about 0.0001% to about 0.10% by weight of the article.

41. The article of claim 35 wherein elemental fluorine is present from about 0.0001% to about 0.010% by weight of the article.

42. The article of claim 35 wherein the fluoroalkylsilyl surface modified nanoparticles is present from about 0.01 to about 3 grams per square meter of surface area of the article.

43. The article of claim 35 wherein the fluoroalkylsilyl surface modified nanoparticles is present from about 0.1 to about 2 grams per square meter of surface area of the article.

44. A process for making a modified substrate that is hydrophobic and soil resistant, comprising:

(i) applying an aqueous dispersion of fluoroalkylsilyl surface modified nanoparticles, wherein said nanoparticles comprises at least one member selected from the group consisting of silica, titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay and mixtures thereof; and

wherein said

fluoroalkylsilyl is;

(F(CF₂)_nCH₂CH₂)_mSi(O—

)_p,

where n is 2, 3 or 4,

where p is 1, 2 or 3, and

where m is (4−

p); and

(ii) drying the substrate.

46. The process of claim 44 or 45 wherein the fluoroalkylsilyl moieties are covalently bonded to the nanoparticle surface.

47. The process of claim 44 or 45 wherein the fluoroalkylsilyl surface modified nanoparticles are formed at a concentration in the range of from about 0.01% to about 50% by weight of the aqueous dispersion.

48. The process of claim 44 or 45 wherein the fluoroalkylsilane surface modified nanoparticles are formed at a concentration in the range of from about 1% to about 40% by weight of the aqueous dispersion.

49. The process of claim 44 or 45 wherein the fluoroalkylsilane surface modified nanoparticles are formed at a concentration in the range of from about 1% to about 8% by weight of the aqueous dispersion.

50. The process of claim 44 or 45, wherein said aqueous dispersion further comprises a fluorinated resin emulsion.

51. The process of claim 44 or 45, wherein said aqueous dispersion further comprises an alkylated inorganic nanoparticle having no fluorine.

52. The process of claim 44 or 45, wherein said aqueous dispersion further comprises at least one member selected from the group consisting of a wetting agent, anti-soil agent, anti-stain agent, fluorochemical resin, surfactant and mixtures thereof.

53. The process of claim 44 or 45, wherein said aqueous dispersion further comprises a component moiety bonded to the surface of the nanoparticles having the formula:

[H(CH₂)_M]_n—

Si—

(O—

)_p.

where M is an integer between 1 and 12,

where p is 1, 2, or 3, and

where n is 4−

p.

54. The process of claim 44 or 45, wherein said substrate is selected from the group consisting of synthetic fiber, natural fiber, stone, ceramic, glass, plastic and composites.

45. The process of claim 45 wherein n is 4, p is 3, m is 1, and the synthetic clay is a hectorite clay.

55. A composition comprising:

a surface modified nanoparticle comprising;

(1) a fluoroalkylsilyl having the following formula;

(F(CF₂)_nCH₂CH₂)_mSi(O—

)_p,

where n is 2, 3 or 4,

where p is 1, 2 or 3, and

where m is (4−

p), and (2) a component moiety having the formula;

[H(CH₂)_M]_nSi—

(O—

)_p.

where M is an integer between 1 and 12,

where p is 1, 2, or 3, and

where n is 4−

p;

wherein the nanoparticle comprises at least one member selected from the group consisting of silica, titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay and mixtures thereof.

56. A composition comprising:

a fluoroalkylsilyl surface modified nanoparticle, wherein the nanoparticle comprises at least one member selected from the group consisting of titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay and mixtures thereof, and wherein the fluoroalkylsilyl is;

(F(CF₂)_nCH₂CH₂)_mSi(O—

)_p,

where n is 2, 3 or 4,

where p is 1, 2 or 3,

and where m is (4−

p).