Nanocomposites and their application as monolith columns

• US 9,289,747 B2
• Filed: 05/12/2014
• Issued: 03/22/2016
• Est. Priority Date: 05/28/2003
• Status: Active Grant

• Current Assignee: Waters Technologies Corporation (Waters Corporation)
• Original Assignee: Waters Technologies Corporation (Waters Corporation)
• Inventors: O'Gara, John E., Ding, Julia, Walsh, Daniel B.
• Primary Examiner(s): MOORE, MARGARET G
• Application Number:
  US14/275,250
• Publication Number:
  US 20140326649A1
• Time in Patent Office: 680 Days
• US Class Current: 1/1
• CPC Class Codes: B01D 15/206 Packing or coating
• CPC Class Codes: B01D 15/22 relating to the construction of the column
• CPC Class Codes: B01D 15/265 Adsorption chromatography
• CPC Class Codes: B01J 20/26 Synthetic macromolecular compounds
• CPC Class Codes: B01J 20/285 based on polymers
• CPC Class Codes: B01J 2220/82 Shaped bodies, e.g. monoliths, plugs, tubes, continuous beds
• CPC Class Codes: B01J 2220/86 Sorbents applied to inner surfaces of columns or capillaries
• CPC Class Codes: B05D 7/22 to internal surfaces, e.g. of tubes
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C08G 77/20 containing silicon bound to unsaturated aliphatic groups C08G77/045 takes precedence
• CPC Class Codes: C08J 5/005 Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
• CPC Class Codes: Y10T 428/26 Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
• CPC Class Codes: Y10T 428/31612 As silicone, silane or siloxane
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

Novel materials for chromatographic separations, processes for their preparation, and separation devices containing the chromatographic materials. In particular, hybrid inorganic/organic monolith materials comprising a polymerized scaffolding nanocomposite (PSN), wherein the nanocomposite contains a scaffolding functionally capable of chemically interacting with a surface of a second material are described. The hybrid inorganic/organic materials have enhanced wall adhesion and increased resistance to shrinkage as compared to prior art monolith materials. The improved adhesion of the monoliths enable the preparation of capillary columns with an internal diameter (I.D.)≧50 μm.

Claims

1. A hybrid inorganic/organic monolith utilized in chromatographic separation comprising a polymerized scaffolding nanocomposite (PSN), wherein the nanocomposite contains a scaffolding functionality which chemically interacts with an anchoring functionality on an internal surface of a chromatographic device;

and wherein the hybrid inorganic/organic monolith is prepared by a method comprising the steps of

a) forming a sol-gel by the reaction of two or more monomers within the chromatographic device;

b) initiating a polymerization reaction; and

c) allowing the monomers to react through a polymerization sol-gel (PSG) reaction, thereby preparing the hybrid inorganic/organic monolith;

wherein

the pore structure of said hybrid inorganic/organic monolith is modified by including a surfactant or combination of different surfactants in said PSG reaction and wherein the surfactant is removed from the monolith structure following said PSG reaction,

and wherein the internal surface of the chromatotgraphic device is derivatized with the anchoring functionality and the monolith structure shows no optical evidence of shrinkage, as observed by optical microscope.

2. The hybrid monolith of claim 1, wherein the chromatotgraphic device is a containment vessel, a column, a capillary column, or a microfluidic channel having at least one surface.

3. The hybrid monolith of claim 1, wherein the scaffolding functionality is selected from the group consisting of vinyl, acrylate, methacrylate, acrylamide, methacrylamide, styrene, divinylbenzene, itaconate, fumarate, alkyne, and combinations thereof.

4. The hybrid monolith of claim 1, wherein the surface of the chromatotgraphic device is derivatized with an anchoring functionality.

5. The hybrid monolith of claim 4, wherein the anchoring functionality is selected from the group consisting of vinyl, acrylate, methacrylate, acrylamide, methacrylamide, styrene, divinylbenzene, itaconate, fumarate, alkyne, azo compounds, and combinations thereof.

6. The hybrid monolith of claim 4, wherein the scaffolding functionality and the anchoring functionality are copolymerizable.

7. The hybrid monolith of claim 2, wherein containment vessel is selected from the group consisting of a capillary column, a glass lined steel column, a radial compression column, a trap column, a microfluidic device, a microchip, a sensor, an electronic circuit, a miniaturized SPE device, and an on-column frit.

8. The hybrid monolith of claim 2, where the containment vessel is a fused silica capillary column.

9. The hybrid monolith of claim 1, wherein chemical interaction is formation of a covalent bond.

10. The hybrid monolith of claim 9, wherein the covalent bond is formed by polymerization.

11. The hybrid monolith of claim 10, wherein the polymerization is initiated with a radical initiator.

12. The hybrid monolith of claim 11, wherein the radical initiator is minimally water soluble.

13. The hybrid monolith of claim 11, wherein the initiator is selected from the group consisting of 2,2′

-azobis(isobutyronitrile), 2,2′

-azobis(2-methylpropionamidine)dihydrochloride, 4,4′

-azobis(4-cyanovaleric acid), potassium persulfate, and peracetic acid.

14. The hybrid monolith of claim 1, wherein the inorganic portion of the hybrid material is a material selected from the group consisting of alumina, silica, titanium oxide, zirconium oxide, and ceramic material.

15. The hybrid monolith of claim 1, wherein the inorganic portion of the hybrid material is silica.

16. The hybrid monolith of claim 1, wherein the PSN is the product of a reaction of an organosilane and an inorganic silane monomer.

17. The hybrid monolith of claim 16, wherein the PSN is the product of a reaction of a tetraalkoxysilane and an organosilane containing at least one polymerizable group.

18. The hybrid monolith of claim 17, wherein said tetraalkoxysilane has the formula Si(OR¹)₄, where R¹ is a C₁-C₃ alkyl moiety.

19. The hybrid monolith of claim 17, wherein said organosilane is an organoalkoxysilane having the formula R²Si(OR¹)₃ or R⁶[Si(OR¹)₃]_m where R² is a styryl, vinyl, an acrylate, methacrylate, acrylamide, methacrylamide, divinylbenzene, itaconate, fumarate, substituted or unsubstituted C₁-C₁₈ alkenylene, alkynylene or arylene, or a combination thereof;

R¹ is a C₁-C₄ alkyl moiety;

R⁶ is a substituted or unsubstituted C₁-C₁₈ alkenylene, alkynylene or arylene moiety bridging two or more silicon atoms; and

m is an integer greater than or equal to two.

20. The hybrid monolith of claim 19 wherein R² is vinyl, methacryloxypropyl, methacrylamidepropyl, or styrylethyl and R¹ is methyl or ethyl;

or R⁶ is a bridging N,N-bis(propylene) acrylamide group, m=2, and R¹ is ethyl or methyl.

21. The hybrid monolith of claim 16, wherein the organosilane is minimally water soluble.

22. The hybrid monolith of claim 16 wherein said tetraalkoxysilane is selected from the group consisting of tetramethoxysilane and tetraethoxysilane.

23. The hybrid monolith of claim 16, wherein the tetraalkoxysilane is tetramethoxysilane.

24. The hybrid monolith of claim 16, wherein the polymerizable group is 3-methacryloxypropyl.

25. The hybrid monolith of claim 16, wherein the polymerizable group is styrylethyl.

26. The hybrid monolith of claim 16, wherein the tetraalkoxysilane is minimally water soluble.

27. The hybrid monolith of claim 16, wherein the organosilane is (3-methacryloxypropyl)trimethoxysilane.

28. The hybrid monolith of claim 1, wherein the pore structure of said hybrid material is modified by further subjecting said material to hydrothermal treatment.

29. The hybrid monolith of claim 1, wherein said surfactant or combination of surfactants are nonionic surfactants.

30. The hybrid monolith of claim 29, wherein the surfactants are selected from the group consisting of surfactants comprised of block copolymers of polyethylene glycol and polypropyleneglycol, surfactants comprised of alkylphenoxypolyethoxyethanol, and polyethyleneglycol.

31. The hybrid monolith of claim 29, wherein the surfactant is polyoxyethylene-polyoxypropylene block copolymer.

32. The hybrid monolith of claim 28, wherein said surfactant or combination of surfactants are selected from surfactants with a hydrophile-lipophile balance ranging from about 0 to 60.

33. The hybrid monolith of claim 28, wherein said surfactant or combination of surfactants are selected from surfactants with a hydrophile-lipophile balance ranging from about 10 to 50.

34. The hybrid monolith of claim 28, wherein said surfactant or combination of surfactants are selected from surfactants with a hydrophile-lipophile balance ranging from about 20 to 40.

35. The hybrid monolith of claim 28, wherein said surfactant or combination of surfactants are selected from surfactants with a hydrophile-lipophile balance ranging from about 30 to 40.

36. The hybrid monolith of claim 28, wherein said surfactant or combination of surfactants are selected from surfactants with a hydrophile-lipophile balance of about 33.

37. The hybrid monolith of claim 1, wherein said monolith has been surface modified by a surface modifier selected from the group consisting of an organic group surface modifier, a silanol group surface modifier, a polymeric coating surface modifier, and combinations thereof.

38. The hybrid monolith of claim 37, wherein said monolith has been surface modified by a polymeric coating surface modifier.

39. The hybrid monolith of claim 37, wherein said monolith has been surface modified by a combination of an organic group surface modifier and a silanol group surface modifier.

40. The hybrid monolith of claim 37, wherein said monolith has been surface modified by a combination of an organic group surface modifier and a polymeric coating surface modifier.

41. The hybrid monolith of claim 37, wherein said monolith has been surface modified by a combination of a silanol group surface modifier and a polymeric coating surface modifier.

42. The hybrid monolith of claim 37, wherein said monolith has been surface modified by a combination of an organic group surface modifier, a silanol group surface modifier, and a polymeric coating surface modifier.

43. The hybrid monolith of claim 37, wherein said monolith has been surface modified by a silanol group surface modifier.

44. The hybrid monolith of claim 37, wherein said monolith has been surface modified via formation of an organic covalent bond between an organic group of the material and a surface modifier.

45. The hybrid monolith of claim 37, wherein the surface modifier has the formula Z_a(R′

)_bSi—

R, where Z=Cl, Br, I, C₁-C₅ alkoxy, dialkylamino or trifluoromethanesulfonate;

a and b are each an integer from 0 to 3 provided that a+b=3;

R′

is a C₁-C₆ straight, cyclic or branched alkyl group, and R is a functionalizing group.

46. The hybrid monolith of claim 45 wherein R′

is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, sec-butyl, pentyl, isopentyl, hexyl and cyclohexyl.

47. The hybrid monolith of claim 45 wherein said functionalizing group R is a C₁-C₃₀ alkyl group.

48. The hybrid monolith of claim 45 wherein said functionalizing group R is a C₁-C₂₀ alkyl group.

49. The hybrid monolith of claim 45 wherein said surface modifier is selected from the group consisting of octyltrichlorosilane, octadecyltrichlorosilane, octadecyldimethyl-N,N-dimethylaminosilane, octyldimethylchlorosilane, and octadecyldimethylchlorosilane.

50. The hybrid monolith of claim 45, wherein said surface modifier is octadecyldimethyl-N,N-dimethylaminosilane.

51. The hybrid monolith of claim 45, wherein said functionalizing group R is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, cyano, amino, diol, nitro, ester, a cation or anion exchange group, an alkyl group containing an embedded polar functionality and an aryl group containing an embedded polar functionality.

52. The hybrid monolith of claim 2, wherein the chromatotgraphic device has an internal surface and an external surface.

53. A method of in situ preparation of a hybrid inorganic/organic monolith in a fused-silica capillary column, said method comprising:

forming an anchoring functionality on an interior surface of said capillary column; and

forming inside said capillary column a hybrid inorganic/organic monolith comprising a polymerized scaffolding nanocomposite (PSN), wherein the nanocomposite contains a scaffolding functionality capable of chemically interacting with the anchoring functionality on said surface, said monolith being formed by;

a) forming a sol-gel by the reaction of two or more monomers;

b) initiating a polymerization reaction; and

c) allowing the monomers to react through a polymerization sol-gel (PSG) reaction;

whereby said scaffolding functionality and said anchoring functionality chemically interact to thereby anchor said monolith to said surface, such that a hybrid inorganic/organic monolith is prepared in situ in the fused-silica capillary column.

54. The method of claim 53 further comprising

modifying the pore structure of the monolith.