Superficially porous materials comprising a substantially nonporous hybrid core having narrow particle size distribution; process for the preparation thereof; and use thereof for chromatographic separations

• US 10,092,893 B2
• Filed: 07/25/2011
• Issued: 10/09/2018
• Est. Priority Date: 07/26/2010
• Status: Active Grant

• Current Assignee: Waters Technologies Corporation (Waters Corporation)
• Original Assignee: Waters Technologies Corporation (Waters Corporation)
• Inventors: Wyndham, Kevin D., Muriithi, Beatrice W.
• Primary Examiner(s): Graber, Kara
• Application Number:
  US13/638,924
• Publication Number:
  US 20130206665A1
• Time in Patent Office: 2,633 Days
• Field of Search: None
• CPC Class Codes: B01J 20/28004 Sorbent size or size distribution, e.g. particle size
• CPC Class Codes: B01J 20/28057 Surface area, e.g. B.E.T specific surface area
• CPC Class Codes: B01J 20/28071 being less than 0.5 ml/g
• CPC Class Codes: B01J 20/283 based on silica
• CPC Class Codes: B01J 20/285 based on polymers
• CPC Class Codes: B01J 20/286 Phases chemically bonded to a substrate, e.g. to silica or to polymers
• CPC Class Codes: B01J 20/3204 Inorganic carriers, supports or substrates
• CPC Class Codes: B01J 20/3219 involving a particular spacer or linking group, e.g. for attaching an active group
• CPC Class Codes: B01J 20/3236 containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
• CPC Class Codes: B01J 20/3257 the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such
• CPC Class Codes: B01J 20/3289 Coatings involving more than one layer of same or different nature
• CPC Class Codes: B01J 20/3293 Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
• CPC Class Codes: Y10T 428/2991 Coated

Abstract

The present invention provides novel chromatographic materials, e.g., for chromatographic separations, processes for its preparation and separations devices containing the chromatographic material; separations devices, chromatographic columns and kits comprising the same; and methods for the preparation thereof. The chromatographic materials of the invention are chromatographic materials comprising having a narrow particle size distribution.

Claims

1. A superficially porous material comprising superficially porous particles, wherein the superficially porous particles comprise an inorganic/organic hybrid core and one or more layers of a porous shell material surrounding the inorganic/organic hybrid core wherein the inorganic/organic hybrid core has a pore volume of less than 0.10 cc/g;

and

wherein the inorganic/organic hybrid core has the formula;

(SiO₂)_d/[R²((R)_p(R¹)_qSiO_t)_m] 

 

(I)

wherein,

R and R¹ are each independently C₁-C₁₈ alkoxy, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₁-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈ aryloxy, or C₁-C₁₈ heteroaryl;

R² is C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₁-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₁-C₁₈ heteroaryl, wherein R² is attached to two or more silicon atoms;

R, R¹ and R² are optionally substituted;

p and q are each independently 0.0 to 2.0,

t is 0.5, 1.0, or 1.5;

d is 0 to about 30; and

m=2-20,

2. The superficially porous material of claim 1, wherein the superficially porous material has chromatographically enhancing pore geometry.

3. The superficially porous material of claim 1 wherein the porous shell material is a porous inorganic/organic hybrid material.

4. The superficially porous material of claim 1 wherein the porous shell material is a porous silica.

5. The superficially porous material of claim 1 wherein the porous shell material is a porous composite material.

6. The superficially porous material of claim 1, wherein the superficially porous particles comprise an inorganic/organic hybrid core and more than one layer of a porous shell material wherein each layer of the porous shell material is independently selected from a porous inorganic/organic hybrid material of formula (I) according to claim 1, a porous silica, a porous composite material, or mixtures thereof.

7. The superficially porous material of claim 1 wherein the superficially porous material has a spherical core morphology, a rod shaped core morphology, a bent-rod shaped core morphology, a toroid shaped core morphology, or a dumbbell shaped core morphology.

8. The superficially porous material of claim 1, wherein the inorganic/organic hybrid core has a particle size of 0.5-10 μ

m.

9. The superficially porous material of claim 1, wherein the superficially porous particles comprise an inorganic/organic hybrid core and more than one layer of a porous shell material, wherein each layer of porous shell material is independently from 0.05 μ

m to 5 μ

m in thickness as measured perpendicular to an outer surface of the inorganic/organic hybrid core.

10. The superficially porous material of claim 1, wherein the superficially porous material has an average particle size between 0.8-10.0 μ

m.

11. The superficially porous material of claim 1, wherein the superficially porous material has an average pore diameter of about 25-600 Å

.

12. The superficially porous material of claim 1, wherein the superficially porous material has an average pore volume of about 0.11-0.50 cm³/g.

13. The superficially porous material of claim 1, wherein pore surface area is between about 10 m²/g and 400 m²/g.

14. The superficially porous material of claim 1, which has been further surface modified.

15. The superficially porous material of claim 1, which has been further surface modified by:

coating with a polymer;

by coating with a polymer by a combination of organic group and silanol group modification;

a combination of organic group modification and coating with a polymer;

a combination of silanol group modification and coating with a polymer;

formation of an organic covalent bond between an organic group of the material and a modifying reagent;

or

a combination of organic group modification, silanol group modification and coating with a polymer.

16. A separations device having a stationary phase comprising the superficially porous material of claim 1.

17. A chromatographic column, comprising

a) a column having a cylindrical interior for accepting a packing material and

b) a packed chromatographic bed comprising the superficially porous material of claim 1.

18. A chromatographic device, comprising

a) an interior channel for accepting a packing material and

b) a packed chromatographic bed comprising the superficially porous material of claim 1.

19. A kit comprising the superficially porous material of claim 1, and instructions for use.

20. The superficially porous material of claim 1, wherein the superficially porous particles comprise an inorganic/organic hybrid core and one or more layer of a porous shell material;

and wherein each layer of the porous shell material is independently selected from a porous inorganic/organic hybrid material of formula (I) according to claim 1.