IP Library Granted Patent US 10,792,620
Granted Patent B2
US 10,792,620 · App. 15/527,094 · Granted Oct 6, 2020

Grafted ultra high molecular weight polyethylene microporous membranes

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Quick Facts
Patent No.
US 10,792,620
App. No.
15/527,094
Granted
Oct 6, 2020
Kind
B2
Abstract

Grafted, asymmetric, porous, ultra high molecular weight polyethylene membranes having a bubble point between about 5.38 bar (78 psi) and 11.03 bar (160 psi) are disclosed. Monomers are grafted to the porous polymeric membrane surfaces, the monomers having one or more of neutral groups or ion exchange groups grafted to one or more surfaces of the membrane. A combination of two photoinitiators can be used to graft the monomers to the asymmetric, porous, ultra high molecular weight membrane resulting in grafted microporous membranes that have water flow rates that are at least 50% of the water flow rate of an ungrafted, asymmetric, porous ultra high molecular weight polyethylene membrane. The grafted membrane also wets in water.

Claims (37)

1. A grafted, asymmetric, porous, ultra high molecular weight polyethylene membrane comprising:

one or more neutral groups or ion exchange groups grafted to one or more surfaces of the membrane; and

benzophenone adsorbed onto the membrane;

wherein the membrane has a bubble point between about 78 psi and 160 psi when determined by an ethoxy nonafluorobutane bubble point test;

wherein the membrane has a water flow rate that is at least 50% of the water flow rate of an ungrafted, asymmetric, porous ultra high molecular weight polyethylene membrane having a bubble point determined by an ethoxy nonafluorobutane bubble point test that is between about 78 psi and about 160 psi; and

wherein the membrane wets in water in 10 seconds or less.

2. The membrane of claim 1 , wherein the ion exchange groups are derived from the group consisting of (3-acrylamidopropyl)trimethylammonium chloride, (vinyl benzyl)trimethyl-ammonium chloride, and combinations thereof.

3. The membrane of claim 1 , wherein the ion exchange groups are derived from the group consisting of acrylic acid, vinyl sulfonic acid, and combinations thereof.

4. The membrane of claim 1 , wherein the grafted, asymmetric, porous, ultra high molecular weight polyethylene membrane has a surface tension that is between about 60% to 75% higher than the surface tension of an ungrafted, asymmetric, porous ultra high molecular weight polyethylene membrane having a bubble point determined by the ethoxy nonafluorobutane bubble point test that is between about 78 psi and about 160 psi when determined by an cthoxy nonafluorobutanc bubble point test.

5. The membrane of claim 1 , wherein the neutral groups are derived from the group consisting of N-(hydroxymethyl)acrylamide, 2-hydroxyethylacrylate, and combinations thereof.

6. The membrane of claim 1 , wherein the ion exchange groups are derived from a cationic monomer selected from the group consisting of 2-(dimethylamino)ethyl hydrochloride acrylate, [2-(acryloyloxy)ethyl]trimethylammonium chloride, 2 aminoethyl methacrylate hydrochloride, N-(3-aminopropyl) methacrylate hydrochloride, 2 (dimethylamino)ethyl methacrylate hydrochloride, [3- (methacryloylamino)propyl]trimethylammonium chloride solution, [2 (methacryloyloxy)ethyl]trimethylammonium chloride, acrylamidopropyl trimethylammonium chloride, 2-aminoethyl methacrylamide hydrochloride, N-(2-aminoethyl) methacrylamide hydrochloride, N-(3-Aminopropyl)-methacrylamide hydrochloride, diallyldimethylammonium chloride, allylamine hydrochloride, vinyl imidazolium hydrochloride, vinyl pyridinium hydrochloride and vinyl benzyl trimethyl ammonium chloride.

7. The membrane of claim 1 , wherein the ion exchange groups are derived from an anionic monomers is selected from the group consisting of 2-ethylacrylic acid, acrylic acid, 2-carboxyethyl acrylate, 3-sulfopropyl acrylate potassium salt, 2-propyl acrylic acid, 2-(trifluoromethyl)acrylic acid, methacrylic acid, 2-methyl-2-propene-1-sulfonic acid sodium salt, mono-2-(methacryloyloxy)ethyl maleate, 3-sulfopropyl methacrylate potassium salt, 2- acrylamido-2-methyl-l-propanesulfonic acid, 3-methacrylamido phenyl boronic acid, vinyl sulfonic acid and vinyl phosphonic acid.

8. The membrane of claim 1 , wherein the grafted, asymmetric, porous, ultra high molecular weight polyethylene membrane has a water flow rate that is at least 75% of the water flow rate of an ungrafted, asymmetric, porous ultra high molecular weight polyethylene membrane having a bubble point determined by the ethoxy nonafluorobutane bubble point test that is between about 78 psi and about 160 psi.

9. A grafted, crosslinked, asymmetric, porous, ultra high molecular weight polyethylene membrane comprising:

one or more neutral groups or ion exchange groups grafted to one or more surfaces of the membrane, wherein the one or more neutral groups or ion exchange groups are crosslinked with a crosslinker; and

benzophenone adsorbed onto the membrane;

wherein the membrane has a bubble point between about 78 psi and 160 psi when determined by an ethoxy nonafluorobutane bubble point test;

wherein the membrane has a water flow rate that is at least 50% of the water flow rate of an ungrafted, asymmetric, porous ultra high molecular weight polyethylene membrane having a bubble point determined by the ethoxy nonafluorobutane bubble point test that is between about 78 psi and about 160 psi;

wherein the membrane wets in water in 10 seconds or less; and

wherein the membrane has a surface tension between 70 dyne/cm and 72 dynes/cm.

10. A method of making a grafted, asymmetric, porous ultra high molecular weight polyethylene membrane of claim 1 , comprising:

a) contacting an asymmetric, ultra high molecular weight polyethylene membrane with an alcohol solution comprising benzophenone;

b) contacting the polyethylene membrane with an aqueous exchange solution;

c) contacting the membrane with an aqueous grafting solution comprising:

i) one or more of an anionic monomer, cationic monomer, and neutral monomer; and

ii) one or more of sodium sulfate and sodium persulfate;

d) exposing the membrane to ultraviolet electromagnetic radiation, thereby resulting in a grafted, asymmetric, porous ultra high molecular weight polyethylene membrane.

11. The method of claim 10 , wherein the neutral monomer is N-(hydroxymethyl)acrylamide.

12. The method of claim 10 , wherein the neutral monomer is 2-hydroxyethylacrylate.

13. The method of claim 10 , wherein the cationic monomer is (3-acrylamidopropyl) trimethylammonium chloride.

14. The method of claim 10 , wherein the cationic monomer is (vinylbenzyl) trimethylammonium chloride.

15. The method of claim 10 , wherein the anionic monomer is acrylamidopropyl sulfonic acid.

16. The method of claim 10 , wherein the cationic monomer is selected from the group consisting of 2-(dimethylamino)ethyl hydrochloride acrylate, [2-(acryloyloxy)-ethyl]trimethylammonium chloride, 2 aminoethyl methacrylate hydrochloride, N-(3-aminopropyl) methacrylate hydrochloride, 2 (dimethylamino)ethyl methacrylate hydrochloride, [3-(methacryloylamino)propyl]trimethylammonium chloride solution, [2 (methacryloyloxy)ethyl]trimethylammonium chloride, acrylamidopropyl trimethylammonium chloride, 2-aminoethyl methacrylamide hydrochloride, N-(2-aminoethyl) methacrylamide hydrochloride, N-(3-Aminopropyl)-methacrylamide hydrochloride, diallyldimethylammonium chloride, allylamine hydrochloride, vinyl imidazolium hydrochloride, vinyl pyridinium hydrochloride and vinyl benzyl trimethyl ammonium chloride.

17. The method of claim 10 , wherein the anionic monomers is selected from the group consisting of 2 ethylacrylic acid, acrylic acid, 2-carboxyethyl acrylate, 3-sulfopropyl acrylate potassium salt, 2-propyl acrylic acid, 2-(trifluoromethyl)acrylic acid, methacrylic acid, 2-methyl-2-propene-1-sulfonic acid sodium salt, mono-2-(methacryloyloxy)ethyl maleate, 3-sulfopropyl methacrylate potassium salt, 2-acrylamido-2-methyl-1-propanesulfonic acid, 3 methacrylamido phenyl boronic acid, vinyl sulfonic acid and vinyl phosphonic acid.

18. The method of claim 10 , wherein the aqueous grafting solution further comprises a crosslinker.

19. The method of claim 10 , wherein the grafting solution comprises one or more of (3 acrylamidopropyl)trimethylammonium chloride, N-(hydroxymethyl)acrylamide), and (vinylbenzyl)trimethylammonium chloride.

20. The method of claim 10 , wherein the aqueous exchange solution comprises one or more of sodium sulfate and sodium persulfate.

Assignments (4)
SECURITY INTEREST Recorded Jul 8, 2022
From: ENTEGRIS, INC.; ENTEGRIS GP, INC.; POCO GRAPHITE, INC.; CMC MATERIALS, INC.; INTERNATIONAL TEST SOLUTIONS, LLC; QED TECHNOLOGIES INTERNATIONAL, INC.
To: TRUIST BANK, AS NOTES COLLATERAL AGENT
Reel/Frame 060613/0072 →
ASSIGNMENT OF PATENT SECURITY INTEREST RECORDED AT REEL/FRAME 048811/0679 Recorded Nov 5, 2019
From: GOLDMAN SACHS BANK USA
To: MORGAN STANLEY SENIOR FUNDING, INC.
Reel/Frame 050965/0035 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 9, 2019
From: JABER, JAD ALI; GJOKA, ALKETA
To: ENTEGRIS, INC.
Reel/Frame 050014/0681 →
SECURITY INTEREST Recorded Nov 13, 2018
From: ENTEGRIS, INC.; SAES PURE GAS, INC.
To: GOLDMAN SACHS BANK USA
Reel/Frame 048811/0679 →