Porous inorganic/organic hybrid monolith materials for chromatographic separations and process for their preparation

• US 9,089,836 B2
• Filed: 03/25/2013
• Issued: 07/28/2015
• Est. Priority Date: 08/09/2001
• Status: Active Grant

• Current Assignee: Waters Technologies Corporation (Waters Corporation)
• Original Assignee: Waters Technologies Corporation (Waters Corporation)
• Inventors: Walter, Thomas H., Ding, Julia, Kele, Marianna, O'Gara, John E., Iraneta, Pamela C.
• Primary Examiner(s): BROOKS, CLINTON A
• Application Number:
  US13/850,212
• Publication Number:
  US 20130324395A1
• Time in Patent Office: 855 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: B01J 20/103 comprising silica
• CPC Class Codes: B01J 20/262 obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds per se C08G
• CPC Class Codes: B01J 20/264 derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
• CPC Class Codes: B01J 20/28033 Membrane, sheet, cloth, pad, lamellar or mat
• CPC Class Codes: B01J 20/28042 Shaped bodies; Monolithic structures
• CPC Class Codes: B01J 20/28057 Surface area, e.g. B.E.T specific surface area
• CPC Class Codes: B01J 20/28069 Pore volume, e.g. total pore volume, mesopore volume, micropore volume
• CPC Class Codes: B01J 20/28078 Pore diameter
• CPC Class Codes: B01J 20/28095 Shape or type of pores, voids, channels, ducts
• 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 20/3212 consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
• CPC Class Codes: B01J 20/3217 Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond
• CPC Class Codes: B01J 20/3227 by end-capping, i.e. with or after the introduction of functional or ligand groups
• CPC Class Codes: B01J 20/3242 Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
• CPC Class Codes: B01J 20/3246 having a well defined chemical structure
• CPC Class Codes: B01J 20/3272 Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
• CPC Class Codes: B01J 2220/46 Materials comprising a mixture of inorganic and organic materials materials coated or impregnated on a carrier B01J20/32
• CPC Class Codes: B01J 2220/54 Sorbents specially adapted for analytical or investigative chromatography
• CPC Class Codes: B01J 2220/58 Use in a single column
• CPC Class Codes: B01J 2220/82 : Shaped bodies, e.g. monoliths, plugs, tubes, continuous beds
• CPC Class Codes: D04H 1/42 : characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
• CPC Class Codes: Y10T 428/2982 : Particulate matter [e.g., sphere, flake, etc.]
• CPC Class Codes: Y10T 428/2993 : Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
• CPC Class Codes: Y10T 428/2995 : Silane, siloxane or silicone coating

Abstract

Novel materials for chromatographic separations, processes for their preparation, and separation devices containing the chromatographic materials. In particular, the novel materials are porous inorganic/organic hybrid monolith materials, which desirably may be surface modified, and which offer more efficient chromatographic separations than that known in the art.

Claims

1. A method of preparation of a porous inorganic/organic hybrid monolith material, comprising coalesced porous particles of hybrid silica having a chromatography-enhancing pore geometry, comprising the steps of

a) prepolymerizing a mixture of one or more organoalkoxysilanes and a tetraalkoxysilane in the presence of an acid catalyst to produce a polyorganoalkoxysiloxane;

b) preparing an aqueous suspension of said polyorganoalkoxysiloxane, said suspension further comprising a surfactant or combination of surfactants, and gelling in the presence of a base catalyst so as to produce porous hybrid particles;

c) modifying the pore structure of said porous hybrid particles by hydrothermal treatment; and

d) coalescing said porous hybrid particles to form a monolith material thereby preparing a porous inorganic/organic hybrid monolith material.

2. A porous inorganic/organic hybrid monolith material comprising coalesced porous hybrid particles of hybrid silica having a chromatographically-enhancing pore geometry, produced by the process of

a) prepolymerizing a mixture of one or more organoalkoxysilanes and a tetraalkoxysilane in the presence of an acid catalyst to produce a polyorganoalkoxysiloxane;

b) preparing an aqueous suspension of said polyorganoallcoxysiloxane, said suspension further comprising a surfactant or a combination of surfactants, and gelling in the presence of a base catalyst so as to produce porous hybrid particles;

c) modifying the pore structure of said porous hybrid particles by hydrothermal treatment; and

coalescing said porous hybrid particles to form a monolith material.

3. A porous inorganic/organic hybrid monolith material, comprising coalesced porous inorganic/organic hybrid particles having a chromatographically-enhancing pore geometry and a formula SiO₂/[C₂H₄(SiO_1.5)₂]_0.25 wherein said hybrid particles have been surface modified with octadecyltrichlorosilane and wherein any free silanol groups remaining from said surface modification are endcapped with chlorotrimethylsilane.

4. A porous inorganic/organic hybrid monolith material comprising coalesced porous hybrid particles of hybrid silica having a chromatographically-enhancing pore geometry and a formula SiO₂/[C₂H₄(SiO_1.5)₂]_0.25 produced by the process of

a) prepolymerizing a 0.25/1.0 mole ratio mixture of bis(triethoxysilyl)ethane and tetraethoxysilane in the presence of 0.1 molar hydrochloric acid to produce a polyorganosiloxane;

b) preparing an aqueous suspension of said polyorganoalkoxysiloxane, said suspension further comprising the surfactant Triton X-100, and gelling said suspension in the presence of a ammonium hydroxide so as to produce porous hybrid particles;

c) modifying the pore structure of said porous hybrid particles by hydrothermal treatment at 155°

C. for 20 h in 0.3 M tris(hydroxymethyl)aminomethane, pH adjusted to 9.80;

d) sizing to a nominal 2 μ

m particle diameter;

acid washing in a 1 molar hydrochloric acid solution;

e) further surface modifying with octadecyltrichlorosilane wherein any free silanol groups remaining from said surface modification are endcapped with chlorotrimethylsilane; and

g) coalescing said porous hybrid particles to form a monolith material.

5. A porous inorganic/organic hybrid monolith material having a chromatographically-enhancing pore geometry and a formula SiO₂/[CH₃SiO_1.5]_0.5 wherein said hybrid material has been surface modified with octadecyltrichlorosilane and wherein any free silanol groups remaining from said surface modification procedure are endcapped with chlorotrimethylsilane and wherein said material contains a plurality of macropores sufficient to result in reduced backpressure at chromatographically-useful flow rates.

6. A porous inorganic/organic hybrid monolith material having a chromatographically-enhancing pore geometry and a formula SiO₂/[CH₃SiO_1.5]_0.5, produced by the process of

a) preparing an aqueous solution of methyltrimethoxysilane and a tetramethoxysilane in the presence of a 0.07 molar acetic acid solution and the surfactant Pluronic P-105 or Trition X-100 to produce a polyorganoalkoxysiloxane;

a) incubating said solution for 3 days at 45°

C., resulting in a three-dimensional gel having a continuous, interconnected pore structure;

b) aging the gel in 1 molar ammonium hydroxide at 60°

C. for 3 days to yield a solid monolith material;

c) rinsing the monolith material with water;

d) modifying the pore structure of said monolith material by hydrothermal treatment at 155°

C. for 20 h in 0.1 molar tris(hydroxymethyl)aminomethane, p1-1 adjusted to 8.0;

e) rinsing the monolith material with water followed by a solvent exchange;

g)

     1) acid washing the monolith material in 1 molar hydrochloric acid for 24 hours at 98°

C.;

rinsing the monolith material with water followed by a solvent exchange;

h) drying the monolith material at room temperature drying and at 80°

C. under vacuum; and

i) further surface modifying with octadecyltrichlorosilane wherein any free silanol groups remaining from said surface modification are endcapped with chlorotrimethylsilane.

7. A porous inorganic/organic hybrid monolith material having a chromatographically-enhancing pore geometry and a formula SiO₂/[C₂H₄(SiO_1.5)₂]_0.25 wherein said hybrid material has been surface modified with octadecyltrichlorosilane and wherein any free silanol groups remaining from said surface modification procedure are endcapped with chlorotrimethylsilane and wherein said material contains a plurality of macropores sufficient to result in reduced backpressure at chromatographically-useful flow rates.

8. A porous inorganic/organic hybrid monolith material having achromatographically-enhancing pore geometry and a formula SiO₂/[C₂H₄(SiO_1.5)₂]_0.25, produced by the process of

a) preparing an aqueous solution 1,2-bis(trimethoxysilyl)ethane and

tetramethoxysilane in the presence of a 0.09 molar acetic acid solution and

the surfactant Pluronic P-123 to produce a polyorganoalkoxysiloxane;

b) incubating said solution for 2 days at 45°

C., resulting in a three-dimensional gel having a continuous, interconnected pore structure;

c) aging the gel in 1 molar ammonium hydroxide at 60°

C. for 2 days to yield a solid monolith material;

d) rinsing the monolith material with water;

modifying the pore structure of said monolith material by hydrothermal treatment at 155°

C. for 24 h in 0.1 M tris(hydroxymethyl)aminomethane, pH adjusted to 10.6;

f) rinsing the monolith material with water followed by a solvent exchange;

g) acid washing the monolith material in 1 molar hydrochloric acid for 24 hours at 98°

C.;

h) rinsing the monolith material with water followed by a solvent exchange;

i) drying the monolith material at room temperature drying and at 80°

C. under vacuum, and

j) further surface modifying with octadecyltrichlorosilane wherein any free silanol groups remaining from said surface modification are endcapped with chlorotrimethylsilane.

9. A porous inorganic/organic hybrid monolith material having a chromatographically-enhancing pore geometry and a formula SiO₂/[HOC₃H₆SiO_1.5]_0.15 wherein said hybrid material has been surface modified with dodecylsiocyante and wherein said material contains a plurality of macropores sufficient to result in reduced backpressure at chromatographically-useful flow rates.

10. A porous inorganic/organic hybrid monolith material having a 30 chromatographically-enhancing pore geometry and a formula SiO₂/[HOC₃H₆SiO_1.5]_0.15, produced by the process of

a) preparing an aqueous solution methacryloxypropyltrimethoxysilane and tetramethoxysilane in the presence of a 0.015 molar acetic acid solution and the surfactant Triton X-100 or Triton 405 to produce a polyorganoalkoxysiloxane;

b) incubating said solution for 3 days at 45°

C., resulting in a three-dimensional gel having a continuous, interconnected pore structure;

c) aging the gel in 1 molar ammonium hydroxide at 60°

C. for 3 days to yield a solid monolith material;

d) rinsing the monolith material with water;

e) modifying the pore structure of said monolith material by hydrothermal treatment at 155°

C. for 24 h in 0.1 M tris(hydroxymethyl)aminomethane, pH

adjusted to 10.6;

f) rinsing the monolith material with water followed by a solvent exchange;

g) acid washing the monolith material in 1 molar hydrochloric acid for 24 hours at 98°

C.;

h) rinsing the monolith material with water followed by a solvent exchange;

i) drying the monolith material at room temperature drying and at 80°

C. under vacuum, and

j) further surface modifying with dodecylisocyanate.