Microporous and hydrophobic polymeric hollow fiber membranes and methods for preparation thereof

• US 9,908,985 B2
• Filed: 09/11/2013
• Issued: 03/06/2018
• Est. Priority Date: 09/11/2012
• Status: Active Grant

• Current Assignee: Universite Laval
• Original Assignee: Universite Laval
• Inventors: Iliuta, Maria Cornelia, Rodrigue, Denis, Sanaz, Mosadegh Sedghi, Brisson, Jose
• Primary Examiner(s): Greene, Jason M
• Application Number:
  US14/426,814
• Publication Number:
  US 20150240045A1
• Time in Patent Office: 1,637 Days
• CPC Class Codes: B01D 19/0073 by a method not covered by groups B01D19/0005 - B01D19/0042
• CPC Class Codes: B01D 2323/04 Hydrophobization
• CPC Class Codes: B01D 2325/38 Hydrophobic membranes
• CPC Class Codes: B01D 61/00 Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor separation of gases or vapours by diffusion B01D53/22
• CPC Class Codes: B01D 63/02 Hollow fibre modules
• CPC Class Codes: B01D 63/021 Manufacturing thereof
• CPC Class Codes: B01D 67/002 from melts
• CPC Class Codes: B01D 67/003 by selective elimination of components, e.g. by leaching
• 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 69/087 Details relating to the spinning process
• CPC Class Codes: B01D 71/26 Polyalkenes
• CPC Class Codes: B01D 71/261 Polyethylene
• CPC Class Codes: C08J 9/26 by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
• CPC Class Codes: C08L 23/06 Polyethene

Abstract

There is provided a method for preparing microporous hollow fiber membranes comprising melt-extruding a polymer-salt blend followed by salt leaching. Microporous hollow fiber membranes are also disclosed.

Claims

1. A method for preparing a microporous hollow fiber membrane, which comprises:

mixing at least one polymer suitable for melt extrusion with at least one suitable water soluble salt having an average particle size of about 1 to about 20 μ

m under conditions suitable to form a mixture comprising about 60 to about 70% by weight of the at least one suitable water soluble salt based on the total weight of the mixture;

extruding the mixture under conditions suitable to form a hollow fiber membrane comprising the mixture; and

leaching the hollow fiber membrane comprising the mixture in water under conditions suitable for at least substantially removing the salt from the hollow fiber membrane,

said prepared microporous hollow fiber membrane having a water contact angle of about 110 to about 140° and

a porosity of about 40 to about 60%.

2. The method of claim 1, wherein the at least one suitable water soluble salt has an average particle size of about 2 to about 15 μ

m.

3. The method of claim 1, wherein the at least one suitable water soluble salt has an average particle size of about 5 to about 10 μ

m.

4. The method of claim 1, wherein the mixture comprises about 60 to about 68% by weight of the at least one suitable water soluble salt based on the total weight of the mixture.

5. The method of claim 1, wherein the conditions suitable to form the mixture comprise:

mixing the at least one polymer suitable for melt extrusion with the at least one suitable water soluble salt so as to form a physical blend; and

feeding the physical blend into an apparatus suitable for melt blending the at least one polymer suitable for melt extrusion with the at least one suitable water soluble salt to form the mixture.

6. The method of claim 1, wherein the conditions suitable to form a hollow fiber membrane comprise feeding the mixture into an apparatus suitable for melt extruding the mixture through a hollow fiber die.

7. The method of claim 6, wherein the hollow fiber die has an inside diameter of about 1 mm to about 10 mm, and an outside diameter of about 1.5 mm to about 11 mm.

8. The method of claim 1, wherein the conditions suitable for at least substantially removing the salt from the hollow fiber membrane comprise leaching the hollow fiber membrane with water in a vessel at a temperature suitable for weakening the mechanical properties of the at least one polymer suitable for melt extrusion, for a time of about 120 min to about 200 min.

9. The method of claim 1, wherein the polymer suitable for melt extrusion is chosen from thermoplastic melt-processable polymers, thermoplastic melt-processable copolymers, thermoplastic melt-processable elastomers, thermoplastic melt-processable composites, heat-curable thermoset polymers, heat-curable thermoset copolymers, heat-curable thermoset elastomers and heat-curable thermoset composites.

10. The method of claim 1, wherein the polymer suitable for melt extrusion is chosen from polyolefins, polyolefin composites, vinyl polymers, polyacrilonitriles, polystyrene, polyesters, polyurethanes, nylons, and polyethersulfones.

11. The method of claim 1, wherein the polymer suitable for melt extrusion is low density polyethylene (LDPE).

12. The method of claim 11, wherein the LDPE has a density of about 910 kg/m³ to about 925 kg/m³.

13. The method of claim 12, wherein the LDPE has a melt index of about 0.8 g/10 min to about 7.5 g/10 min.

14. The method of claim 13, wherein the hollow fiber membrane is leached with water at a temperature of about 10°

C. to about 60°

C.

15. The method of claim 5, wherein the suitable water soluble salt is sodium chloride.

16. The method of claim 1, wherein the suitable water soluble salts is chosen from alkali metal salts and alkaline-earth metal salts.

17. The method of claim 1, wherein the suitable water soluble salts is chosen from alkali metal chlorides, alkali metal bromides, alkali metal iodides, alkali metal fluorides, alkali metal acetates, alkali metal carbonates, alkali metal phosphates, alkali metal sulfates and alkali metal nitrates.

20. The method of claim 1, wherein the prepared microporous hollow fiber membrane has a mean roughness (R_a) of about 600 to about 800 nm.

21. The method of claim 1, wherein the at least one suitable water soluble salt has an average particle size of about 1 to about 10 μ

m.

22. The method of claim 1, wherein the at least one suitable water soluble salt has an average particle size of about 2 to about 10 μ

m.

23. The method of claim 1, wherein the prepared hollow fiber membrane has microporous pores having an average diameter of about 1 to about 10 μ

m.

24. The method of claim 1, wherein the prepared microporous hollow fiber membrane has a water contact angle of about 128 to about 140°

.

25. The method of claim 1, wherein the prepared microporous hollow fiber membrane has a porosity of about 49 to about 51%.

18. A microporous hydrophobic hollow fiber membrane comprising:

a porosity of about 40 to about 60%;

a mean roughness (R_a) of about 600 nm to about 800 nm;

a water contact angle of about 110 to about 140°

; and

microporous pores having an average diameter of about 1 to about 20 μ

m.

19. The microporous hydrophobic hollow fiber membrane of claim 18, wherein said membrane comprises:

a water contact angle of about 128 to about 140°

; and

microporous pores having an average diameter of about 1 to about 10 μ

m.

26. The microporous hydrophobic hollow fiber membrane of claim 18, wherein said membrane comprises a porosity of about 49 to about 51%.