Macroporous hydrogels, their preparation and their use

• US 20090170973A1
• Filed: 05/11/2006
• Published: 07/02/2009
• Est. Priority Date: 05/13/2005
• Status: Abandoned Application

• Current Assignee: Protista Biotechnology AB
• Original Assignee: Protista Biotechnology AB
• Inventors: Savina, Irina, Mattiasson, Bo, Galaev, Igor
• Application Number:
  US11/920,255
• Publication Number:
  US 20090170973A1
• Time in Patent Office: Days
• US Class Current: 521/134
• CPC Class Codes: 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
• 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 20/265 modified or post-treated polymers polymer carriers or substrates subjected to further impregnating or coating B01J20/3208
• CPC Class Codes: B01J 20/267 Cross-linked polymers
• CPC Class Codes: B01J 20/28042 Shaped bodies; Monolithic structures
• CPC Class Codes: B01J 20/28047 Gels
• CPC Class Codes: B01J 20/28085 being more than 50 nm, i.e. macropores
• 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 20/3092 Packing of a container, e.g. packing a cartridge or column of chromatography columns B01D15/206
• CPC Class Codes: B01J 20/321 consisting of a polymer obtained by reactions involving only carbon to carbon unsaturated bonds
• CPC Class Codes: B01J 20/327 Polymers obtained by reactions involving only carbon to carbon unsaturated bonds
• CPC Class Codes: B01J 20/3278 Polymers being grafted on the carrier
• CPC Class Codes: B01J 20/328 Polymers on the carrier being further modified
• 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: C08F 220/06 Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• CPC Class Codes: C08F 261/04 on to polymers of vinyl alcohol
• CPC Class Codes: C08F 265/00 Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
• CPC Class Codes: C08F 265/04 on to polymers of esters
• CPC Class Codes: C08F 265/10 : on to polymers of amides or imides

Abstract

A macroporous cryogen is disclosed which has grafted thereon polymer chains formed by polymerizing at least one monomer of the general formula (I) CR1R2=CR3R4 (I) wherein R1 and R2 are equal of different and each represents a hydrogen atom or substituent group which is not detrimental to the polymerization reaction; and R3 and R4 each represents a hydrogen atom or a substituent group which is not detrimental to the polymerization reaction, provided that R3 and R4 are not both a hydrogen atom, on said macroporous cryogel. A method for the preparation of said macroporous cryogel by graft (co)polymerization and the use of said macroporous cryogel in a separation process are also disclosed.

Claims

1. Macroporous cryogel having grafted thereon polymer chains formed by polymerizing at least one monomer of the general formula (I)

CR₁R₂═

CR₃R₄ 

 

(I)

wherein R₁ and R₂ are equal or different and each represents a hydrogen atom or a substituent group which is not detrimental to the polymerization reaction; and

R₃ and R₄ each represents a hydrogen atom or a substituent group which is not detrimental to the polymerization reaction, provided that R₃ and R₄ are not both a hydrogen atom, on said macroporous cryogel.

2. Macroporous cryogel according to claim 1, wherein R₁ and R₂ are both a hydrogen atom or one of R₁ and R₂ represents a hydrogen atom and the other represents a substituent selected from the group consisting of alcohols, organic acids, ethers, esters amides and N-substituted amides thereof, amines, N-substituted amines, heterocyclic aromatic rings and derivatives thereof.

3. Macroporous cryogel according to claim 1 or claim 2, wherein one of R₃ and R₄ represents a hydrogen atom or an alkyl group and the other is a member selected from the group consisting of a carboxyl group and derivatives such as alcohols, organic acids, ethers, esters, amides and N-substituted amides thereof, amines, N-substituted amines, heterocyclic aromatic rings etc.

4. Macroporous cryogel according to claim 3, wherein said derivative of a carboxyl group is one containing an affinity ligand bound thereto.

5. Macroporous cryogel according to claim 1, wherein said at least one monomer of the general formula (I) is at least one member selected from the group consisting of acrylic acid (AAc), methacrylic acid (MAc), N,N-dimethyl-aminoethylmethacrylate (DMAEMA), (2-(methacryloyloxy)ethyl)-trimethyl ammonium chloride (META), N-isopropylacrylamide (NIPAM), N-vinyl imidazole (VI), glycidylmethacrylate (GMA), hydroxyethyl methacrylate (HEMA), acrylamide, methylene-bis-acrylamide (MBAA) diallyltartaramide (DATAm), diallylacryalamide (DAAm), polyethyleneglycol di(meth)acrylate (PEGD(M)A), polypropylene glycol diglycidyl ether (PEG-DGE), 3-(acrylamido)phenylboronic acid (APBA) and derivatives thereof.

6. Macroporous cryogel according to any of claims 1 to 5, wherein the macroporous cryogel is a cryogel prepared by copolymerizing monomers selected from the group consisting of acrylic acid and derivatives thereof, one of said monomers being an acrylamide.

7. Macroporous cryogel according to claim 6, wherein the macroporous cryogel is a cryogel prepared by radical copolymerization of acrylamide and N,N′

-methylene-bis-acrylamide.

8. Macroporous gel according to claim 1, wherein the macroporous cryogel is a poly(vinyl alcohol) cryogel cross-linked by means of a bifunctional reagent e.g. glutaraldehyde and said at least one monomer of the general formula (I) is a member selected from the group consisting of alcohols, organic acids, ethers, esters amides and N-substituted amides thereof, amines, N-substituted amines, heterocyclic aromatic compounds, all containing a polymerizable double bond.

9. Macroporous cryogel according to any of claims 1-8, which is in the shape of a monolith.

15. The use of a macroporous cryogel as defined in any of claims 1 to 9 in a separation process.

16. Use according to claim 15, wherein said macroporous cryogel is a macroporous polyacrylamide cryogel carrying tertiary and quarternary amino groups prepared by graft polymerization of a monomer selected from the group consisting of N,N-dimethylaminoethyl methacrylate (DMAEMA) and (2-(methacryloyloxy)ethyl)-trimethyl ammonium chloride onto the surface of said polyacrylamide cryogel, and wherein said macroporous cryogel is used for chromatography of RNA and gDNA.

10. Method for graft (co)polymerization of at least one monomer of the general formula (I)

CR₁R₂═

CR₃R₄ 

 

(I)

wherein R₁ and R₂ are equal or different and each represents a hydrogen atom or a substituent group which is not detrimental to the polymerization reaction; and

R₃ and R₄ each represents a hydrogen atom or a substituent group which is not detrimental to the polymerization reaction, provided that R₃ and R₄ are not both a hydrogen atom;

on a macroporous cryogel, which method comprises reacting said at least one monomer of the general formula (I) as defined above with a macroporous polyacrylamide cryogel in the presence of potassium diperiodatocuprate as an initiator.

11. Method according to claim 10, wherein dry macroporous polyacrylamide cryogel is brought in contact with an alkaline aqueous solution of said at least one monomer of the general formula (I) and potassium disperiodatocuprate.

12. Method according to claim 10, wherein dry macroporous polyacrylamide cryogel is saturated with an alkaline aqueous solution of potassium disperiodatocuprate in a column, where after said alkaline aqueous solution is displaced from the cryogel by passing an aqueous or aqueous-organic solution of said at least one monomer of the general formula (I) therethrough whereafter graft (co)polymerization is allowed to proceed.

13. Method according any of claims 10 to 12, wherein the macroporous cryogel thus prepared, having polymer chains grafted thereon, is further reacted with a reagent introducing an affinity ligand thereon.

14. Method for graft polymerization of a monomer selected from the group consisting of acrylamide and acrylic acid on a macroporous cryogel, which method comprises reacting said monomer with a macroporous poly(vinyl alcohol) cryogel in the presence of at least one member selected from the group consisting of initiators and activators for the polymerization reaction.