Poly(ethylene chlorotrifluoroethylene) membranes
View Patent ↗Porous polymeric membranes including HALAR® (poly(ethylene chlorotrifluoroethylene)) and related compounds and the methods of production thereof which avoid the use of toxic solvents. Preferred solvents, coating agents and pore forming agents are citric acid ethyl ester or glycerol triacetate. The membranes may be in the form of a hollow fiber or flat sheet, and may include other agents to modify the properties of the membranes, such as the hydrophilic/hydrophilic balance. Leachable agents may also be incorporated into the membranes.
1. A method of forming a membrane comprising casting a membrane from a solution at a temperature greater than 200° C. consisting essentially of poly(ethylene chlorotrifluoroethylene) and at least one solvent selected from the group consisting of a compound according to formula I and formula II:
wherein R 1 , R 2 , and R 3 are alkyl; R 4 is selected from the group consisting of H, OH, OR 5 , OCOR 5 , an alkyl, and an alkoxy; and R 5 is an alkyl.
2. The method of claim 1 , wherein the solvent according to formula I is citric acid ethyl ether.
3. The method of claim 1 , wherein the solvent according to formula II is glycerol triacetate.
4. The method of claim 1 , further comprising inducing a phase separation of poly(ethylene chlorotrifluoroethylene) and the solvent.
5. The method of claim 4 , further comprising contacting a first surface with a lumen forming fluid.
6. The method of claim 5 , wherein the act of contacting a first surface with the lumen forming fluid comprises contacting the surface with diethylene glycol.
7. The method of claim 5 , further comprising contacting a second surface with a coating fluid.
8. The method of claim 7 , wherein the act of contacting the second surface with the coating fluid comprises contacting the surface with a fluid selected from the group consisting of glycerol triacetate, citric acid ethyl ester, diethylene glycol, and mixtures thereof.
9. The method of claim 4 , further comprising removing the solvent from the membrane.
10. The method of claim 4 wherein R 1 , R 2 , and R 3 are selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, and hexyl.
11. A method of forming a hollow fiber membrane comprising:
forming a blend at a temperature greater than 200° C. consisting essentially of poly(ethylene chlorotrifluoroethylene) and at least one solvent selected from the group consisting of a compound according to formula I and formula II:
wherein R 1 , R 2 , and R 3 are alkyl; R 4 is selected from the group consisting of H, OH, OR 5 , OCOR 5 , an alkyl, and an alkoxy; and R 5 is an alkyl;
forming the blend into a hollow fiber shape;
contacting a first surface of the hollow fiber shape with a lumen forming fluid;
inducing a phase separation in the hollow fiber shape to form a hollow fiber membrane; and
removing the compound according to formula I or formula II from the membrane.
12. The method of claim 11 , wherein the solvent according to formula I is citric acid ethyl ether.
13. The method of claim 11 , wherein the solvent according to formula II is glycerol triacetate.
14. The method of claim 11 , wherein the blend comprises about 14-25% poly(ethylene chlorotrifluoroethylene).
15. The method of claim 11 , further comprising an act of contacting a second surface of the hollow fiber shape with a coating fluid.
16. The method of claim 15 , wherein the coating fluid is selected from the group consisting of glycerol triacetate, citric acid ethyl ester, diethylene glycol, and mixtures thereof.
17. The method of claim 11 , wherein the lumen forming fluid comprises diethylene glycol.
18. The method of claim 11 , wherein the blend further comprises a solid pore forming agent.
19. The method of claim 18 , further comprising an act of removing the pore forming agent from the hollow fiber with a leachant.
20. The method of claim 19 , wherein the leachant comprises a caustic solution.
21. The method of claim 18 , wherein the pore forming agent is an inorganic solid with a particle size of less than 1 micron.
22. The method of claim 18 , wherein the pore forming agent comprises silica.
23. The method of claim 22 , further comprising an act of preparing from the blend, a dope comprising from about 3 weight percent to about 9 weight percent silica.
24. A method of preparing a porous polymeric material comprising:
heating a mixture to a temperature greater than 200° C. to form a solution consisting essentially of poly(ethylene chlorotrifluoroethylene) and at least one solvent selected from the group consisting of a compound according to formula I and formula II:
wherein R 1 , R 2 , and R 3 are alkyl; R 4 is selected from the group consisting of H, OH, OR 5 , OCOR 5 , an alkyl, and an alkoxy; and R 5 is an alkyl;
forming a polymer rich phase and a polymer lean phase, wherein the polymer rich phase and the polymer lean phase form a matrix;
cooling the matrix to form a solid polymeric material; and
removing the polymer lean phase from the solid polymeric material after cooling the matrix.
25. The method of claim 24 , wherein R 1 , R 2 , and R 3 , are selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl and hexyl.