Hollow fiber membranes and method of manufacture

• US 5,683,584 A
• Filed: 05/18/1995
• Issued: 11/04/1997
• Est. Priority Date: 04/12/1991
• Status: Expired due to Term

• Current Assignee: Medivators, Inc. (Steris PLC)
• Original Assignee: Minntech Corporation
• Inventors: Andrus, Robert G., Cosentino, Louis C., Hall, Robert T. II, Wenthold, Randal M.
• Primary Examiner(s): FORTUNA, ANA M
• Application Number:
  US08/443,482
• Time in Patent Office: 901 Days
• Field of Search: 210/500.39, 210/490, 210/651, 210/500.23, 264/41, 264/49
• US Class Current: 210/500.23
• CPC Class Codes: A61M 1/1672 using membrane filters, e.g. for sterilising the dialysate
• CPC Class Codes: B01D 2323/12 Specific ratios of components used
• CPC Class Codes: B01D 2325/022 Asymmetric membranes
• CPC Class Codes: B01D 61/30 Accessories; Auxiliary operation
• CPC Class Codes: B01D 67/0011 Casting solutions therefor
• CPC Class Codes: B01D 69/02 characterised by their properties
• CPC Class Codes: B01D 69/08 Hollow fibre membranes manufacture of hollow fibres D01D5/24, D01F1/08
• CPC Class Codes: B01D 69/085 Details relating to the spinneret
• CPC Class Codes: B01D 71/64 Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: B01D 71/68 Polysulfones; Polyethersulfones
• CPC Class Codes: B29C 48/0012 combined with shaping by internal pressure generated in the material, e.g. foaming
• CPC Class Codes: B29C 48/0015 producing hollow articles having components brought in contact outside the extrusion die
• CPC Class Codes: B29C 48/0018 combined with shaping by orienting, stretching or shrinking, e.g. film blowing B29C48/0017 takes precedence
• CPC Class Codes: B29C 48/05 Filamentary, e.g. strands
• CPC Class Codes: B29C 48/09 Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
• CPC Class Codes: B29C 48/10 flexible, e.g. blown foils
• CPC Class Codes: B29C 48/21 the layers being joined at their surfaces
• CPC Class Codes: B29K 2039/06 Polymers of N-vinyl-pyrrolidones
• CPC Class Codes: B29K 2081/06 PSU, i.e. polysulfones; PES, i.e. polyethersulfones or derivatives thereof
• CPC Class Codes: B29K 2105/0073 Solution
• CPC Class Codes: B29K 2105/04 : cellular or porous
• CPC Class Codes: B29L 2023/00 : Tubular articles B29L2024/00 takes precedence ; catheters B29L2031/7542
• CPC Class Codes: B29L 2031/731 : Filamentary material, i.e. comprised of a single element, e.g. filaments, strands, threads, fibres cables B29L2031/707
• CPC Class Codes: B29L 2031/753 : Medical equipment; Accessories therefor bloodbags, medical bags B29L2031/7148; artificial eyes B29L2011/0008
• CPC Class Codes: B29L 2031/755 : Membranes, diaphragms
• CPC Class Codes: D01D 5/24 : with a hollow structure; Spinnerette packs therefor D01D5/38 takes precedence; producing tubes of plastic material B29D; addition of agents forming hollow filaments D01F1/08
• CPC Class Codes: D01F 6/74 : from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles

Abstract

An asymmetric, microporous hollow fiber membrane comprising a polyimide is disclosed. The hollow fiber membrane is chemically inert to aqueous solutions and/or blood, is immediately rewettable after repeated steam and chemical sterilizations, has superior clearance, sieving, and water permeability characteristics and is usable over a wide range of applications such as dialysis and water filtration. Also disclosed is the process for manufacturing the polyimide hollow fiber membrane.

Claims

1. An asymmetric, microporous, hollow fiber membrane comprising a polyimide polymer wherein said polyimide polymer has a molecular weight of about 30,000 daltons to about 125,000 daltons and wherein said hollow fiber membrane has an inner diameter of approximately 280 microns and an outer diameter of approximately 380 microns and a pore size range of approximately 0.001 microns to about 0.5 microns and wherein said hollow fiber membrane is characterized by a uniform sponge structure and the absence of voids.

2. The hollow fiber membrane of claim 1 wherein said polyimide polymer comprises a polymer having the structure:

##STR11## wherein 10% to 90% of the R groups are ##STR12## and the remaining R groups are ##STR13##

3. The hollow fiber membrane of claim 1 wherein said polyimide polymer comprises a polymer having the structure:

##STR14##

4. The hollow fiber membrane of claim 1 wherein said membrane has a water permeability of at least 500 mL/hr/mmHg/m².

5. The hollow fiber membrane of claim 1 wherein said membrane is uniformly porous throughout and wherein said membrane is characterized by the absence of voids.

6. The hollow fiber membrane of claim 1 wherein said fiber can withstand take-up rates in excess of 40 m/min.

7. The hollow fiber membrane of claim 1 wherein said membrane rewets by maintaining a flux of at least 500 mL/hr/mmHg/m² for about six sterilizations and wherein said fiber is further characterized by having 0.0% wetting agent additives selected from the group of hydrophilic polymers, nonionic, anionic, or amphoteric surfactants.

8. The hollow fiber membrane of claim 7 wherein said hydrophilic polymers comprise polyvinylpyrrolidone.

9. A process for the manufacture of an asymmetric, microporous hollow fiber membrane comprising the steps of:

(a) passing, through an outer annular orifice of a tube-in-orifice spinneret, a polymeric solution comprising about 15-25 wt. % of a highly polar polyimide polymer dissolved in a solvent with respect to the polymer, said solution having a viscosity of about 1500-5000 cps, to form an annular liquid;

(b) passing, though the inner tube of the spinneret, into the center of the annular liquid, a precipitating solution comprising about

(I) 99-65 wt. % of a solvent with respect to the polymer, and

(ii) 1-35 wt. % of a non-solvent with respect to the polymer,

wherein the precipitating solution interacts with the polymeric solution to form an annular polymer precipitate;

(c) dropping the polymer precipitate through the atmosphere or an augmented atmosphere at a distance of about 0.5-0.2 meters;

(d) quenching the polymer precipitate in a bath maintained at about 15°

-45°

C. to form a hollow fiber; and

(e) taking up the fiber at a rate of about 40-70 meters/min, wherein said hollow fiber membrane is characterized by uniform sponge structure and the absence of voids.

10. The process of claim 9 wherein said organic solvent is selected from the group consisting of dimethylformamide, dimethylsulfoxide, dimethylacetamide, n-methylpyrrolidone and mixtures thereof.

11. The process of claim 9 wherein said solvent with respect to the polymer comprises dimethylformamide.

12. The process of claim 11 wherein said solvent comprises dimethylformamide.

13. The process of claim 9 wherein said precipitating solution comprises:

(i) 75-90 wt. % of a solvent with respect to the polymer;

(ii) 20-10 wt. % water; and

(iii) 5-0 wt. % additional non-solvent with respect to the polymer.

14. The process of claim 13 wherein said solvent comprises dimethylformamide.

15. The process of claim 13 wherein said non-solvent comprises isopropanol.

16. The process of claim 9 wherein said polyimide polymer comprises a polymer having the structure:

##STR15## wherein 10% to 90% of the R groups are ##STR16## and the remaining R groups include either ##STR17##

17. The process of claim 9 wherein said polyimide polymer comprises a polymer having the structure:

##STR18##

18. The process of claim 9 wherein said precipitating solution comprises about 81 wt. % dimethylformamide and 19 wt. % water.

19. The process of claim 9 wherein said precipitating solution comprises about 85 wt. % dimethylformamide and 15 wt. % water.

20. The process of claim 9 wherein said precipitating solution comprises about 85.5 wt. % dimethylformamide and 14.5 wt. % water.

21. The process of claim 9 wherein said precipitating solution comprises 50 wt. % dimethylformamide and 50 wt. % water.

22. The process of claim 9 wherein said polymeric solution comprises about 15 wt. % of a polyimide polymer, about 80 wt. % dimethylformamide, and 5.0 wt. % glacial acetic acid.

23. The product prepared in accordance with the process of claim 9.

24. A process for the manufacture of an asymmetric, microporous hollow fiber membrane comprising the steps of:

(a) passing, through an outer annular orifice of a tube-in-orifice spinneret, a polymeric solution comprising about 16-18 wt. % of a highly polar polyimide polymer dissolved in a solvent with respect to said polymer, said solution having a viscosity of about 1500-5000 cps, to form an annular liquid;

(b) passing, through the inner tube of the spinneret, into the center of the annular liquid, a precipitating solution comprising about

(i) about 80 wt. % of a solvent with respect to said polymer, and

(ii) about 20 wt. % water,

wherein the precipitating solution interacts with the polymeric solution to form an annular polymer precipitate;

(c) dropping the polymer precipitate through the atmosphere or an augmented atmosphere for about 0.5-2.0 meters;

(d) quenching the polymer precipitate in a bath maintained at about 15°

-45°

C. to form a hollow fiber; and

(e) taking up the fiber at a rate of about 40-70 meters/min;

wherein said fiber membrane is uniformly porous, characterized by the absence of voids, and has a water permeability of at least 500 mL/hr/mmHg/m².

25. The process of claim 24 wherein said polyimide polymer comprises a polymer having the structure:

##STR19## wherein 10% to 90% of the R groups are ##STR20## and the remaining R groups include either ##STR21##

26. The process of claim 24 wherein said polyimide polymer comprises a polymer having the structure:

##STR22##

27. The product prepared in accordance with the process of claim 24.

28. An asymmetric, microporous, hollow fiber membrane comprising a polyimide polymer having the structure:

##STR23## wherein 10% to 90% of the R groups are ##STR24## an the remaining R groups are ##STR25## wherein at a blood flow rate of 200 mL/min, said membrane has a high rate of water permeability of about 17 mL/min/mmHg/m² ;

a high clearance rate of 175-190 mL/min for urea, 150-180 mL/min for creatinine and phosphorous, about 88-125.1 mL/min for Vitamin B₁₂ and about 125-165 mL/min for Cytochrome C; and

high sieving coefficients of from about 0.01 or less for albumin, and from about 0.65 to about 1.0 for myoglobin for fibers having 1.25 m² active surface area; and

wherein said hollow fiber membrane is characterized by a uniform sponge-like structure and the absence of voids.

29. The hollow fiber membrane of claim 28 wherein said fiber can withstand take-up rates in excess of 40 m/min.

30. The hollow fiber membrane of claim 29 wherein said membrane rewets by maintaining a flux of at least 500 mL/hr/mmHg/m² for about six sterilizations and wherein said membrane is further characterized by having 0.0% wetting agent additives selected from the group of hydrophilic polymers, nonionic, anionic, or amphoteric surfactants.

31. The hollow fiber membrane of claim 29 wherein said hydrophilic polymers comprise polyvinylpyrrolidone.