Method for purifying polyethylene glycol having one amino group

• US 9,458,292 B2
• Filed: 03/24/2014
• Issued: 10/04/2016
• Est. Priority Date: 03/27/2013
• Status: Active Grant

• Current Assignee: NOF Corporation
• Original Assignee: NOF Corporation
• Inventors: Kimura, Shingo, Yoshioka, Hiroki, Hirai, Midori
• Primary Examiner(s): Kumar, Shailendra
• Application Number:
  US14/780,310
• Publication Number:
  US 20160046762A1
• Time in Patent Office: 925 Days
• US Class Current: 1/1
• CPC Class Codes: C08G 65/30 Post-polymerisation treatment, e.g. recovery, purification, drying
• CPC Class Codes: C08G 65/333 containing nitrogen
• CPC Class Codes: C08G 65/34 from hydroxy compounds or their metallic derivatives C08G65/26 takes precedence

Abstract

A method for purifying a polyethylene glycol compound having one amino group, which includes (A) preparing an aqueous solution of the compound having a pH of 1 to 5, (B) an extracting step of mixing the aqueous solution with a mixed organic solvent to cause layer separation into organic and aqueous layers, wherein a ratio of an organic solvent I is 25 to 65% by mass and a ratio of an organic solvent II is 75 to 35% by mass, the organic solvent I is selected from an aromatic hydrocarbon and an ester, the organic solvent II is a halogenated hydrocarbon, and a mixing ratio Y of I to II, temperature T (° C.) at mixing, and molecular weight M of the compound satisfy the following relationship:
1.9×10⁻⁶M+0.09≦Y−0.015T≦−1.4×10⁻⁶M+0.44
and (C) recovering the compound from the aqueous layer.

Claims

1. A method for purifying a polyethylene glycol compound having one amino group and having a total average molar number of ethylene oxide units added in a molecule thereof of 20 to 2300,

the method comprising the following steps (A), (B) and (C):

(A) a step of preparing an aqueous solution of the polyethylene glycol compound having one amino group, the solution having a pH of 1 to 5,

(B) an extraction step of mixing the aqueous solution obtained in the step (A) with a mixed organic solvent at a temperature of 10°

C. or higher and 55°

C. or lower and causing layer separation into an organic layer and an aqueous layer, wherein a ratio of an organic solvent I is 25 to 65% by mass and a ratio of an organic solvent II is 75 to 35% by mass in the mixed organic solvent, the organic solvent I is selected from an aromatic hydrocarbon-based solvent having a total carbon number of 8 or less and an ester compound solvent containing no hetero atom and having a total carbon number of 5 or less, the organic solvent II is a halogenated hydrocarbon-based solvent, and a mixing ratio Y of the organic solvent I to the organic solvent II (organic solvent I/organic solvent II), temperature T (°

C.) at the mixing, and molecular weight M of the polyethylene glycol compound satisfy the following relationship;

1.9×

10<sup>−

6</sup>M+0.09Y−

0.015T≦

−

1.4×

10<sup>−

6</sup>M+0.44,

and

(C) a step of recovering the polyethylene glycol compound from the aqueous layer.

2. The method according to claim 1, wherein, in the step (B), the mixing ratio Y of the organic solvent I to the organic solvent II (organic solvent I/organic solvent II), the temperature T (°

C.) at the mixing, and the molecular weight M of the polyethylene glycol compound satisfy the following relationship;

1.0×

10<sup>−

6</sup>M+0.19≦

Y−

0.015T≦

−

1.4×

10<sup>−

6</sup>M+0.44.

3. The method according to claim 1, wherein the extraction step (B) is repeated one or more times for the aqueous layer separated in the step (B).

4. The method according to claim 1, wherein the aqueous solution contains an acidic reagent selected from the group consisting of hydrochloric acid, phosphoric acid, and trifluoroacetic acid, in the step (A).

5. The method according to claim 1, wherein the organic solvent I is selected from the group consisting of toluene and ethyl acetate.

6. The method according to claim 1, wherein the organic solvent II is chloroform.

7. The method according to claim 1, wherein a mass of the organic solvent I and a mass of the organic solvent II in the step (B) are each 1 to 50 times a mass of the polyethylene glycol compound and a mass of the water contained in the aqueous solution in the step (A) is 1 to 50 times the mass of the polyethylene glycol compound.

8. The method according to claim 1, wherein after the aqueous layer is made neutral or alkaline, the polyethylene glycol is recovered by concentration, crystallization or drying via extraction into an organic layer, in the step (C).

9. The method according to claim 1, wherein the total average molar number of ethylene oxide units added in the polyethylene glycol compound molecule is 40 to 2050.

10. The method according to claim 2, wherein the extraction step (B) is repeated one or more times for the aqueous layer separated in the step (B).

11. The method according to claim 2, wherein the aqueous solution contains an acidic reagent selected from the group consisting of hydrochloric acid, phosphoric acid, and trifluoroacetic acid, in the step (A).

12. The method according to claim 2, wherein the organic solvent I is selected from the group consisting of toluene and ethyl acetate.

13. The method according to claim 2, wherein the organic solvent II is chloroform.

14. The method according to claim 2, wherein a mass of the organic solvent I and a mass of the organic solvent II in the step (B) are each 1 to 50 times a mass of the polyethylene glycol compound and a mass of the water contained in the aqueous solution in the step (A) is 1 to 50 times the mass of the polyethylene glycol compound.

15. The method according to claim 2, wherein after the aqueous layer is made neutral or alkaline, the polyethylene glycol is recovered by concentration, crystallization or drying via extraction into an organic layer, in the step (C).

16. The method according to claim 2, wherein the total average molar number of ethylene oxide units added in the polyethylene glycol compound molecule is 40 to 2050.