Nanocomposites and their application as monolith columns

• US 10,092,859 B2
• Filed: 03/21/2016
• Issued: 10/09/2018
• 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 P.
• Primary Examiner(s): Moore, Margaret G
• Application Number:
  US15/075,520
• Publication Number:
  US 20160199753A1
• Time in Patent Office: 932 Days
• 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 functionality 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 separations device comprising

a) a surface capable of accepting a monolith material comprising a polymerized scaffolding nanocomposite (PSN) material, said surface comprising an anchoring functionality and

b) 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, and wherein said hybrid organic/inorganic monolith is anchored to said surface by a chemical interaction between said scaffolding functionality and anchoring functionality,

wherein the hybrid inorganic/organic monolith is prepared by a method comprising:

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

wherein the surfactant is removed from the monolith structure following said PSG reaction, and

wherein (a) the scaffolding functionality is selected from vinyl, acrylate, methacrylate, acrylamide, methacrylamide, styrene, divinylbenzene, itaconate, fumarate, alkyne, and combinations thereof, (b) wherein the anchoring functionality is selected from vinyl, acrylate, methacrylate, acrylamide, methacrylamide, styrene, divinylbenzene, itaconate, fumarate, alkyne, azo compounds, and combinations thereof, or (c) both (a) and (b).

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

3. The separations device of claim 2, wherein said device is a chromatographic column.

4. The separations device of claim 3, wherein the chromatographic column has an inner diameter (I.D.) greater than 50 μ

m.

5. The separations device of claim 1, wherein the scaffolding functionality is selected from vinyl, acrylate, methacrylate, acrylamide, methacrylamide, styrene, divinylbenzene, itaconate, fumarate, alkyne, and combinations thereof.

6. The separations device of claim 1, wherein the anchoring functionality is selected from vinyl, acrylate, methacrylate, acrylamide, methacrylamide, styrene, divinylbenzene, itaconate, fumarate, alkyne, azo compounds, and combinations thereof.

7. The separations device of claim 1, wherein the inorganic portion of the hybrid material is a material selected from alumina, silica, titanium oxide, zirconium oxide, and ceramic material.

8. The separations device of claim 1, wherein the PSN is the product of a reaction of an organosilane and an inorganic silane monomer.

9. The separations device of claim 8, 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.

10. The separations device of claim 8, wherein the organosilane is (3-methacryloxypropyl) trimethoxysilane.

11. The separations device of claim 1, wherein said surfactant or combination of surfactants are nonionic surfactants.

12. The separations device of claim 1, wherein said material has been surface modified by a surface modifier selected from an organic group surface modifier, a silanol group surface modifier, a polymeric coating surface modifier, and combinations thereof.

13. A fused-silica capillary column comprising

a) a fused-silica capillary column having a cylindrical interior surface capable of accepting a monolith comprising a polymerized scaffolding nanocomposite (PSN) material, said interior surface comprising an anchoring functionality, and

b) 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, and wherein said hybrid organic/inorganic monolith is anchored to said surface by a chemical interaction between said scaffolding functionality and anchoring functionality,

wherein the hybrid inorganic/organic monolith is prepared by a method comprising:

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,

wherein the surfactant is removed from the monolith structure following said PSG reaction, and

wherein (a) the scaffolding functionality is selected from vinyl, acrylate, methacrylate, acrylamide, methacrylamide, styrene, divinylbenzene, itaconate, fumarate, alkyne, and combinations thereof, (b) the anchoring functionality is selected from vinyl, acrylate, methacrylate, acrylamide, methacrylamide, styrene, divinylbenzene, itaconate, fumarate, alkyne, azo compounds, and combinations thereof, or (c) both (a) and (b).

14. The fused-silica capillary column of claim 13, wherein the chromatographic column has an inner diameter (I.D.) greater than 50 μ

m.

15. The fused-silica capillary column of claim 13, wherein the scaffolding functionality is selected from vinyl, acrylate, methacrylate, acrylamide, methacrylamide, styrene, divinylbenzene, itaconate, fumarate, alkyne, and combinations thereof.

16. The fused-silica capillary column of claim 13, wherein the anchoring functionality is selected from vinyl, acrylate, methacrylate, acrylamide, methacrylamide, styrene, divinylbenzene, itaconate, fumarate, alkyne, azo compounds, and combinations thereof.

17. The fused-silica capillary column of claim 13, wherein the inorganic portion of the hybrid material is a material selected from alumina, silica, titanium oxide, zirconium oxide, and ceramic material.

18. The fused-silica capillary column of claim 13, wherein the PSN is the product of a reaction of an organosilane and an inorganic silane monomer.

19. The fused-silica capillary column of claim 18, 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 fused-silica capillary column of claim 18, wherein the organosilane is (3-methacryloxypropyl) trimethoxysilane.