# US 2014/0194283 A1 · Porous inorganic/organic homogenous copolymeric hybrid materials for chromatographic separations and process for the preparation thereof

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 2014/0194283 A1
- Document ID: US20140194283A1
- Status: Published application
- Kind: A1
- Application number: 14/206,538
- Filed: 2014-03-12
- Published: 2014-07-10
- Earliest claimed: 2005-04-29
- Assignees: Waters Technologies Corporation
- Applicants: Waters Technologies Corporation
- Inventors: Zhiping Jiang; John E. O'Gara; Raymond P. Fisk; Kevin D. Wyndham
- Web page: https://patentgrep.com/patent/US20140194283A1

## CPC

- C08F 230/085: {the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes}
- B01J 20/26: Synthetic macromolecular compounds
- B01J 20/265: {modified or post-treated polymers (polymer carriers or substrates subjected to further impregnating or coating B01J20/3208)}
- B01J 20/28019: {Spherical, ellipsoidal or cylindrical}
- B01J 20/28042: {Shaped bodies; Monolithic structures}
- B01J 20/285: based on polymers
- B01J 20/286: Phases chemically bonded to a substrate, e.g. to silica or to polymers
- C08G 77/442: containing vinyl polymer sequences
- C08J 9/35: Composite foams, i.e. continuous macromolecular foams containing discontinuous cellular particles or fragments
- C08L 53/00: Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L 53/005: {Modified block copolymers}
- B01J 2220/82: Shaped bodies, e.g. monoliths, plugs, tubes, continuous beds
- C08J 2329/04: Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
- C08J 2383/06: containing silicon bound to oxygen-containing groups (C08J2383/12 takes precedence)
- Y10T 428/2982: Particulate matter [e.g., sphere, flake, etc.]
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

The present invention relates to porous inorganic/organic homogenous copolymeric hybrid material materials, including particulates and monoliths, methods for their manufacture, and uses thereof, e.g., as chromatographic separations materials.

## Claims

### Claim at position 1

1-140. (canceled)

### Claim 141

A porous inorganic/organic homogenous copolymeric hybrid material of the formula:
(A)x(B)y(C)z
wherein the order of repeat units A, B, and C may be random, block, or a combination of random and block;
A is selected from the group consisting of
wherein each R is independently H or a C1-C10 alkyl group; m is an integer of from 1 to 20; n is an integer of from 0 to 10; and Q is hydrogen, N(C1-6alkyl)3, N(C1-6alkyl)2(C1-6alkylene-SO3), or C(C1-6hydroxyalkyl)3;
B is an organosiloxane repeat unit selected from the group consisting of:
an organosiloxane repeat unit derived from a monomer selected from the group consisting of: ethacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, (3-acryloxypropyl)trimethoxysilane, O-(methacryloxyethyl)-N-(triethoxysilylpropyl)urethane, N-(3-methacryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropyltris(methoxyethoxy)silane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane hydrochloride, which is bonded to one or more repeat units B or C via an inorganic siloxane bond and which may be further bonded to one or more repeat units A or B via an organic bond;
C is an inorganic repeat unit which is bonded to one or more repeat units B or C via an inorganic bond; and
x,y are positive numbers and z is a non negative number, wherein
when z=0, then 0.002≦x/y≦210, and when z≠0, then 0.0003≦y/z≦500 and 0.002≦x/(y+z)≦210;
wherein the porous inorganic/organic homogenous copolymeric hybrid material has specific pore volumes of about 0.25 to 2.5 cm3/g and an average pore diameter of about 50 to 300 Å.

### Claim 142

A porous inorganic/organic homogenous copolymeric hybrid material of the formula:
(A)x(B)y(B*)y*(C)z
wherein the order of repeat units A, B, B*, and C may be random, block, or a combination of random and block;
A is selected from the group consisting of
wherein each R is independently H or a C1-C10 alkyl group; m is an integer of from 1 to 20; n is an integer of from 0 to 10; and Q is hydrogen, N(C1-6alkyl)3, N(C1-6alkyl)2(C1-6alkylene-SO3), or C(C1-6hydroxyalkyl)3;
B is an organosiloxane repeat unit selected from the group consisting of:
an organosiloxane repeat unit derived from a monomer selected from the group consisting of: ethacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, (3-acryloxypropyl)trimethoxysilane, O-(methacryloxyethyl)-N-(triethoxysilylpropyl)urethane, N-(3-methacryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropyltris(methoxyethoxy)silane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane hydrochloride, which is bonded to one or more repeat units B or B* or C via an inorganic siloxane bond and which may be further bonded to one or more repeat units A or B via an organic bond;
B* is an organosiloxane repeat unit which is bonded to one or more repeat units B or B* or C via an inorganic siloxane bond, wherein B* is an organosiloxane repeat unit that does not have reactive (i.e., polymerizable) organic components and may further have a protected functional group that may be deprotected after polymerization;
C is an inorganic repeat unit which is bonded to one or more repeat units B or B* or C via an inorganic bond; and
x,y are positive numbers and z is a non negative number, wherein
when z=0, then 0.002≦x/(y+y*)≦210, and when z≠0, then
0.0003≦(y+y*)/z≦500 and 0.002≦x/(y+y*+z)≦210;
wherein the porous inorganic/organic homogenous copolymeric hybrid material has specific pore volumes of about 0.25 to 2.5 cm3/g and an average pore diameter of about to 300 Å.

### Claim 143 (depends on 141)

The material according to claim 141, wherein 0.003≦y/z≦50 and 0.02≦x/(y+z)≦21.

### Claim 144 (depends on 141)

The material according to claim 141, wherein said material has a specific surface area of about 50-800 m2/g.

### Claim 145 (depends on 141)

The material according to claim 141, wherein said material is hydrolytically stable at a pH of about 1 to about 13.

### Claim 146 (depends on 142)

The material according to claim 142, wherein 0.003≦y/z≦50 and 0.02≦x/(y+z)≦21.

### Claim 147 (depends on 142)

The material according to claim 142, wherein said material has a specific surface area of about 50-800 m2/g.

### Claim 148 (depends on 142)

The material according to claim 142, wherein said material is hydrolytically stable at a pH of about 1 to about 13.

### Claim 149 (depends on 141)

A separations device comprising a material according to claim 141.

### Claim 150 (depends on 149)

The separations device according to claim 149, wherein said device is selected from the group consisting of chromatographic columns, thin layer plates, filtration membranes, sample cleanup devices, and microtiter plates.

### Claim 151 (depends on 142)

A separations device comprising a material according to claim 142.

### Claim 152 (depends on 151)

The separations device according to claim 151, wherein said device is selected from the group consisting of chromatographic columns, thin layer plates, filtration membranes, sample cleanup devices, and microtiter plates.

### Claim 153 (depends on 141)

The porous inorganic/organic homogenous copolymeric hybrid material of claim 141, wherein z=0 and the hybrid material is of the formula:
(A)x(B)y
wherein the order of repeat units A and B may be random, block, or a combination of random and block;
A is selected from the group consisting of
wherein each R is independently H or a C1-C10 alkyl group; m is an integer of from 1 to 20; n is an integer of from 0 to 10; and Q is hydrogen, N(C1-6alkyl)3, N(C1-6alkylene)2(C1-6alkylene-SO3), or C(C1-6hydroxyalkyl)3;
B is an organosiloxane repeat unit selected from the group consisting of:
an organosiloxane repeat unit derived from a monomer selected from the group consisting of: ethacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, (3-acryloxypropyl)trimethoxysilane, O-(methacryloxyethyl)-N-(triethoxysilylpropyl)urethane, N-(3-methacryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropyltris(methoxyethoxy)silane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane hydrochloride, which may or may not be bonded to one or more repeat units B via an inorganic siloxane bond and which may be further bonded to one or more repeat units A or B via an organic bond; and 0.002≦x/y≦210;
wherein the porous inorganic/organic homogenous copolymeric hybrid material has specific pore volumes of about 0.25 to 2.5 cm3/g and an average pore diameter of about 50 to 300 Å.

### Claim 154 (depends on 142)

The porous inorganic/organic homogenous copolymeric hybrid material of claim 142, wherein z=0 and the hybrid material is of the formula:
(A)x(B)y(B*)y*
wherein the order of repeat units A, B, and B* may be random, block, or a combination of random and block;
A is selected from the group consisting of
wherein each R is independently H or a C1-C10 alkyl group; m is an integer of from 1 to 20; n is an integer of from 0 to 10; and Q is hydrogen, N(C1-6alkyl)3, N(C1-6alkyl)2(C1-6alkylene-SO3), or C(C1-6hydroxyalkyl)3;
B is an organosiloxane repeat unit selected from the group consisting of:
an organosiloxane repeat unit derived from a monomer selected from the group consisting of: ethacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, (3-acryloxypropyl)trimethoxysilane, O-(methacryloxyethyl)-N-(triethoxysilylpropyl)urethane, N-(3-methacryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropyltris(methoxyethoxy)silane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane hydrochloride, which may or may not be bonded to one or more repeat units B or B* via an inorganic siloxane bond and which may be further bonded to one or more repeat units A or B via an organic bond
B* is an organosiloxane repeat unit that does not have reactive (i.e., polymerizable) organic components and may further have a protected functional group that may be deprotected after polymerization; and 0.002≦x/(y+y*)≦210;
wherein the porous inorganic/organic homogenous copolymeric hybrid material has specific pore volume of about 0.25 to 2.5 cm3/g and an average pore diameter of about 50 to 300 Å.