# US 2014/0155565 A1 · Hydrophilic crosslinked polymer

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- Number: US 2014/0155565 A1
- Document ID: US20140155565A1
- Status: Published application
- Kind: A1
- Application number: 14/173,218
- Filed: 2014-02-05
- Published: 2014-06-05
- Earliest claimed: 2005-08-03
- Assignees: Merck Patent GmbH
- Applicants: Merck Patent GmbH
- Inventors: Matthias JOEHNCK; Eckhard SABROWSKII
- Web page: https://patentgrep.com/patent/US20140155565A1

## CPC

- C08F 216/1416: {Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether}
- B01J 20/26: Synthetic macromolecular compounds
- B01J 20/261: {obtained by reactions only involving carbon to carbon unsaturated bonds (macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds per se C08F)}
- B01J 20/265: {modified or post-treated polymers (polymer carriers or substrates subjected to further impregnating or coating B01J20/3208)}
- B01J 20/267: {Cross-linked polymers}
- B01J 20/285: based on polymers
- C08F 216/14: Monomers containing only one unsaturated aliphatic radical
- C08F 222/385: {Monomers containing two or more (meth)acrylamide groups, e.g. N,N'-methylenebisacrylamide}
- 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
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

The present invention relates to a hydrophilic crosslinked polymer, preferably in the form of porous particles, and to the preparation and use thereof. The polymer according to the invention is produced by polymerisation from chain-forming hydrophilic vinyl ethers and crosslinking, preferably heterocyclic divinyl ethers.

## Claims

### Claim at position 1

1-20. (canceled)

### Claim 21

A polymer based on a copolymer, which is in the form of polymeric particles, comprising
a) at least one hydrophilically substituted alkyl vinyl ether of formula I
where
R1, R2, R3, independently of one another, is H or C1 to C6 alkyl, and
R4 is a radical which carries at least one hydroxyl group,
and
b) at least one crosslinking agent of formula II and/or III and/or IV
where
X is a divalent alkyl radical having 2 to 5 C atoms in which one or more methylene groups which are not adjacent and are not located in the direct vicinity of N may be replaced by O, C═O, S, S═O, SO2, NH, NOH or N and one or more H atoms of the methylene groups may be substituted, independently of one another, by hydroxyl, C1-C6-alkyl, halogen, NH2, C5-C10-aryl, NH—(C1-C8)-alkyl, N—(C1-C8)-alkyl2, C1-C6-alkoxy or C1-C6-alkyl-OH,
where
Y1 and Y2 in formula III and IV
are, independently of one another, C1 to C10 alkyl or cycloalkyl, where one or more non-adjacent methylene groups or methylene groups which are not located in the direct vicinity of N may be replaced by O, C═O, S, S═O, SO2, NH, NOH or N and one or more H atoms of the methylene groups may be substituted, independently of one another, by hydroxyl, C1-C6-alkyl, halogen, NH2, C5-C10-aryl, NH(C1-C8)alkyl, N(C1-C8)alkyl2, C1-C6-alkoxy or C1-C6-alkyl-OH, or
C6 to C18 aryl, where one or more H atoms in the aryl system may be substituted, independently of one another, by hydroxyl, C1-C6-alkyl, halogen, NH2, NH(C1-C8)alkyl, N(C1-C8)alkyl2, C1-C6-alkoxy or C1-C6-alkyl-OH, and
A is a divalent alkyl radical having 2 to 5 C atoms in which one or more non-adjacent methylene groups or methylene groups which are not located in the direct vicinity of N may be replaced by O, C═O, S, S═O, SO2, NH, NOH or N and one or more H of the methylene groups may be substituted, independently of one another, by hydroxyl groups, C1-C6-alkyl, halogen, NH2, C5-C10-aryl, NH(C1-C8)alkyl, N(C1-C8)alkyl2, C1-C6-alkoxy or C1-C6-alkyl-OH,
wherein a) and b) have been copolymerized and the resultant polymer is in the form of polymeric particles.

### Claim 22 (depends on 21)

A polymer according to claim 21, wherein R4 in formula I is a straight-chain or branched C1 to C10 alkyl radical, in which one or more non-adjacent methylene groups may be replaced by O, C═O, S, S═O, SO2, NH, NOH, or N and/or in which one or more H atoms may be substituted, independently of one another, by C1-C6-alkyl, C5-C10-aryl, halogen, NH2, NH(C1-C8)alkyl, N(C1-C8)alkyl2, C1-C6-alkoxy or C1-C6-alkyl-OH and in which at least one OH group is present either on the C1 to C10 alkyl radical or on a substituent, or
a cycloaliphatic radical, in which one or more non-adjacent methylene groups may be replaced by O, C═O, S, S═O, SO2, NH, NOH, or N and/or in which one or more H atoms of the cycloaliphatic radical may be substituted, independently of one another, by C1-C6-alkyl, C5-C10-aryl, halogen, NH2, NH(C1-C8)alkyl, N(C1-C8)alkyl2, C1-C6-alkoxy or C1-C6-alkyl-OH, where at least one OH group is present either on the cycloaliphatic ring or on a side chain or substituent, or
a C6 to C18 aryl radical, where one or more H atoms in the aryl radical may be substituted, independently of one another, by hydroxyl, C1-C6-alkyl, C5-C10-aryl, halogen, NH2, NH(C1-C8)alkyl, N(C1-C8)alkyl2, C1-C6-alkoxy or C1-C6-alkyl-OH, where at least one OH group is present either on the aryl radical or on a side chain or substituent, or
a C5 to C18 heteroaryl radical, where one or more H atoms in the heteroaryl radical may be substituted, independently of one another, by hydroxyl, C1-C6-alkyl, C5-C10-aryl, halogen, NH2, NH(C1-C8)alkyl, N(C1-C8)alkyl2, C1-C6-alkoxy or C1-C6-alkyl-OH, where at least one OH group is present either on the heteroaryl radical or on a side chain or substituent.

### Claim 23 (depends on 21)

A polymer according to claim 21, wherein the hydrophilically substituted alkyl vinyl ether is a compound of formula I in which R4 is a radical which carries a hydroxyl group.

### Claim 24 (depends on 21)

A polymer according to claim 21, wherein the hydrophilically substituted alkyl vinyl ether is 1,2-ethanediol monovinyl ether, 1,3-propanediol monovinyl ether, 1,4-butanediol monovinyl ether, 1,5-pentanediol monovinyl ether, 1,6-hexanediol monovinyl ether, diethylene glycol monovinyl ether or cyclohexanedimethanol monovinyl ether.

### Claim 25 (depends on 21)

A polymer according to claim 21, wherein the crosslinking agent is divinylethyleneurea (1,3-divinylimidazolin-2-one) or divinylpropyleneurea (1,3-divinyltetrahydropyrimidin-2-one).

### Claim 26 (depends on 21)

A polymer according to claim 21, wherein the hydrophilically substituted alkyl vinyl ether is 1,2-ethanediol monovinyl ether, 1,3-propanediol monovinyl ether, 1,4-butanediol monovinyl ether, 1,5-pentanediol monovinyl ether, 1,6-hexanediol monovinyl ether, diethylene glycol monovinyl ether or cyclohexanedimethanol monovinyl ether, and the crosslinking agent is divinylethyleneurea (1,3-divinylimidazolin-2-one) or divinylpropyleneurea (1,3-divinyltetrahydropyrimidin-2-one).

### Claim 27 (depends on 21)

A polymer according to claim 21, wherein R4 in formula I is a straight-chain or branched C1 to C10 alkyl radical, in which one or more non-adjacent methylene groups may be replaced by O, C═O, S, S═O, SO2, NH, NOH, or N and/or in which one or more H atoms may be substituted, independently of one another, by C1-C6-alkyl, C5-C10-aryl, halogen, NH2, NH(C1-C8)alkyl, N(C1-C8)alkyl2, C1-C6-alkoxy or C1-C6-alkyl-OH and in which at least one OH group is present either on the C1 to C10 alkyl radical or on a substituent, or
a cycloaliphatic radical having 5 to 10 C atoms, in which one or more non-adjacent methylene groups may be replaced by O, C═O, S, S═O, SO2, NH, NOH, or N and/or in which one or more H atoms of the cycloaliphatic radical may be substituted, independently of one another, by C1-C6-alkyl, C5-C10-aryl, halogen, NH2, NH(C1-C8)alkyl, N(C1-C8)alkyl2, C1-C6-alkoxy or C1-C6-alkyl-OH, where at least one OH group is present either on the cycloaliphatic ring or on a side chain or substituent, or
a C6 to C18 aryl radical, where one or more H atoms in the aryl radical may be substituted, independently of one another, by hydroxyl, C1-C6-alkyl, C5-C10-aryl, halogen, NH2, NH(C1-C8)alkyl, N(C1-C8)alkyl2, C1-C6-alkoxy or C1-C6-alkyl-OH, where at least one OH group is present either on the aryl radical or on a side chain or substituent, or
a C5 to C18 heteroaryl radical, where one or more H atoms in the heteroaryl radical may be substituted, independently of one another, by hydroxyl, C1-C6-alkyl, C5-C10-aryl, halogen, NH2, NH(C1-C8)alkyl, N(C1-C8)alkyl2, C1-C6-alkoxy or C1-C6-alkyl-OH, where at least one OH group is present either on the heteroaryl radical or on a side chain or substituent.

### Claim 28 (depends on 21)

A polymer according to claim 21, wherein b) is a crosslinking agent of formula III.

### Claim 29

A process for preparing a polymer, which is in the form of polymeric particles, comprising copolymerizing at least one hydrophilically substituted alkyl vinyl ether of the formula I and at least one crosslinking agent of formula II and/or III and/or IV to form said polymeric particles
where
R1, R2, R3, independently of one another, are H or C1 to C6 alkyl, and
R4 is a radical which carries at least one hydroxyl group,
and
where
X is a divalent alkyl radical having 2 to 5 C atoms in which one or more methylene groups which are not adjacent and are not located in the direct vicinity of N may be replaced by O, C═O, S, S═O, SO2, NH, NOH or N and one or more H atoms of the methylene groups may be substituted, independently of one another, by hydroxyl, C1-C6-alkyl, halogen, NH2, C5-C10-aryl, NH—(C1-C8)-alkyl, N—(C1-C8)-alkyl2, C1-C6-alkoxy or C1-C6-alkyl-OH,
where
Y1 and Y2 in formula III and IV
are, independently of one another, C1 to C10 alkyl or cycloalkyl, where one or more non-adjacent methylene groups or methylene groups which are not located in the direct vicinity of N may be replaced by O, C═O, S, S═O, SO2, NH, NOH or N and one or more H of the methylene groups may be substituted, independently of one another, by hydroxyl, C1-C6-alkyl, halogen, NH2, C5-C10-aryl, NH(C1-C8)alkyl, N(C1-C8)alkyl2, C1-C6-alkoxy or C1-C6-alkyl-OH, or
C6 to C18 aryl, where one or more H in the aryl system may be substituted, independently of one another, by hydroxyl, C1-C6-alkyl, halogen, NH2, NH(C1-C8)alkyl, N(C1-C8)alkyl2, C1-C6-alkoxy or C1-C6-alkyl-OH, and
A is a divalent alkyl radical having 2 to 5 C atoms in which one or more non-adjacent methylene groups or methylene groups which are not located in the direct vicinity of N may be replaced by O, C═O, S, S═O, SO2, NH, NOH or N and one or more H of the methylene groups may be substituted, independently of one another, by hydroxyl, C1-C6-alkyl, halogen, NH2, C5-C10-aryl, NH(C1-C8)alkyl, N(C1-C8)alkyl2, C1-C6-alkoxy or C1-C6-alkyl-OH.

### Claim 30 (depends on 29)

A process according to claim 29, wherein in the compound of formula I, R4 is a straight-chain or branched C1 to C10 alkyl radical, in which one or more non-adjacent methylene groups may be replaced by O, C═O, S, S═O, SO2, NH, NOH, or N and/or in which one or more H atoms may be substituted, independently of one another, by C1-C6-alkyl, C5-C10-aryl, halogen, NH2, NH(C1-C8)alkyl, N(C1-C8)alkyl2, C1-C6-alkoxy or C1-C6-alkyl-OH and in which at least one OH group is present either on the C1 to C10 alkyl radical or on a substituent, or a cycloaliphatic radical, in which one or more non-adjacent methylene groups may be replaced by O, C═O, S, S═O, SO2, NH, NOH, or N and/or in which one or more H atoms of the cycloaliphatic radical may be substituted, independently of one another, by C1-C6-alkyl, C5-C10-aryl, halogen, NH2, NH(C1-C8)alkyl, N(C1-C8)alkyl2, C1-C6-alkoxy or C1-C6-alkyl-OH, where at least one OH group is present either on the cycloaliphatic ring or on a side chain or substituent, or
a C6 to C18 aryl radical, where one or more H atoms in the aryl radical may be substituted, independently of one another, by hydroxyl, C1-C6-alkyl, C5-C10-aryl, halogen, NH2, NH(C1-C8)alkyl, N(C1-C8)alkyl2, C1-C6-alkoxy or C1-C6-alkyl-OH, where at least one OH group is present either on the aryl radical or on a side chain or substituent, or
a C5 to C18 heteroaryl radical, where one or more H atoms in the heteroaryl radical may be substituted, independently of one another, by hydroxyl, C1-C6-alkyl, C5-C10-aryl, halogen, NH2, NH(C1-C8)alkyl, N(C1-C8)alkyl2, C1-C6-alkoxy or C1-C6-alkyl-OH, where at least one OH group is present either on the heteroaryl radical or on a side chain or substituent.

### Claim 31 (depends on 29)

A process according to claim 29, wherein the temperature during the polymerisation is between 40 and 100° C.

### Claim 32 (depends on 29)

A process according to claim 29, wherein hydrophilically substituted alkyl vinyl ethers and crosslinking agents are in a weight ratio between 10:90 and 80:20.

### Claim 33 (depends on 1)

In a method for solid-phase synthesis of a biopolymer, such as a nucleic acid or peptide, wherein the improvement is to perform said solid-phase synthesis on a polymer according to claim 1.