US4969998A
Expired / Lapsed
US
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Composite semipermeable membrane
Assignee: W.L. Gore and Associates Inc
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Filing: 1984-04-23
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Granted: 1990-11-13
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Expires: 2004-04-23
Abstract
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/m2x24 hours, preferably 100,000 gms/m2x24 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.
Inventors
- 👤 Robert L. Henn
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-27 05:47
CPC Classifications
B; B01; B01D; B01D69/00; B01D69/12; B01D69/125; B32; B32B; B32B5/00; B32B5/18; B32B27/00; B32B27/06; B32B27/065; B32B27/28; B32B5/22; B32B5/24; B32B5/245; B32B7/00; B32B7/02; C; C08; C08G; C08G75/00; C08G75/02; C08G75/0204; C08G75/0245; C08G75/04; C08G75/045; C08G75/12; B32B2266/00; B32B2266/02; B32B2266/0214; B32B2266/025; B32B2305/00; B32B2305/72; B32B2307/00; B32B2307/70; B32B2307/724; B32B2307/7242; B32B2307/728; B32B2307/73
Claims Analysis
Total Claims: 39
Claim 1
Independent Claim
180 words
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/m 2 · 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: 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.
Claim 2
Dependent Claim
180 words
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/m 2 · 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: 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.
Claim 3
Dependent Claim
148 words
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/m 2 · 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: 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.
Claim 4
Dependent Claim
148 words
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/m 2 · 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: 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.
Claim 5
Dependent Claim
18 words
The composite membrane of claim 1 wherein said polyoxyethylene has a molecular weight ranging from 600 to 1,500.
Claim 6
Dependent Claim
18 words
The composite membrane of claim 2 wherein said polyoxyethylene has a molecular weight ranging from 600 to 1,500.
Claim 7
Dependent Claim
11 words
The composite membrane of claim 1 wherein both R's are polyoxyethylene.
Claim 8
Dependent Claim
29 words
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.
Claim 9
Dependent Claim
20 words
The composite membrane of claim 1 or 2 wherein said hydrophilic layer contains at least 40 percent by weight polyoxyethylene.
Claim 10
Dependent Claim
18 words
The composite membrane of claim 7 wherein said hydrophilic layer contains at least 60 percent by weight polyoxyethylene.
Claim 11
Dependent Claim
18 words
The composite membrane of claim 8 wherein said hydrophilic layer contains at least 80 percent by weight polyoxyethylene.
Claim 12
Dependent Claim
16 words
The composite membrane of claim 1 or 2 wherein said hydrophilic layer is impermeable to air.
Claim 13
Dependent Claim
27 words
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.
Claim 14
Dependent Claim
98 words
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: 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.
Claim 15
Dependent Claim
98 words
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: 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.
Claim 16
Dependent Claim
66 words
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: 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.
Claim 17
Dependent Claim
66 words
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: 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.
Claim 18
Dependent Claim
17 words
The polymer of claim 12 wherein said polyoxyethylene has a molecular weight ranging from 600 to 1,500.
Claim 19
Dependent Claim
17 words
The polymer of claim 13 wherein said polyoxyethylene has a molecular weight ranging from 600 to 1,500.
Claim 20
Dependent Claim
24 words
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.
Claim 21
Dependent Claim
18 words
The polymer of claim 12 or 13 wherein said photoinitiator is a combination of benzophenone and 1-hydroxycyclohyexylphenyl ketone.
Claim 22
Dependent Claim
10 words
The polymer of claim 12 wherein both R's are polyoxyethylene.
Claim 23
Dependent Claim
28 words
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.
Claim 24
Dependent Claim
90 words
A photocurable chemical formulation comprising (a) a terminally unsaturated polyene component comprising the formula: R--[(CH.sub.2).sub.m CH═CH.sub.2 ].sub.x, (a) a terminally unsaturated polyene component comprising the formula: 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.
Claim 25
Dependent Claim
90 words
A photocurable chemical formulation comprising (a) a terminally unsaturated polyene component comprising the formula: R--[(CH.sub.2).sub.m CH═CH.sub.2 ].sub.x, (a) a terminally unsaturated polyene component comprising the formula: 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.
Claim 26
Dependent Claim
30 words
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.
Claim 27
Dependent Claim
19 words
The photocurable chemical formulation of claim 20 wherein said polyoxyethylene has a molecular weight ranging from 600 to 1500.
Claim 28
Dependent Claim
12 words
The photocurable chemical formulation of claim 20 wherein both R's are polyoxyethylene.
Claim 29
Dependent Claim
47 words
A photocurable chemical formulation comprising (a) a terminally unsaturated polyether polyene component comprising the formula: 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.
Claim 30
Dependent Claim
47 words
A photocurable chemical formulation comprising (a) a terminally unsaturated polyether polyene component comprising the formula: 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.
Claim 31
Dependent Claim
19 words
The photocurable chemical formulation of claim 24 wherein said polyoxyethylene has a molecular weight ranging from 600 to 1,500.
Claim 32
Dependent Claim
27 words
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.
Claim 33
Dependent Claim
20 words
The photocurable chemical formulation of claim 20 or 24 wherein said photoinitiator is a combination of benzophenone and 1-hydroxycyclohexylphenyl ketone.
Claim 34
Independent Claim
214 words
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/m 2 · 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: 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.
Claim 35
Independent Claim
214 words
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/m 2 · 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: 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.
Claim 36
Independent Claim
180 words
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/m 2 · 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: 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.
Claim 37
Independent Claim
180 words
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/m 2 · 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: 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.
Claim 38
Dependent Claim
29 words
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.
Claim 39
Dependent Claim
15 words
The method of claim 28 or 29 wherein said hydrophobic layer is expanded, microporous polytetrafluoroethylene.
References Cited (Backward Citations)
US3225107A
Cited
US4280970A
Cited
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