Modified polysaccharide supports

• US 4,663,163 A
• Filed: 02/02/1984
• Issued: 05/05/1987
• Est. Priority Date: 02/14/1983
• Status: Expired due to Term

• Current Assignee: Specialty Minerals Incorporated (Minerals Technologies Incorporated)
• Original Assignee: Specialty Minerals Incorporated (Minerals Technologies Incorporated)
• Inventors: Hou, Kenneth C., Liao, Tung-Ping D.
• Primary Examiner(s): Rosen, Sam
• Application Number:
  US06/576,448
• Time in Patent Office: 1,188 Days
• Field of Search: 527/300, 527/312, 527/313, 527/315, 435/178, 435/179, 502/402, 502/403, 502/404, 424/101
• US Class Current: 210/645
• CPC Class Codes: B01J 20/28028 Particles immobilised within fibres or filaments
• CPC Class Codes: B01J 20/28033 Membrane, sheet, cloth, pad, lamellar or mat
• CPC Class Codes: B01J 20/28052 Several layers of identical or different sorbents stacked in a housing, e.g. in a column
• 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 20/3278 Polymers being grafted on the carrier
• CPC Class Codes: B01J 20/328 Polymers on the carrier being further modified
• CPC Class Codes: B01J 20/3282 Crosslinked polymers
• CPC Class Codes: B01J 39/22 Cellulose or wood; Derivatives thereof
• CPC Class Codes: B01J 39/26 Cation exchangers for chromatographic processes
• CPC Class Codes: B01J 41/16 Cellulose or wood; Derivatives thereof
• CPC Class Codes: B01J 41/20 Anion exchangers for chromatographic processes
• CPC Class Codes: B01J 47/127 in the form of filaments or fibres
• CPC Class Codes: C08F 251/00 Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
• CPC Class Codes: C08G 81/02 at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
• CPC Class Codes: G01N 2030/386 Radial chromatography, i.e. with mobile phase traversing radially the stationary phase
• CPC Class Codes: G01N 30/6091 Cartridges

Abstract

A modified polysaccharide material which comprises: (1) polysaccharide covalently bonded to a synthetic polymer; (2) the synthetic polymer being made from (a) a polymerizable compound which is capable of being covalently coupled directly or indirectly to said polysaccharide, and (b) one or more polymerizable compounds containing (i) an ionizable chemcial group, (ii) a chemical group capable of transformation to an ionizable chemical group, (iii) a chemical group capable of causing the covalent coupling of the compound (b) to an affinity ligand or a biologically active molecule or (iv) a hydrophobic compound.

Claims

1. A modified polysaccharide material which comprises:

(1) a water insoluble polysaccharide covalently bonded to a synthetic polymer

(2) said synthetic polymer comprising a copolymer made from a free-radical polymerization of

(a) a polymerizable compound containing an epoxy group capable of direct covalent coupling to a hydroxy group of said polysaccharide and a vinyl group, capable of free-radical polymerization; and

(b) a polymerizable compound having the formula ##STR11## wherein R is an alpha, beta-unsaturated polymerizable radical, R'"'"' and R" are the same or different C₁ -C₆ alkyl or alkanoyl groups, and R"'"'"' is a direct bond or a C₂ -C₃ alkyl group, wherein R'"'"' and R" taken together with the N atom may form a heterocyclic ring.

2. The material of claim 1 wherein said polysaccharide is cellulose.

3. The material of claim 1 wherein the amount of said compound (a) in said synthetic polymer is sufficient to cause substantial covalent coupling of the polymer to said polysaccharide, yet insufficient to cause substantial loss of porosity of the modified polysaccharide.

4. The material of claim 3 wherein said polymer contains more of said compound (b) than of said compound (a).

5. The material of claim 4 wherein the ratio of said compound (b) to said compound (a) is about 88-96% by weight of (b) to 4-12% by weight of (a).

6. The material of claim 1 wherein said polymer is crosslinked and said crosslinking is provided by means of bifunctional reagents capable of reacting with at least two nitrogen atoms of said polymerizable compound (b) per reagent.

7. The material of claim 6 wherein said reagent is ##STR12## where Hal is a halogen atom, or ##STR13## and n is 2 to 12.

8. A self-supporting cellulosic fibrous matrix which comprises the material of claim 1.

9. The matrix of claim 8 which also comprises highly refined cellulose pulp with a Canadian Standard Freeness of between +100 to -600 ml.

10. The matrix of claim 8 which also comprises a particulate material.

11. The matrix of claim 8 which is in the form of a sheet.

12. A process for preparing the modified polysaccharide material of claim 1 which comprises:

(1) polymerizing said compound (a), with said compound (b) in the presence of said polysaccharide, under temperature conditions insufficient to cause the covalent binding of said compound (a) to said polysaccharide, to thereby form a synthetic polymer of (a) and (b); and

(2) reacting said polysaccharide with the chemical group of compound (a) in said synthetic polymer under temperature conditions sufficient to cause said covalent bonding.

13. The process of claim 12 wherein said step (2) is carried out at a temperature which is higher than that used for step (1).

14. The process of claim 12 wherein said compound (a) carries nitrogen atom-containing groups and which further comprises the step of cross-linking said synthetic polymer with a bifunctional cross-linking reagent capable of reacting with at least two nitrogen atoms per reagent.

15. A chromatography column for effecting chromatographic separation of at least two components of a sample flowing therethrough comprising:

at least one solid stationary phase, said phase having chromatographic functionality and being effective for chromatographic separation;

a means for distributing the sample through the stationary phase;

wherein the stationary phase comprises;

(a) a plurality of layers of sheets of swellable fibrous matrix having chromatographic functionality and being effective for chromatographic separation; and

(b) a spacer means between each layer for permitting controlled swelling thereof and enhancing the distribution of sample flowing through the stationary phase, and further wherein the swellable fibrous matrix in sheet form comprises a modified cellulose material, said modified cellulose material comprising the material of claim 2.

16. A modified polysaccharide material according to claim 1, wherein said synthetic polymer comprises a copolymer of diethylaminoethyl methacrylate and glycidyl methacrylate.

17. The modified polysaccharide material of claim 1 wherein said copolymer is quaternized with a quaternizing agent selected from the group consisting of 1-chloro-2-propanol;

1,2,-dichloro-2-propanol;

methyl chloroacetate;

chloroethyldiethylamine; and

ethyl iodide.

18. The modified polysaccharide material of claim 1 wherein compound (a) is selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, 4,5 epoxypentylacrylate, 4-(2,3)-epoxypropyl-N-butyl-methacrylate, 9,10-epoxysteoryl acrylate, 4-(2,3-epoxypropyl)-cyclohexyl methacrylate, allyl glycidyl ether and ethylene glycol-monoglycidyl-etheracrylate.

20. A method of fractionating plasma comprising passing said plasma through the chromatographic column of claim 15.

21. The method of claim 20 wherein the synthetic polymer is a copolymer of dimethylaminoethyl methacrylate and glydicyl methacrylate.

19. The process of claim 56 wherein said bifunctional cross-linking agent is selected from ##STR14## where Hal is halogen atom, or ##STR15## and n is 2 to 12.

22. A process for effecting chromatographic separation of at least two components of a sample comprising contacting said sample with a self-supporting fibrous matrix comprising a modified polysaccharide material, said modified polysaccharide material comprising:

(1) a water insoluble polysaccharide covalently bonded to a synthetic polymer;

(2) said synthetic polymer comprising a copolymer made from a free-radical polymerization of

(a) a polymerizable compound containing an epoxy group capable of direct covalent coupling to a hydroxy group of said polysaccharide and a vinyl group, capable of free-radical polymerization; and

(b) a polymerizable compound having the formula ##STR16## wherein R is an alpha, beta-ethylenically unsaturated polymerizable radical, R'"'"' and R" are the same or different C₁ -C₆ alkyl or alkanoyl groups, and R"'"'"' is a direct bond or a C₂ -C₃ alkyl group, wherein R'"'"' and R", taken together with the N atom may form a heterocyclic ring.

23. The process of claim 22, wherein compound (a) is selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, 4,5 epoxypentylacrylate, 4-(2,3)-epoxypropyl-N-butyl-methacrylate, 9,10-epoxysteoryl acrylate, 4-(2,3-epoxypropyl)-cyclohexyl methacrylate, allyl glycidyl ether and ethylene glycol-monoglycidyl-etheracrylate.

24. The process according to claim 22, wherein said synthetic polymer comprises a copolymer of diethylaminoethyl methacrylate and glycidyl methacrylate.

25. The process according to claim 24, wherein said copolymer of glycidyl methacrylate and diethylaminoethyl methacrylate is in its quaternized form.

26. The process according to claim 25, wherein said copolymer is quaternized with a quaternizing agent selected from the group consisting of 1-chloro-2-propanol;

1,2,-dichloro-2-propanol;

methyl chloroacetate;

chloroethyldiethylamine; and

ethyl iodide.