Ultrathin polyphenylene oxide polymer films and their preparation

• US 4,746,476 A
• Filed: 10/10/1986
• Issued: 05/24/1988
• Est. Priority Date: 10/10/1986
• Status: Expired due to Fees

• Current Assignee: Hoechst Celanese Corporation (Sanofi )
• Original Assignee: Hoechst Celanese Corporation (Sanofi )
• Inventors: Kohn, Rachel S.
• Primary Examiner(s): NOT, DEFINED
• Application Number:
  US06/917,998
• Time in Patent Office: 592 Days
• Field of Search: 428/220, 264/298, 264/41, 264/331.11, 524/466
• US Class Current: 264/41
• CPC Class Codes: B01D 69/122 Separate manufacturing of ultra-thin membranes
• CPC Class Codes: B01D 71/52 Polyethers
• CPC Class Codes: B01D 71/5223 Polyphenylene oxide, phenyl ether polymers or polyphenylethers
• CPC Class Codes: B29C 41/003 characterised by the choice of material
• CPC Class Codes: B29C 41/12 Spreading-out the material on a substrate , e.g. on the surface of a liquid
• CPC Class Codes: B29K 2071/00 Use of polyethers , e.g. PEEK, i.e. polyether-etherketone or PEK, i.e. polyetherketone or derivatives thereof, as moulding material
• CPC Class Codes: B29K 2105/0073 Solution
• CPC Class Codes: C08J 2371/12 Polyphenylene oxides
• CPC Class Codes: C08J 5/18 Manufacture of films or sheets

Abstract

Disclosed herein are free-standing, pinhole-free, ultrathin, polyphenylene oxide films having thicknesses of about 400 angstroms or less and a process for preparing them. The films find particular utility in separatory applications.

Claims

1. A process for preparing a polyphenylene oxide polymer film having a thickness of 400 angstroms or less and having no holes about one micron or more in diameter wherein the process comprises:

(a) preparing a polymer solution containing a polyphenylene oxide polymer, having a molecular weight, Mw, greater than about 1000, at about the two to about the twelve percent level, based upon the total weight of the casting solution, in a mixture of chlorinated solvents;

(b) depositing the polymer solution on about 60 to about 85 percent aqueous ortho-phosphoric acid to form a free-standing film; and

(c) removing the film from the aqueous ortho-phosphoric liquid.

4. The process of claim 1 wherein R and R'"'"' are hydrocarbon groups of from one to eight carbon atoms.

5. The process of claim 4 wherein R and R'"'"' are the same.

6. The process of claim 1 wherein the chlorinated solvents are selected from tetrachloroethylene, 1,1,2,2-tetrachloroethane, 1,2,3-trichloropropane and ortho-dichlorobenzene.

7. The process of claim 6 wherein the mixture of chlorinated solvents is about a 4:

6 to about a 6;

4 by volume ratio of tetrachloroethylene;

1,2,3-trichloropropane or tetrachloroethylene;

1,1,2,2-tetrachloroethylene.

8. The process of claim 7 wherein the ratio is about a 9:

11 to about a 11;

9 by volume ratio.

9. The process of claim 8 wherein the ratio is about a 1:

1 by volume ratio.

10. The process of claim 6 wherein the mixture of chlorinated solvents is about a 4:

1;

1 to about a 2;

2;

1 by volume ratio of tetrachloroethylene;

1,2,3-trichloropropane;

orthodichlorobenzene.

11. The process of claim 10 wherein the ratio is about a 2:

1;

1 by volume ratio.

12. The process of claims 1, 2, 8, 9, 10 or 11 wherein the polymer is a poly(2,6-dimethyl-p-phenylene oxide) polymer.

13. The process of claims 1, 2 or 3 wherein the polyphenylene oxide polymer has a molecular weight in the range of about 3,000 to about 60,000.

14. The process of claim 13 wherein the molecular weight is in the range of about 18,000 to 60,000.

15. The process of claims 1, 2, 3, 8, 9, 10 or 11 wherein the polyphenylene oxide polymer is present at about the four to about the seven percent by weight level in the casting solution based upon the total weight of the casting solution.

16. The process of claim 15 wherein the polymer is present at about the five percent by weight level.

19. The process of claims 1, 2, 17 or 18 wherein the ortho-phosphoric acid is about 60 to about 70 percent aqueous ortho-phosphoric acid.

20. The process of claims 1, 2, 3, 8, 9, 10, 11 or 17 wherein the aqueous ortho-phosphoric acid is about 64 percent aqueous ortho-phosphoric acid.

21. The process of claims 1, 2 or 3 wherein the casting solution contains a polyphenylene oxide polymer at about the 50 to about the 100 percent by weight level and another polymer or polymers at about the 50 to about the 0 percent by weight level based upon the total weight of the polymers dissolved in the casting solution.

23. The process of claim 16 wherein the aqueous ortho-phosphoric acid is about 64 percent aqueous ortho-phosphoric acid.

2. A process for preparing a polyphenylene polymer film having a thickness of about 400 angstroms or less and having no holes about one micron or more in diameter wherein the process comprises:

(a) preparing a casting solution containing a polyphenylene oxide polymer having a molecular weight, Mw, greater than about 1000 and having repeating units of the general formula;

##STR2## wherein R and R'"'"' may be the same or different and are hydrogen atoms, halogen atoms, substituted and unsubstituted hydrocarbon groups, halohydrocarbons, alkoxy groups or phenoxy groups, at about the two to about the twelve percent by weight level, based upon the total weight of the casting solution, in about a 4;

6 to about a 6;

4 by volume ratio of trichloroethylene;

1,2,3-trichloropropane or trichloroethylene;

1,1,2,2-tetrachloroethane;

(b) depositing the casting solution on about 60 to about 85 percent aqueous ortho-phosphoric acid to form a free-standing film;

(c) removing the film from the ortho-phosphoric acid.

17. The process of claim 2 wherein the casting solution contains about a 9:

11 to about a 11;

9 by volume ratio of trichloroethylene;

1,2,3-trichloropropane or trichloroethylene;

1,1,2,2-tetrachloroethane.

18. The process of claim 17 wherein the ratio is about 1:

1.

22. The process of claim 17 wherein the polymer is a poly(2,6-dimethyl-p-phenylene oxide) polymer.

3. A process for preparing a polyphenylene oxide polymer film having a thickness of about 400 angstroms or less and having no holes about one micron or more in diameter wherein the process comprises:

(a) preparing a casting solution containing a poly(2,6-dimethyl-p-phenylene oxide) polymer having a molecular weight, Mw, greater than about 1000 at about the two to about the twelve percent by weight level, based upon total weight of the casting solution, in about a 1;

1 by volume ratio of trichloroethylene;

1,2,3-trichloropropane or trichloroethylene 1,1,2,2-tetrachloroethane;

(b) depositing the casting solution on about 60 to about 70 percent by weight aqueous ortho-phosphoric acid to form a free-standing film; and

(c) removing the film from the ortho-phosphoric acid.