Method of preparing acrylic ion-transfer membranes

• US 4,434,249 A
• Filed: 06/28/1982
• Issued: 02/28/1984
• Est. Priority Date: 06/28/1982
• Status: Expired due to Fees

• Current Assignee: Electrochemical Technology Corporation
• Original Assignee: Electrochemical Technology Corporation
• Inventors: Ruggeri, Robert T., Ballestrasse, Cindy L.
• Primary Examiner(s): Schofer, Joseph L.
• Assistant Examiner(s): Kulkosky, Peter F.
• Application Number:
  US06/392,731
• Time in Patent Office: 610 Days
• Field of Search: 521/27
• US Class Current: 521/27
• CPC Class Codes: B01J 47/12 characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes electrodialysis or electro-osmosis B01D61/42
• CPC Class Codes: C08J 2333/12 Homopolymers or copolymers of methyl methacrylate
• CPC Class Codes: C08J 5/2231 based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
• CPC Class Codes: G01N 27/3335 the membrane containing at least one organic component G01N27/3271 takes precedence; aspects concerning the enzyme reagent in enzyme electrodes C12Q1/001
• CPC Class Codes: H01M 50/46 Separators, membranes or diaphragms characterised by their combination with electrodes
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Ion exchange resins can be prepared by co-polymerizing a major amount (>88 mol %) of non-ionic acrylic monomer, such as methyl methacrylate, with a minor amount (3 to 12 mol %) of an ionogenous monomer such as methacrylamidopropyltrimethylammonium chloride or 2-acrylamido-2-methyl propane sulfonic acid. The resultant anion-conductive or cation conductive membranes exhibit low swelling in water and high ion-transference numbers. The membranes may be applied as coatings on neural prosthesis electrodes.

Claims

1. A process for forming ion-transfer membranes which comprises the following steps in sequence:

preparing a reaction mixture consisting essentially of;

(A) a major, non-ionic component selected from the group consisting of a hydrophobic acrylic monomer having the formula;

##STR4## where R is H or CH₃ and R₁ is methyl, ethyl or butyl, and mixtures of two or more of said hydrophobic monomers;

(B) a minor, ionogenous acrylic monomer component selected from the group consisting of;

(i) acrylic acid;

(ii) methacrylic acid;

(iii) monomers represented by the formula;

##STR5## wherein;

R is H or CH₃,

and X is ##STR6## R₁ is alkylene or hydroxyalkylene R₂, R₃ and R₄ are hydrogen, alkyl, or hydroxyalkyl, and

Z^- is a halide, acetate, or methyl sulfate ion; and

, (iv) mixtures of two or more of said ionogenous acrylic monomers; and

(C) an organic solvent,

wherein the concentration of said major, non-ionic component in said solvent is in the range 2.5 to 7.5 molar, and the concentration of said minor, ionogenous component in said solvent is in the range 0.10 to 0.75 molar, and wherein the molar concentration of said ionogenous component is between 3 and 12% of the total monomer content in said reaction mixture;

depositing a thin film of said reaction mixture on a substrate; and

heating said deposited film in a substantially oxygen-free environment at a temperature between 55 degrees C. and 80 degrees C.

2. The process of claim 1 wherein said organic solvent is a water soluble alcohol.

3. The process of claim 1 wherein said organic solvent is a water soluble acid.

4. The process of claim 1 wherein said organic solvent is selected from the group consisting of ethanol and acetic acid.

5. The process of claim 1 wherein said reaction mixture further includes a polymerization initiator.

6. The process of claim 1 wherein said reaction mixture further includes a cross-linker.

7. The process of claim 5 wherein said polymerization initiator is azobisisobutyronitrile.

11. The process of claim 1, 8, or 9, wherein said ionogenous monomer is methacrylamidopropyltrimethylammonium chloride.

8. A process for forming ion-transfer membranes which comprises the following steps in sequence:

preparing a reaction mixture consisting essentially of;

(A) a major, non-ionic component selected from the group consisting of a hydrophobic acrylic monomer having the formula;

##STR7## where R is H or CH₃ and R₁ is methyl, ethyl or butyl, and mixtures of two or more of said hydrophobic monomers;

(B) a minor, ionogenous acrylic monomer component selected from the group consisting of;

(i) acrylic acid;

(ii) methacrylic acid;

(iii) monomers represented by the formula;

##STR8## wherein;

R is H or CH₃,

12. The process of claim 8 wherein said organic solvent is a water soluble alcohol.

13. The process of claim 8 wherein said organic solvent is a water soluble acid.

14. The process of claim 8 wherein said organic solvent is selected from the group consisting of ethanol and acetic acid.

15. The process of claim 8 wherein said reaction mixture further includes a polymerization initiator.

16. The process of claim 8 wherein said reaction mixture further includes a cross-linker.

17. The process of claim 8 wherein said polymerization initiator is azobisisobutyronitrile.

9. and X is ##STR9## R₁ is alkylene or hydroxyalkylene R₂, R₃ and R₄ are hydrogen, alkyl, or hydroxyalkyl, and

Z^- is a halide, acetate, or methyl sulfate ion;

and, (iv) mixtures of two or more of said ionogenous monomers; and

(C) an organic solvent,

wherein the concentration of said major, non-ionic component in said solvent is in the range 2.5 to 7.5 molar, and the concentration of said minor, ionogenous component in said solvent is in the range 0.10 to 0.75 molar, and wherein the molar concentration of said ionogenous component is between 2 and 12% of the total monomer content in said reaction mixture;

heating said reaction mixture to a viscous consistency at a temperature between 55 and 80 degrees C. in a substantially oxygen-free environment;

coating a substrate with a film of said viscous reaction mixture; and

heating said deposited film to a temperature between 55 and 80 degrees C. in a substantially oxygen-free environment until said film becomes rubbery.

18. The process of claim 9 wherein said organic solvent is a water soluble alcohol.

19. The process of claim 9 wherein said organic solvent is a water soluble acid.

20. The process of claim 9 wherein said organic solvent is selected from the group consisting of ethanol and acetic acid.

21. The process of claim 9 wherein said reaction mixture further includes a polymerization initiator.

22. The process of claim 9 wherein said reaction mixture further includes a cross-linker.

23. The process of claim 9 wherein said polymerization initiator is azobisisobutyronitrile.

10. A process for forming ion-transfer membranes which comprises the following steps in sequence

preparing a reaction mixture consisting essentially of:

(A) a major, non-ionic component selected from the group consisting of a hydrophobic acrylic monomer having the formula;

##STR10## where R is H or CH₃ and R₁ is methyl, ethyl or butyl and mixtures of two or more of said hydrophobic monomers;

(B) a minor, ionogenous acrylic monomer component selected from the group consisting of;

(i) acrylic acid;

(ii) methacrylic acid;

(iii) monomers represented by the formula;

##STR11## wherein;

R is H or CH₃,

and X is ##STR12## R₁ is alkylene or hydroxyalkylene R₂, R₃ and R₄ are hydrogen, alkyl, or hydroxyalkyl, and

Z^- is a halide, acetate, or methyl sulfate ion; and

, (iv) mixtures of two or more of said ionogenous monomers; and

(C) an organic solvent,

wherein the concentration of said major, non-ionic component in said solvent is in the range 2.5 to 7.5 molar, and the concentration of said minor, ionogenous component in said solvent is in the range 0.10 to 0.75 molar, and wherein the molar concentration of said ionogenous component is between 3 and 12% of the total monomer content in said reaction mixture;

introducing a quantity of said reaction mixture into a mold cavity and thereafter maintaining said mold cavity in a substantially oxygen-free condition;

heating said mold cavity to a temperature between 55 and 80 degrees C. and maintaining said temperature until the mold cavity contents becomes rubbery; and

removing said rubbery contents from said mold cavity.