Sulphated ion exchanger and method for preparation thereof

• US 4,178,439 A
• Filed: 03/01/1977
• Issued: 12/11/1979
• Est. Priority Date: 03/04/1976
• Status: Expired due to Term

• Current Assignee: Development Finance Corporation Of New Zealand
• Original Assignee: Development Finance Corporation Of New Zealand
• Inventors: Ayers, John S., Husbands, David R.
• Primary Examiner(s): Griffin, Ronald W.
• Application Number:
  US05/773,269
• Time in Patent Office: 1,015 Days
• Field of Search: 260/2.1 R, 260/2.2 R, 536/59, 536/57, 536/92, 536/106, 536/1, 536/112, 536/3
• US Class Current: 536/59
• CPC Class Codes: B01J 39/22 Cellulose or wood; Derivatives thereof
• CPC Class Codes: C08B 15/005 Crosslinking of cellulose derivatives
• CPC Class Codes: C08B 37/00 Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof cellulose D21; microbiological processes C12P
• CPC Class Codes: C08B 5/14 Cellulose sulfate

Abstract

The invention relates to a novel sulphated cationic ion exchanger and to a method for preparation thereof. In addition it relates to a method of improving the capacity of an exchange matrix to receive sulphated groups. Although the general attraction of sulphate groups to proteins is known we have found that sulphated ion exchangers selectively bind lipoproteins in blood serum or plasma under suitable conditions. We have also discovered that when hydroxyalkyl groups are introduced into the ion exchanger matrix its capacity for taking up sulphate groups is unexpectedly increased. A method of use of the ion exchanger is also described.

Claims

1. A cationic ion exchanger comprising a water insoluble hydrophilic, water swellable matrix;

a plurality of sulphate groups chemically bonded to said matrix, the ion exchange capacity of said exchanger being provided by said sulphate groups;

said matrix being a member selected from the group consisting of;

(a) a cross-linked carbohydrate, and,

(b) a cross-linked carbohydrate having a plurality of hydroxy C_a -C₄ alkyl groups chemically bonded thereto.

2. The ion exchanger according to claim 1 wherein the degree of sulphation is at least 0.5 meq/g.

3. The ion exchanger according to claim 1 wherein said matrix is regenerated cellulose cross-linked with at least 50% epichlorohydrin expressed as volume epichlorohydrin to weight of cellulose.

4. The ion exchanger according to claim 3 wherein said matrix is regenerated cellulose cross-linked with at least 5% volume of epichlorohydrin to weight cellulose, there being present hydroxypropyl groups introduced by at least 30% propylene oxide expressed as volume propylene oxide added to weight of cellulose matrix.

5. The ion exchanger according to claim 1 wherein said cross-linked carbohydrate is a member selected from the group consisting of an unsubstituted cross-linked polysaccharide, an unsubstituted hydroxyl containing derivative thereof, a cross-linked polysaccharide substituted with a plurality of hydroxy C₂ -C₄ alkyl groups and hydroxyl containing polysaccharide derivative substituted with a plurality of hydroxy C₂ -C₄ alkyl groups.

6. The ion exchanger according to claim 5 wherein said cross-linked polysaccharide is a member selected from the group consisting of unsubstituted cross-linked cellulose in any one of its native fibrous, microgranular, microcrystalline or regenerated forms, and a cross-linked cellulose in any one of its native fibrous, microgranular, microcrystalline or regenerated forms substituted with a plurality of hydroxy C₂ -C₄ alkyl groups.

7. The ion exchanger according to claim 6 wherein said matrix is microgranular or microcrystalline cellulose cross-linked with less than 25% of epichlorohydrin expressed as volume epichlorohydrin to weight of cellulose.

8. The ion exchanger according to claim 7 wherein said microgranular or microcrystalline cellulose is cross-linked with from 5-10% of epichlorohydrin expressed as volume epichlorohydrin to weight of cellulose.

9. The ion exchanger according to claim 1 wherein said cross-linked carbohydrate matrix is substituted to a degree of substitution produced by reaction of at least 20% volume of hydroxyalkylating agent to weight of the matrix.

10. A process for the preparation of a cationic ion exchanger which comprises the steps of:

hydroxy C₂ -C₄ alkylating a water insoluble, hydrophilic water swellable cross-linked cellulose selected from the group consisting of native fibrous, microgranular, microcrystalline and regenerated cellulose, said cellulose being further selected from the group consisting of unsubstituted cellulose and cellulose substituted by hydroxy C₂ -C₄ alkyl groups; and

sulphating the product of step 1.

11. The method according to claim 10 wherein said matrix is hydroxy alkylated by the addition of propylene oxide.

12. The method according to claim 10 wherein said sulphating agent is either the reaction product of sulphur trioxide and a Lewis Base or the reaction product of chlorosulphonic acid and a Lewis base.

13. A method to claim 12 wherein said sulphating agent is a pyridine sulphur trioxide complex.

14. The method according to claim 12 wherein said sulphating is conducted in dimethylformamide or formamide at a temperature of between 0°

and 60°

C. for from 0.5 to 6 hours, there being from 2 to 20 millimoles sulphating agent per gram of matrix and 5-25 ml of dimethylformamide or formamide per gram of matrix.

15. The method according to claim 12 wherein said sulphating is conducted in pyridine at a temperature of between 50°

and 90°

C. for from 0.5 to 6 hours, there being from 2 to 20 millimoles sulphating agent per gram of matrix and 5-25 ml of pyridine per gram of matrix.

16. The method according to claim 10 wherein said matrix is preswollen for from 0 to 16 hours prior to the addition of a sulphating agent.