Electrolytic cell membrane and method of preparation by plasma polymerization of polyamide or polytetrafluoroethylene thin films onto polymeric substrates

• US 4,100,113 A
• Filed: 04/01/1976
• Issued: 07/11/1978
• Est. Priority Date: 04/01/1976
• Status: Expired due to Term

• Current Assignee: Eltech Systems Corporation (Industrie De Nora S.p.A)
• Original Assignee: Diamond Shamrock Corp (Valero Energy Corporation)
• Inventors: McCain, G. Howard
• Primary Examiner(s): Schofer, Joseph L.
• Assistant Examiner(s): Kulkosky, Peter F.
• Application Number:
  US05/672,781
• Time in Patent Office: 831 Days
• Field of Search: 260/2.2 R, 260/857 UN, 260/900, 260/884, 260/886, 260/79.3 R, 526/901, 526/913, 526/255, 526/247, 526/201, 526/17, 526/49, 204/296, 204/195 P, 204/180 P, 204/165, 428/333, 428/422, 428/474
• US Class Current: 521/38
• CPC Class Codes: C08J 2327/18 Homopolymers or copolymers of tetrafluoroethylene
• CPC Class Codes: C08J 5/2237 containing fluorine
• CPC Class Codes: C08J 5/2293 After-treatment of fluorine-containing membranes
• CPC Class Codes: Y10T 428/261 In terms of molecular thickness or light wave length
• CPC Class Codes: Y10T 428/31544 Addition polymer is perhalogenated
• CPC Class Codes: Y10T 428/31725 Of polyamide

Abstract

Disclosed is an improved hydraulically impermeable cation exchange membrane for an electrolytic cell and a method for the preparation of such a membrane using a copolymeric substrate and applying to the surface thereof by means of plasma polymerization, a very thin top coating of a second polymeric material to drastically reduce the permeability of the substrate material with a minimal effect upon the bulk properties of the resultant membrane. Such top coatings may be applied over the basic substrate or over surface treated substrates to enhance the chemical resistivity of the membrane to chemical breakdown occasioned by the electrolyte within the electrolytic cell.

Claims

1. An improved hydraulically impermeable cation exchange membrane consisting essentially of:

a substrate selected from the group of a film of copolymer having the repeating structural units of the formula ##STR4## in which R'"'"' is fluorine, or perfluoroalkyl of 1 to 10 carbon atoms;

Y is fluorine or trifluoromethyl;

m is 1, 2 or 3;

n is 0 or 1;

x is fluorine, chlorine or trifluoromethyl; and

x'"'"' is x or CF₃ --CF₂ --_a O--;

wherein a is 0 or an integer from 1 to 5;

the units of formula (I) being present in an amount to provide a copolymer having an --SO₃ H equivalent weight of about 1000 to 1400;

copolymers of tetrafluoroethylene and hexafluoropropylene having grafted thereon a 50-50 mixture of styrene and alpha methylstyrene which has been sulfonated;

or

an insoluble, infusible copolymeric matrix formed from at least 20 percent by weight of a polyvinyl aromatic compound and not more than 80 percent of a monovinyl aromatic compound with a reinforcing material therein and no more than 70 percent by weight of a monovinyl aromatic compound without a reinforcing material therein, sulfonate groups chemically bonded to the aromatic nuclei of the matrix and a solvating liquid in gel relationship with the matrix, the sulfonate groups being present in an amount no more than four equivalents or sulfonate groups for each mole of polyvinyl aromatic compound and not less than one equivalent of sulfonate groups for each 10 moles of poly- and monovinyl aromatic compound the solvating liquid being at least 25 percent by volume of the resin; and

a top coating deposited upon the surface of at least one side of said substrate by plasma polymerization to produce a thin pinhole free coating in the range of 50 to 2000 Angstroms having a chemical makeup selected from the group of polyamide or polytetrafluoroethylene.

2. An improved hydraulically impermeable cation exchange membrane according to claim 1 wherein said second polymeric material has a thickness in the preferred range of 100 to 600 Angstrom units.

4. An improved hydraulically impermeable cation exchange membrane according to claim 1 wherein at least one surface of said substrate material has been chemically treated by reacting the sulfonyl fluoride pendant groups with substances which will yield less polar bonding and therefor absorb fewer water molecules by hydrogen bonding prior to the deposition of said top coating thereon.

3. A method for the preparation of an improved hydraulically impermeable cation exchange membrane comprising the steps of:

selecting a substrate material from a group of

copolymers having the repeating structural units of the formula ##STR5## in which R¹ is fluorine, or perfluoroalkyl of 1 to 10 carbon atoms;

Y is fluorine or trifluoromethyl;

m is 1, 2 or 3;

n is 0 or 1;

x is fluorine, chlorine or trifluoromethyl; and

x¹ is x or CF₃ --CF₂ --_a O--, wherein a is 0 or an integer from 1 to 5;

the units of formula (I) being present in an amount to provide a copolymer having an --SO₃ H equivalent weight of about 1000 to 1400;

copolymers of tetrafluoroethylene and hexafluoropropylene having grafted thereon a 50-50 mixture of styrene and alpha methylsytrene which has been sulfonated;

or

an insoluble, infusible copolymeric matrix formed from at least 20 percent by weight of a polyvinyl aromatic compound and not more than 80 percent of a monovinyl aromatic compound with a reinforcing material therein and no more than 70 weight percent by weight of a monovinyl aromatic compound without a reinforcing material therein, sulfonate groups chemically bonded to the aromatic nuclei of the matrix and a solvating liquid in gel relationship with the matrix, the sulfonate groups being present in an amount no more than four equivalents or sulfonate groups for each mole of polyvinyl aromatic compound and not less than one equivalent of sulfonate groups for each 10 moles of poly- and monovinyl aromatic compound the solvating liquid being at least 25 percent by volume of the resin; and

applying a top coating selected from the group of polyamide or polytetrafluoroethylene to the surface of at least one side of said substrate by means of plasma polymerization to produce a thin pinhole free coating in the range of 100 to 2000 Angstroms.

5. A method for the preparation of an improved hydraulically impermeable cation exchange membrane according to claim 3 comprising the additional step of treating at least one surface of the substrate material chemically by reacting the sulfonyl fluoride pendant groups with substances which will yield less polar bonding and thereby absorb fewer water molecules by hydrogen bonding prior to applying the top coating.