Nanocomposites and their application as monolith columns

Patent metadata

Field	Value
Publication number	US-10092859-B2
Application number	US-201615075520-A
Country	US
Kind code	B2
Filing date	Mar 21, 2016
Priority date	May 28, 2003
Publication date	Oct 9, 2018
Grant date	Oct 9, 2018

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.

First claim

What is claimed is:

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 μm.

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 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.

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 μm.

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

Assignees

• Waters Technologies Corp

Inventors

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

Classifications

• C08G77/20

  containing silicon bound to unsaturated aliphatic groups · CPC title

• Y10T428/26

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

• B01D15/22

  relating to the construction of the column · CPC title

• B05D7/22

  to internal surfaces, e.g. of tubes · CPC title

• B82Y30/00

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