Microporous polyester membranes and polymer assisted phase inversion process for their manufacture

• US 3,957,651 A
• Filed: 04/30/1975
• Issued: 05/18/1976
• Est. Priority Date: 12/16/1971
• Status: Expired due to Term

• Current Assignee: Gelsub Incorporated
• Original Assignee: Chemical Systems Incorporated
• Inventors: Kesting, Robert E.
• Primary Examiner(s): Anderson, Philip
• Application Number:
  US05/572,887
• Time in Patent Office: 384 Days
• Field of Search: 264/41, 264/49, 264/46.4, 264/5, 264/13, 210/500 M, 210/490, 210/31 C, 260/2.5 M, 260/30.4 R, 260/31.2 R, 260/31.2, 260/33.4 R
• US Class Current: 210/490
• CPC Class Codes: B01D 2323/12 Specific ratios of components used
• CPC Class Codes: B01D 67/003 by selective elimination of components, e.g. by leaching
• CPC Class Codes: B01D 71/48 Polyesters

Abstract

Microporous membrane filters composed of polyesters derived from aromatic dibasic acids and especially polytetramethylene terephthalate are produced. These membranes are produced by a polymer assisted phase inversion process involving casting a solution of the polyester and assisting polymer to form a film, evaporating the solvent to form a membrane having inchoate micropores filled with the assisting polymer and subsequently at least partially leaching out the assiting polymer.

Claims

1. An integral microporus membrane having inchoate pores which are at least partially filled with an assisting polymer, the membrane consisting essentially of a polyester resin of the general formula:

##EQU8## wherein a is an integer of from 3 to 7 and n is an integer greater than about 45, and wherein the assisting polymer is soluble in a solvent which is a nonsolvent for the polyester.

2. The membrane defined in claim 1 wherein the assisting polymer consists essentially of the polyvinyl alcohol or polyvinyl pyrrolidone.

3. The membrane set forth in claim 2 wherein the polyvinyl alcohol has a molecular weight of from about 5,000 to about 25,000 and an acetyl content up to about 50 percent.

4. The membrane set forth in claim 1 wherein a is 3, 4 or 5.

5. The membrane set forth in claim 4 wherein a is 4.

6. An integral microporous polyester membrane prepared by the process comprising the steps of casting a solution consisting of a polyester resin having the general formula:

##EQU9## where in a is an integer of from 3 to 7 and n is an integer greater than about 45 and an assisting polymer, in concentrations of from about 2 percent to about 20 percent by weight of total polymer in a mutual solvent for the polymers onto a substrate to form a film and extracting the mutual solvent for the polymers from the film to thereby form a membrane of similar configuration, the membrane having inchoate pores filled with the assisting polymer, and leaching at least some of the assisting polymer from the pores by exposing the membrane to a solvent for the assisting polymer which is a nonsolvent for the polyester.

8. The membrane defined in claim 6 wherein a is 4.

9. The membrane defined in claim 6 wherein the assisting polymer is polyvinyl alcohol or polyvinyl pyrrolidone.

7. The membrane claimed in 6 wherein a is 3, 4 or 5.

10. An integral microporous polyester membrane prepared by the process comprising casting a solution containing a polyester resin having the general formula:

##EQU10## wherein a is an integer of 3 to 7 and n is an integer greater than about 45 in concentrations of from about 2 percent to about 20 percent by weight of total polymer in a solvent for the polymer upon a substrate to form a film and extracting the solvent from the film to thereby form a membrane.

11. A casting solution for forming microporous membranes consisting essentially of a polyester derived from the condensation polymerization of terephthalic acid or an ester of terephthalic acid with a 3 to 7 carbon atom containing alkyl diol and hexafluoroisopropanol or trifluoroacetic acid or mixtures of hexafluoroisopropanol and trifluoroacetic acid.

12. The casting solution defined in claim 11 containing polyvinyl alcohol, polyvinyl pyrrolidone or tetrahydrofuran.

13. A polymer assisted phase inversion process for forming integral microporous membranes, comprising the steps of:

forming a solution of a solvent resistant membrane forming polyester resin derived from the condensation polymerization of terephthalic acid or an ester of terephthalic acid with a 3 to 7 carbon atom containing alkyl diol and an assisting polymer in a mutual solvent for said polymers;

casting said solution upon a substrate to form a film; and

evaporating the mutual solvent from said cast film to form a membrane having generally the same configuration as the substrate and having inchoate micropores filled with the assisting polymer, the assisting polymer being soluble in a solvent which is a non-solvent for the solvent resistant polyester.

14. The process for forming integral membrane constructions comprising the steps of:

casting a membrane from a solution containing a solvent resistant polymer and an assisting polymer to form a membrane having inchoate pores filled with the assisting polymer; and

casting at least one additional layer of polymer from a solution onto the membrane formed in the preceding step.

15. A microporous powder product comprising beads formed by spraying a solution consisting of polyester resins derived from the condensation polymerization of terephthalic acid or an ester of terephthalic acid with a 3 to 7 carbon atom containing alkyl diol and an assisting polymer in a mutual solvent for said polymers to form fine droplets and allowing the droplets to dry into a fine powder, said assisting polymer being soluble in a solvent which is a non-solvent for the polyester resin and thereafter leaching the assisting polymer.

16. A method for forming microporous beads comprising the steps of spraying a solution consisting of polyester resins derived from the condensation polymerization of terephthalic acid or an ester or terephthalic acid with a 3 to 7 carbon atom containing alkyl diol and an assisting polymer in a mutual solvent for said polymers to form fine droplets and allowing the droplets to dry into a fine powder, said assisting polymer being soluble in a solvent which is a non-solvent for the polyester resin and thereafter leaching the assisting polymer.

17. The method defined in claim 16 wherein the assisting polymer is polyvinyl alcohol or polyvinyl pyrrolidone.