Integral asymmetric polyether-sulfone membrane, process for its production, and use for ultrafiltration and microfiltration

• US 4,976,859 A
• Filed: 09/01/1989
• Issued: 12/11/1990
• Est. Priority Date: 09/01/1988
• Status: Expired due to Term

• Current Assignee: Membrana GmbH (Asahi Kasei Corporation)
• Original Assignee: Akzo Nobel N.V. (Nouryon BV)
• Inventors: Wechs, Friedbert
• Primary Examiner(s): Sever, Frank
• Application Number:
  US07/401,859
• Time in Patent Office: 466 Days
• Field of Search: 210/651, 210/500.41, 210/500.23, 264/41, 264/45.1, 264/45.5, 264/DIG. 48, 264/DIG. 62
• US Class Current: 210/500.23
• CPC Class Codes: B01D 69/00 Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
• CPC Class Codes: B01D 71/68 Polysulfones; Polyethersulfones
• CPC Class Codes: C08J 2381/06 Polysulfones; Polyethersulfones
• CPC Class Codes: C08J 3/091 characterised by the chemical constitution of the organic liquid

Abstract

An integral polyether-sulfone membrane with a pore system open at the outer boundaries is in the form of flat films, tubular films or hollow fibers having a maximum pore diameter of 0.02 μm to 2 μm. The pore system is cellular throughout with cells having polyhedrally symmetrical boundaries. The cells are arranged asymmetrically from one surface of the membrane to the other, the asymmetry factor AF relative to the maximum pore diameter being 0.01 to 2.0. The ratio of the maximum mean free path length of the flow path to the diameter of the largest pore is greater than 3. The cell size changes steadily from one surface to the other surface. The membrane is produced by dissolving 12 to 35% by weight, relative to the total solution, of polyethersulfone in a mixture of 15 to 65% by weight of ε-caprolactam, 0 to 85% by weight of latent solvent, 0 to 15% by weight of thickener and 0 to 50% by weight of non-solvent, and if appropriate up to 1% by weight of auxiliaries, forming the solution into flat films, tubular films or hollow fibers (the latter preferably with the aid of an internal fluid), and transformation into the solid phase and removal of the mixture forming the solvent. The membrane may be used for ultrafiltration and microfiltration.

Claims

1. An integral polyether-sulfone membrane having properties sufficient for allowing a flow of fluid therethrough which is largely independent of membrane thickness, said membrane having two surfaces and comprising a pore diameter of 0.02μ

m to 2 μ

m, measured by the blow point method, wherein the pore system is cellular throughout with cells having polyhedrally symmetrical boundaries and the cells being arranged asymmetrically from one surface of the membrane to the other surface, as asymmetry factor AF relative to the maximum pore diameter being 0.01 to 2.0, and a ratio of a maximum mean free path length of a flow path to a diameter of the largest pore being greater than 3, and a cell size changing steadily from one surface to the other surface.

2. A membrane as claimed in claim 1 in the form of a flat film, tubular film or hollow fiber.

3. A membrane as claimed in claim 1, wherein the ratio of the maximum mean free path length of the flow path to the diameter of the largest pore is 5-100.

4. A membrane as claimed in claim 1, said membrane having been formed from a mixture containing at least 15% by weight of ε

-caprolactam.

5. A membrane as claimed in claim 1, wherein passages between adjacent cells are rounded.

6. A membrane as claimed in claim 1, wherein additives conferring a hydrophillic character have been added during membrane formation.

7. A membrane as claimed in claim 1, wherein the polyether-sulfone is at least partially sulfonated.

8. A membrane as claimed in claim 1, wherein the maximum pore diameter is 0.05 to 0.5 μ

m.

9. A process comprising producing a polyethersulfone membrane, having properties sufficient for allowing a flow of fluid therethrough which is largely independent of membrane thickness, by dissolving 12 to 35% by weight, relative to a total solution, of polyethersulfone in a mixture of 15 to 65% by weight of ε

-caprolactam, 0 to 85% by weight of latent solvent, 0 to 15% by weight of thickener and 0 to 5% by weight of non-solvent, and a 0 to 1% by weight of auxiliaries, each relative to the mixture;

forming a resultant solution into flat films, tubular films or hollow fibers;

transforming said films or fibers into a solid phase; and

removing the mixture forming solvent.

10. The process as claimed in claim 9, wherein said hollow fibers are formed with the aid of an internal fluid.

11. The process as claimed in claim 9, wherein the dissolution of the polyether-sulfone is carried out at temperatures from 60°

to 140°

C.

12. The process as claimed in claim 9, wherein, relative to the total solution, 15 to 25% by weight of polyethersulfone is dissolved in a mixture containing 40 to 60% by weight of ε

-caprolactam.

13. The process as claimed in claim 9, wherein the transformation into the solid phase is effected by spontaneous crystallization of the solvent mixture after supercooling.

14. The process as claimed in claim 9, wherein the transformation into the solid phase is effected by coagulation in a non-solvent bath, the temperature of the solution and the temperature of the non-solvent bath being 40°

to 60°

C.

15. The process as claimed in claim 9, wherein the membrane is heat-treated for at least one hour at temperatures of 170°

-210°

C.

16. A membrane formed by the process of claim 9.

17. A membrane as claimed in claim 16, said membrane being in the form of an ultrafiltration membrane.

18. A membrane as claimed in claim 16, said membrane being in the form of a microfiltration membrane.

19. An integral polyether-sulfone membrane having properties sufficient for allowing a flow of fluid therethrough which is largely independent of membrane thickness, said membrane having two surfaces and comprising a pore system open at the outer boundaries, the pore system being cellular throughout with cells having polyhedrally symmetrical boundaries and the cells being arranged asymmetrically from one surface of the membrane to the other surface,

said membrane having been formed from a mixture comprising ε

-caprolactam.

20. A membrane as claimed in claim 19 in the form of a flat film, tubular film or hollow fiber.