Hydrophilic-oleophobic copolymer composition and uses thereof

• US 10,569,234 B2
• Filed: 11/03/2016
• Issued: 02/25/2020
• Est. Priority Date: 11/15/2013
• Status: Expired due to Fees

• Current Assignee: BL Technologies Inc. (Ashland Global Holdings, Inc.)
• Original Assignee: BL Technologies Inc. (Ashland Global Holdings, Inc.)
• Inventors: Carr, Louisa Ruth, Smigelski, Jr., Paul Michael, Nichols, Jason Michael, Silva, James Manio
• Primary Examiner(s): Fortuna, Ana M
• Application Number:
  US15/342,370
• Publication Number:
  US 20170050154A1
• Time in Patent Office: 1,209 Days
• CPC Class Codes: B01D 2325/0283 Pore size
• CPC Class Codes: B01D 2325/18 Membrane materials having mixed charged functional groups
• CPC Class Codes: B01D 2325/36 Hydrophilic membranes
• CPC Class Codes: B01D 61/145 Ultrafiltration
• CPC Class Codes: B01D 61/147 Microfiltration
• CPC Class Codes: B01D 71/76 Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 rubbers in general B01D71/24
• CPC Class Codes: B01D 71/82 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
• CPC Class Codes: C02F 1/444 by ultrafiltration or microfiltration
• CPC Class Codes: C02F 1/58 by removing specified dissolved compounds using ion-exchange C02F1/42; softening water C02F5/00
• CPC Class Codes: C02F 2101/32 Hydrocarbons, e.g. oil
• CPC Class Codes: C02F 2303/20 Prevention of biofouling
• CPC Class Codes: C02F 2305/00 Use of specific compounds during water treatment
• CPC Class Codes: C08F 220/14 Methyl esters , e.g. methyl (meth)acrylate
• CPC Class Codes: C08F 220/24 containing perhaloalkyl radicals
• CPC Class Codes: C08F 220/283 and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
• CPC Class Codes: C08F 220/387 and containing nitrogen and oxygen
• CPC Class Codes: C08F 220/603 and containing oxygen in addition to the carbonamido oxygen and nitrogen
• CPC Class Codes: C08F 220/606 and containing other heteroatoms
• CPC Class Codes: C08J 2327/18 Homopolymers or copolymers of tetrafluoroethylene
• CPC Class Codes: C08J 2433/14 of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• CPC Class Codes: C08J 7/0427 : with only one layer of a composition containing a polymer binder with more layers C08J7/042
• CPC Class Codes: C08J 7/056 : Forming hydrophilic coatings
• CPC Class Codes: C08J 9/365 : Coating
• CPC Class Codes: C09D 133/14 : of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen

Abstract

Provided herein are copolymers and copolymer compositions that are both hydrophilic and oleophobic. The copolymers include structural units derived from a fluoroalkyl monomer and a zwitterionic monomer. It further relates to membranes formed by coating a porous substrate with the copolymeric compositions. The copolymeric coating imparts hydrophilicity and oleophobicity/oil-tolerance to the membranes. The uses of such membranes as microfiltration membrane or ultrafiltration membrane are also provided.

Claims

1. A membrane comprising:

a porous substrate; and

a coating attached to the porous substrate, wherein the coating comprises a copolymer comprising 1 to 10 mole % of a structural unit of formula I and 90 to 99 mole % of a structural unit of formula II,

2. The membrane of claim 1, wherein

R¹ is a linear or branched C₃-C₁₀ fluoroalkyl group;

R₂ and R₃ are independently at each occurrence a hydrogen, or a methyl group;

R⁴ and R⁵ are independently at each occurrence a linear or branched C₁-C₃ alkyl group;

R⁶ and R⁷ are independently at each occurrence a linear C₁-C₅ alkylene group;

X is —

O—

; and

m and n are independently at each occurrence an integer ranging from 2 to 4.

3. The membrane of claim 2, wherein R¹ is a C₅-C₈ perfluoroalkyl group.

4. The membrane of claim 3, wherein R¹ is —

C₆F₁₃.

5. The membrane of claim 4, wherein the porous substrate comprises a polymer selected from the group consisting of polytetrafluoroethylene, expanded polytetrafluoroethylene, polysulfone, polyethersulfone, polypropylene, polyvinylidine fluoride, polyamide, polystyrene, polyethylene, polyacrylonitrile, cellulose-based materials, and combinations thereof.

6. The membrane of claim 5, wherein the porous substrate is expanded polytetrafluoroethylene.

7. The membrane of claim 6, wherein the porous substrate has a pore size ranging from about 0.01 micron to about 50 micron.

8. The membrane of claim 1, wherein:

R¹ is a linear C₅-C₈ perfluoroalkyl group;

R², R³, R⁴ and R⁵ are methyl groups;

R⁶ is a C₁ alkylene group;

R⁷ is a linear C₃ alkylene group;

X is —

O—

;

Y is a sulfite group;

m is 2; and

n is 1.

9. A membrane comprising:

a porous substrate; and

a coating attached to the porous substrate, wherein the coating comprises a copolymer comprising 1 to 10 mole % of a structural unit of formula VII and 90 to 99 mole % of a structural unit of formula VIII, and wherein R¹ is a linear C₅-C₈ fluoroalkyl group.

10. The membrane of claim 9, wherein R¹ of the copolymer is —

C₆F₁₃.

11. The membrane of claim 10, wherein the copolymer comprises a structural unit of formula IX

12. The membrane of claim 11, wherein the porous substrate comprises a polymer selected from the group consisting of polytetrafluoroethylene, expanded polytetrafluoroethylene, polysulfone, polyethersulfone, polypropylene, polyvinylidine fluoride, polyamide, polystyrene, polyethylene, polyacrylonitrile, cellulose-based materials and combinations thereof.

13. The membrane of claim 12, wherein the porous substrate is expanded polytetrafluoroethylene.

14. The membrane of claim 13, wherein the porous substrate has a pore size ranging from about 0.01 micron to about 50 micron.

15. The membrane of claim 14, wherein the copolymer comprises 10 mole % of the structural unit of formula VII, and 90 mole % of the structural unit of formula VIII.

16. The membrane of claim 15, wherein the membrane has a contact angle of up to 20°

for water and a contact angle of at least 60°

for a hydrocarbon.