Method of preparing membranes from blends of polymers

• US 5,733,657 A
• Filed: 10/11/1994
• Issued: 03/31/1998
• Est. Priority Date: 10/11/1994
• Status: Expired due to Fees

• Current Assignee: L'Air Liquide SA
• Original Assignee: Praxair Technology Incorporated (Linde Plc)
• Inventors: Bikson, Benjamin, Nelson, Joyce Katz, Macheras, James Timothy
• Primary Examiner(s): Ryan, Patrick
• Assistant Examiner(s): GRAY, JILL M
• Application Number:
  US08/320,725
• Time in Patent Office: 1,267 Days
• Field of Search: 428/397, 428/398, 428/395, 428/394, 96/8, 96/10, 96/12, 96/13, 96/14, 55/527, 55/522, 55/528, 55/524, 210/500.23, 210/500.24, 210/500.39, 264/41, 264/177.17, 264/211.14, 264/178 F, 264/177.14
• US Class Current: 428/398
• CPC Class Codes: B01D 2325/022 Asymmetric membranes
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• CPC Class Codes: B01D 67/00111 Polymer pretreatment in the casting solutions
• 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 71/643 Polyether-imides
• CPC Class Codes: B01D 71/76 Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 rubbers in general B01D71/24
• CPC Class Codes: B01D 71/80 Block polymers
• CPC Class Codes: B01D 71/82 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
• CPC Class Codes: Y10T 428/2967 Synthetic resin or polymer
• CPC Class Codes: Y10T 428/2969 Polyamide, polyimide or polyester
• CPC Class Codes: Y10T 428/2973 Particular cross section
• CPC Class Codes: Y10T 428/2975 Tubular or cellular
• CPC Class Codes: Y10T 428/3154 Of fluorinated addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31544 Addition polymer is perhalogenated

Abstract

Improved anisotropic fluid separation membranes are prepared from blends of polymers with surface energy differences. The membranes are formulated by processes wherein low surface energy polymer with desirable fluid separation and permeation characteristics is preferentially concentrated in the surface discriminating layer of the membrane.

Claims

1. An anisotropic fluid separation membrane comprising a blend of at least two polymers, one of which is a polyetherimide containing siloxane groups, having a measured surface energy that is at least 10 percent lower than the measured surface energy of the other polymers in the blend, said polyetherimide containing siloxane groups comprising less than 20 percent by weight of the overall membrane material in said blend and being concentrated in a surface discriminating layer of said fluid separation membrane, said surface discriminating layer being less than 1000Å

thick.

2. The membrane of claim 1 in which the bulk of said membrane material comprises a polyetherimide which does not contain siloxane groups.

3. The membrane of claim 1, wherein the membrane is a hollow fiber membrane.

4. The membrane of claim 3, wherein said hollow fiber membrane is further coated to provide a composite coated hollow fiber membrane.

5. The membrane of claim 1, wherein said low energy polymer comprises less than 10 percent by weight of the overall membrane material.

6. The membrane of claim 1, wherein said low energy polymer comprises less than 5 percent by weight of the overall membrane material.

7. The membrane of claim 1, wherein said low surface energy polymer lowers the overall surface energy of the membrane by more than 5 dynes/cm.

8. An anisotropic gas separation hollow fiber membrane comprising a blend of a polyimide polymer and polyimide containing siloxane groups, said polyimide containing siloxane groups having a measured surface energy that is at least 10 percent lower than the measured surface energy of said polyimide polymer, said low surface energy copolymer comprising less than 20 percent by weight of the overall membrane material and being concentrated in a surface discriminating layer of said anisotropic gas separation hollow fiber membrane, wherein said anisotropic gas separation hollow fiber membrane is prepared by a process comprising:

(a) forming a mixture of said blend of polymers and at least one solvent, said polyimide containing siloxane groups, having a measure surface energy that is at least 10 percent lower than the measured surface energy of said polyimide polymer;

(b) extruding said mixture, as a hollow fiber, through a gaseous atmosphere and into a liquid medium wherein said fiber solidifies; and

(c) recovering the solidified fiber, said surface discriminating layer being less than 1000Å

thick.

9. The hollow fiber membrane of claim 8, wherein said polyimide polymer is polyetherimide and the polyimide containing siloxane groups is polyetherimide containing siloxane groups.

10. The membrane of claim 8, wherein said low energy polymer comprises less than 10 percent by weight of the overall membrane material.

11. The membrane of claim 8, wherein said low energy polymer comprises less than 5 percent by weight of the overall membrane material.

12. The membrane of claim 8, wherein said low surface energy polymer lowers the overall surface energy of the membrane by more than 5 dynes/cm.

13. The membrane of claim 8, wherein said hollow fiber membrane is further coated to provide a composite coated hollow fiber membrane.

14. The membrane of claim 8, wherein said gaseous atmosphere is maintained at a subatmospheric pressure.