Nanocomposites and their application as monolith columns

Patent metadata

Field	Value
Publication number	US-9289747-B2
Application number	US-201414275250-A
Country	US
Kind code	B2
Filing date	May 12, 2014
Priority date	May 28, 2003
Publication date	Mar 22, 2016
Grant date	Mar 22, 2016

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.

First claim

What is claimed is:

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(OR 1 ) 4 , where R 1 is a C 1 -C 3 alkyl moiety.

19. The hybrid monolith of claim 17 , wherein said organosilane is an organoalkoxysilane having the formula R 2 Si(OR 1 ) 3 or R 6 [Si(OR 1 ) 3 ] m where R 2 is a styryl, vinyl, an acrylate, methacrylate, acrylamide, methacrylamide, divinylbenzene, itaconate, fumarate, substituted or unsubstituted C 1 -C 18 alkenylene, alkynylene or arylene, or a combination thereof; R 1 is a C 1 -C 4 alkyl moiety; R 6 is a substituted or unsubstituted C 1 -C 18 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 R 2 is vinyl, methacryloxypropyl, methacrylamidepropyl, or styrylethyl and R 1 is methyl or ethyl; or R 6 is a bridging N,N-bis(propylene) acrylamide group, m=2, and R 1 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

Assignees

• Waters Technologies Corp

Inventors

• O'Gara John E
• Ding Julia
• Walsh Daniel B

Classifications

• B82Y30/00

  Nanotechnology for materials or surface science, e.g. nanocomposites · CPC title

• C08G77/20

  containing silicon bound to unsaturated aliphatic groups · CPC title

• B01D15/206 Primary

  Packing or coating · CPC title

• Y10T428/26

  Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension · CPC title

• B01J2220/86

  Sorbents applied to inner surfaces of columns or capillaries · CPC title