Dispersing casting of integral skinned highly asymmetric polymer membranes

• US 4,774,039 A
• Filed: 11/19/1986
• Issued: 09/27/1988
• Est. Priority Date: 03/14/1980
• Status: Expired due to Term

• Current Assignee: Memtec America Corporation
• Original Assignee: Brunswick Corporation
• Inventors: Wrasidlo, Wolfgang J.
• Primary Examiner(s): SPEAR JR, FRANK
• Application Number:
  US06/932,372
• Time in Patent Office: 678 Days
• Field of Search: 210/500.34, 210/500.38, 210/500.4, 210/500.41, 210/500.43, 210/490, 264/41
• US Class Current: 264/41
• CPC Class Codes: B01D 2323/08 Specific temperatures applied
• CPC Class Codes: B01D 2323/12 Specific ratios of components used
• CPC Class Codes: B01D 2325/02 Details relating to pores or porosity of the membranes
• CPC Class Codes: B01D 2325/022 Asymmetric membranes
• CPC Class Codes: B01D 2325/0283 Pore size
• CPC Class Codes: B01D 61/145 Ultrafiltration
• CPC Class Codes: B01D 61/147 Microfiltration
• CPC Class Codes: B01D 65/102 Detection of leaks in membranes
• CPC Class Codes: B01D 67/0011 Casting solutions therefor
• CPC Class Codes: B01D 67/00111 Polymer pretreatment in the casting solutions
• CPC Class Codes: B01D 69/02 characterised by their properties

Abstract

There is disclosed, in one aspect, an improved highly asymmetric membrane comprising a skin and a porous asymmetric support. The skin contains pores which have an mean pore diameter of from about 0.005 to about 3.0 microns and the asymmetric support comprises a reticulated structure which contains pores which have pore diameters of from about 10 to about 20,000 times as large as the pore diameter of the pores of the skin. The membrane has a bulk porosity greater than about 70%. In another aspect, there is disclosed a process for preparing these membranes. This process comprises casting a polymer dope while the dope is in an unstable liquid dispersion condition. The concentration of polymer in the polymer dope should be high enough to produce a coherent membrane yet low enough to form a substantially all-reticulated structure within the asymmetric support. The membranes are characterized by high flow rates, excellent retention properties, and improved resistance to fouling.

Claims

1. A method of making a highly asymmetric integrally skinned polymer membrane with excellent retention properties, a high flow rate, and improved resistance to fouling, said method comprising:

A. mixing a polymer and a solvent to produce a polymer solution,

B. adding a non-solvent in an amount sufficient to produce an unstable dispersion within the binodal or spinodal,

C. casting said dispersion on a support,

D. quenching said dispersion with a non-solvent quenching liquid in which the solvent is freely soluble but in which the polymer is substantially insoluble, and

E. recovering a membrane having a bulk porosity greater than 70%, an integral skin with an mean pore diameter of from about 0.003 to about 3.0 microns and a reticulated integral porous support layer with a gradually increasing mean pore diameter from the skin face to the opposite face, so that at the opposite face the pores have an mean diameter of from at least about 10 to about 20,000 times the average pore diameter of the pores of the skin.

2. The method of claim 1 wherein the properties of the dispersion prior to casting are controlled as a function of the optical density of the dispersion.

3. The method of claim 2 wherein the mean skin pore diameter is a function of optical density at the quenching step.

4. The method of claim 2 wherein said optical density is maintained in the range of from about 0.2 to 0.5 at 420 nanometers.

5. The method of claim 2 wherein said optical density is maintained in the range of from about 0.2 to 0.3 at 420 nanometers.

6. The method of claim 1 wherein the properties of the dispersion prior to casting are controlled as a function of the temperature of the dispersion.

7. The method of claim 6 wherein the mean skin pore diameter is a function of temperature of the dispersion at the quenching step.

8. The method of claim 1 where the optical density and temperature of the dispersion prior to casting are controlled, with the adjustment of the proportion of non-solvent to the polymer dope necessary to maintain the dispersion within the spinodal or binodal, in order to control the mean skin pore diameter of the resulting membrane.

9. The method of claim 1, wherein said polymer is selected from the group comprising polyamides, polyvinylidene halides, polysulfones, polyacrilonitriles and mixtures thereof.

10. The method of claim 1, wherein the solvent is selected from the group comprising dimethyformamide, dimethylacetamide, dioxane, n-methyl pyrrolidone, dimethylsulfoxide, chloroform, tetramethylurea, and tetrachloroethane.

11. The method of claim 1, wherein the non-solvent is selected from the group comprising methanol, ethanol, isopropanol, amyl alcohol, hexanol, heptanol, octanol, propane, hexane, heptane, octane, acetone, methylethylketone, methylisobutyl ketone, nitropropane, butyl ether, ethyl acetate, and amyl acetate.