Composite semipermeable membrane

• US 4,969,998 A
• Filed: 04/23/1984
• Issued: 11/13/1990
• Est. Priority Date: 04/23/1984
• Status: Expired due to Fees

• Current Assignee: W. L. Gore & Associates (W.L. Gore & Associates)
• Original Assignee: W. L. Gore & Associates (W.L. Gore & Associates)
• Inventors: Henn, Robert L.
• Primary Examiner(s): SPEAR JR, FRANK
• Application Number:
  US06/603,186
• Time in Patent Office: 2,395 Days
• Field of Search: 55/16, 55/158, 210/500.2, 210/490, 210/491, 210/500.36, 428/252, 428/422, 264/22, 264/49, 427/245, 427/246
• US Class Current: 210/490
• CPC Class Codes: B01D 69/125 In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
• CPC Class Codes: B01D 71/66 Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
• CPC Class Codes: B32B 2266/025 Polyolefin vinyl or acrylic copolymers B32B2266/0221, B32B2266/0242
• CPC Class Codes: B32B 2305/72 Cured, e.g. vulcanised, cross-linked
• CPC Class Codes: B32B 2307/7242 Non-permeable
• CPC Class Codes: B32B 2307/728 Hydrophilic
• CPC Class Codes: B32B 2307/73 Hydrophobic
• CPC Class Codes: B32B 27/065 of foam
• CPC Class Codes: B32B 27/28 comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
• CPC Class Codes: B32B 5/18 characterised by features of a layer of foamed material
• CPC Class Codes: B32B 5/245 another layer next to it being a foam layer
• CPC Class Codes: B32B 7/02 Physical, chemical or physicochemical properties
• CPC Class Codes: C08G 75/0245 Block or graft polymers
• CPC Class Codes: C08G 75/045 from mercapto compounds and unsaturated compounds
• CPC Class Codes: C08G 75/12 Polythioether-ethers C08G75/0245 takes precedence

Abstract

A composite semipermeable membrane is provided comprised of:

(a) a flexible film of microporous hydrophobic material having a polar molecule vapor transmission rate in excess of 10,000 gms/m² ·24 hours, preferably 100,000 gms/m² ·24 hours, and an advancing polar liquid contact angle exceeding 90 degrees, and

(b) a continuous, crosslinked amorphous hydrophilic layer penetrated to an extent into the face of the hydrophobic layer. The hydrophilic layer, when appropriately located in the structure of the microporous hydrophobic material provides a composite membrane having a polar vapor transmission rate of the complete ensemble comparable to or even exceeding that of the hydrophobic material alone, and simultaneously offering two mechanisms of separation; that imposed by the microporous layer and that imposed by the continuous, dense amporphous polymer layer, and as such is capable of numerous separation operations.

Claims

1. A flexible, layered composite semipermeable membrane comprising:

(a) a flexible film of a microporous material having a polar molecular vapour transmission rate in excess of 10,000 gms/m²·

24 hours, and an advancing polar liquid contact angle exceeding 90 degrees, and

(b) a continuous, hydrophilic layer penetrated to an extent into the face of said hydrophobic layer and physically attached thereto, said composite membrane having a transmission rate of a polar vapour exceeding 80 percent that of said material alone, wherein said hydrophobic layer is an essentially odorless solid polyether polythioether comprised of the free radical chain extended reaction product of;

(a) a terminally unsaturated polyene comprising the formula;

space="preserve" listing-type="equation">R--[(CH.sub.2).sub.m CH═

CH.sub.2 ].sub.x,

wherein m=O or 1 and x≧

2;

(b) a polythiol component comprising the formula;

##STR12## wherein N=O or 1, R'"'"'=H or OH and y≧

2;

(c) a free radical initiator; and

(d) a suitable energy source,

wherein at least one R is polyoxyethylene and the other R may be polyoxyethylene or a polyvalent organic moiety free from hydrolytically sensitive functional groups and other carbon-to-carbon unsaturation or thiol functional groups.

3. The composite membrane of claim 1 wherein said polyoxyethylene has a molecular weight ranging from 600 to 1,500.

5. The composite membrane of claim 1 wherein both R'"'"'s are polyoxyethylene.

6. The composite membrane of claim 1 wherein said other R is selected from the group consisting of an isocyanurate ring, polyoxypropylene, poly(tetramethylene oxide), pentaerythritol, silicate, diethyl ether and glycerol.

7. The composite membrane of claim 1 or 2 wherein said hydrophilic layer contains at least 40 percent by weight polyoxyethylene.

8. The composite membrane of claim 7 wherein said hydrophilic layer contains at least 60 percent by weight polyoxyethylene.

9. The composite membrane of claim 8 wherein said hydrophilic layer contains at least 80 percent by weight polyoxyethylene.

10. The composite membrane of claim 1 or 2 wherein said hydrophilic layer is impermeable to air.

11. The composite membrane of claim 1 or 2 having at least one additional textile layer affixed to at least one surface thereof and in laminate attachment thereto.

2. A flexible, layered composite semipermeable membrane comprising:

(a) a flexible film of a microporous material having a polar molecular vapour transmission rate in excess of 10,000 gms/m²·

24 hours, and an advancing polar liquid contact angle exceeding 90 degrees, and

(b) a continuous, hydrophilic layer penetrated to an extent into the face of said hydrophobic layer and physically attached thereto, said composite membrane having a transmission rate of a polar vapour exceeding 80 percent that of said material alone, wherein said hydrophilic layer is an essentially odorless solid polyether polythioether, comprised of the free radical chain extended reaction product of;

(a) a terminally unsaturated polyether polyene comprising the formula;

space="preserve" listing-type="equation">R--[O--CH.sub.2 CH.sub.2 --O--(CH.sub.2).sub.m CH═

CH.sub.2 ].sub.x,

wherein m=O or 1 and x≧

2;

(b) a polyether polythiol component comprising the formula;

##STR13## wherein y≧

2;

(c) a free radical initiator; and

(d) a suitable energy source,

wherein R is polyoxyethylene.

4. The composite membrane of claim 2 wherein said polyoxyethylene has a molecular weight ranging from 600 to 1,500.

12. A synthetic polymer comprising an essentially odorless solid polyether polythioether comprised of the free radical chain extended reaction product of:

(a) a terminally unsaturated polyene comprising the formula;

space="preserve" listing-type="equation">R--[(CH.sub.2).sub.m CH═

CH.sub.2 ].sub.x,

wherein m=O or 1 and x≧

2;

(b) a polythiol component comprising the formula;

##STR14## wherein n=0 or 1, R'"'"'=H or OH and y≧

2;

(c) a free radical photoinitiator; and

(d) a suitable energy source,

wherein at least one R is polyoxyethylene and the other R may be polyoxyethylene or a polyvalent organic moiety free from hydrolytically sensitive functional groups and other carbon-to-carbon unsaturation or thiol functional groups.

14. The polymer of claim 12 wherein said polyoxyethylene has a molecular weight ranging from 600 to 1,500.

16. The polymer of claim 12 or 13 said photoinitiator is selected from the class consisting of benzophenone, acetophenone(s), dibenzosuberone, 1-hydroxycyclohexylphenyl ketone, benzoin isopropyl ether.

17. The polymer of claim 12 or 13 wherein said photoinitiator is a combination of benzophenone and 1-hydroxycyclohyexylphenyl ketone.

18. The polymer of claim 12 wherein both R'"'"'s are polyoxyethylene.

19. The polymer of claim 12 wherein said other R is selected from the group consisting of an isocyanurate ring, polyoxypropylene, poly(tetramethylene oxide), pentaerythritol, silicate, diethyl ether and glycerol.

13. A synthetic polymer comprising an essentially odorless solid polyether polythioether, comprised of the free radical chain extended reaction product of:

(a) a terminally unsaturated polyether polyene comprising the formula;

space="preserve" listing-type="equation">R--[O--CH.sub.2 CH.sub.2 --O--(CH.sub.2).sub.m CH═

CH.sub.2 ].sub.x,

wherein m=0 or 1 and x≧

2;

(b) a polyether polythiol component comprising the formula;

##STR15## wherein y≧

2;

(c) a free radical photoinitiator; and

(d) a suitable energy source, wherein R is polyoxyethylene.

15. The polymer of claim 13 wherein said polyoxyethylene has a molecular weight ranging from 600 to 1,500.

20. A photocurable chemical formulation comprising (a) a terminally unsaturated polyene component comprising the formula:

space="preserve" listing-type="equation">R--[(CH.sub.2).sub.m CH═

CH.sub.2 ].sub.x,

(a) a terminally unsaturated polyene component comprising the formula;

space="preserve" listing-type="equation">R--[(CH.sub.2).sub.m CH═

CH.sub.2 ].sub.x,

wherein m=0 or 1 and x≧

2;

(b) a polythiol component comprising the formula;

##STR16## wherein n=0 or 1, R'"'"'=H or OH and y≧

2; and

(c) a free radical initiator;

wherein at least one R is polyoxyethylene and the other R may be polyoxyethylene or a polyvalent moiety free from hydrolytically sensitive functional groups and other carbon-to-carbon unsaturation or thiol functional groups.

21. The photocurable chemical formulation of claim 20 wherein said other R is selected from the group consisting of an isocyanurate ring, polyoxypropylene, poly(tetramethylene oxide), pentaerythritol, silicate, diethyl ether and glycerol.

22. The photocurable chemical formulation of claim 20 wherein said polyoxyethylene has a molecular weight ranging from 600 to 1500.

23. The photocurable chemical formulation of claim 20 wherein both R'"'"'s are polyoxyethylene.

26. The photocurable chemical formulation of claim 20 or 24 wherein said photoinitiator is selected from the class consisting of benzophenone, acetophenone(s), dibenzosuberone, 1-hydroxycyclohexylphenyl ketone, benzoin isopropyl ether.

27. The photocurable chemical formulation of claim 20 or 24 wherein said photoinitiator is a combination of benzophenone and 1-hydroxycyclohexylphenyl ketone.

24. A photocurable chemical formulation comprising

(a) a terminally unsaturated polyether polyene component comprising the formula:

space="preserve" listing-type="equation">R--[O--CH.sub.2 CH.sub.2 --O--(CH.sub.2).sub.m CH═

CH.sub.2 ].sub.x,

wherein m=0 or 1, R =polyoxyethylene and x≧

2;

(b) a polyether polythiol component comprising the formula;

##STR17## wherein y≧

2 and R=polyoxyethylene; and

(c) a free radical initiator.

25. The photocurable chemical formulation of claim 24 wherein said polyoxyethylene has a molecular weight ranging from 600 to 1,500.

28. A method for forming a flexible, layered composite semipermeable membrane comprising the steps of:

(a) forming a flexible layer of a microporous hydrophobic material having a water vapour transmission rate exceeding 10,000 gms/m²·

24 hours and an advancing polar liquid contact angle exceeding 90 degrees,

(b) casting a flowable liquid formulation comprising;

(1) a terminally unsaturated polyene component comprising the formula;

space="preserve" listing-type="equation">R--[(CH.sub.2).sub.m CH═

CH.sub.2 ].sub.x,

wherein m=0 or 1 and x≧

2;

(2) a polythiol component comprising the formula;

##STR18## wherein n=0 or 1, R'"'"'=H or OH and y≧

2; and

(3) a free radical initiator;

wherein at least one R is polyoxyethylene and the other R may be a polyoxyethylene or a polyvalent moiety free from hydrolytically sensitive functional groups and other carbon-to-carbon unsaturation or thiol functional groups,

to form a continuous layer directly onto said microporous hydrophobic layer, the rheology of said liquid being such that, with sufficient hydraulic pressure applied, controllable penetration of said liquid into the microporous hydrophobic layer is achieved,

(c) applying said hydraulic pressure

(d) followed by curing of said liquid to form a continuous solid polymeric hydrophilic layer impregnated to an extent into the pores of said microporous hydrophobic layer, said composite membrane having a water vapour transmission rate exceeding 80 percent that of said hydrophobic layer alone.

30. The method of claim 28 or 29 wherein said hydrophobic layer is selected from the class consisting of microporous polytetrafluoroethylene, polypropylene, poly(vinyl chloride), polyurethane, polycarbonate, polystyrene, polyethylene and polyamide.

31. The method of claim 28 or 29 wherein said hydrophobic layer is expanded, microporous polytetrafluoroethylene.

29. A method for forming a flexible, layered composite semipermeable membrane comprising the steps of:

(a) forming a flexible layer of a microporous hydrophobic material having a water vapour transmission rate exceeding 10,000 gms/m²·

24 hours and an advancing polar liquid contact angle exceeding 90 degrees,

(b) casting a flowable liquid formulation comprising;

(1) a terminally unsaturated polyether polyene comprising the formula;

space="preserve" listing-type="equation">R--[O--CH.sub.2 CH.sub.2 --O--(CH.sub.2).sub.m CH═

CH.sub.2 ].sub.x,

wherein m=0 or 1, R=polyoxyethylene and x≧

2;

(2) a polyether polythiol component comprising the formula;

##STR19## wherein y≧

2 and R=polyoxyethylene; and

(3) a free radical initiator, to form a continuous layer directly onto said microporous hydrophobic layer, the rheology of said liquid being such that, with sufficient hydraulic pressure applied, controllable penetration of said liquid into the microporous hydrophobic layer is achieved,

(c) applying said hydraulic pressure

(d) followed by curing of said liquid to form a continuous solid polymeric hydrophilic layer impregnated to an extent into the pores of said microporous hydrophobic layer, said composite membrane having a water vapour transmission rate exceeding 80 percent that of said hydrophobic layer alone.