Polysulfone-urethane copolymer, membranes and products incorporating same, and methods for making and using same

• US 10,822,461 B2
• Filed: 09/28/2018
• Issued: 11/03/2020
• Est. Priority Date: 10/05/2017
• Status: Active Grant

• Current Assignee: Fresenius Medical Care Holdings Incorporated (Fresenius Medical Care AG)
• Original Assignee: Fresenius Medical Care Holdings Incorporated (Fresenius Medical Care AG)
• Inventors: Russell, Geoffrey, White, James, Teo, Jiunn, Hudson, Kevin, Hall, Monica, Kosaraju, Praveen
• Primary Examiner(s): Dollinger, Michael M
• Application Number:
  US16/145,225
• Publication Number:
  US 20190106545A1
• Time in Patent Office: 767 Days
• CPC Class Codes: A61M 1/1698 Blood oxygenators with or without heat-exchangers intracorporal A61M1/1678; manufacturing of membranes therefor B01D67/00; semi-permeable membranes for separation processes characterised by their properties B01D69/00; semi-permeable membranes characterised by their material B01D71/00
• CPC Class Codes: A61M 1/34 Filtering material out of the blood by passing it through a membrane, i.e. hemofiltration or diafiltration
• CPC Class Codes: B01D 61/24 Dialysis ; Membrane extraction
• CPC Class Codes: B01D 67/00111 Polymer pretreatment in the casting solutions
• CPC Class Codes: B01D 67/00135 Air gap characteristics
• CPC Class Codes: B01D 69/06 Flat membranes
• CPC Class Codes: B01D 71/441 Polyvinylpyrrolidone
• CPC Class Codes: B01D 71/5211 Polyethylene glycol or polyethyleneoxide
• CPC Class Codes: B01D 71/522 Aromatic polyethers
• CPC Class Codes: B01D 71/54 Polyureas; Polyurethanes
• CPC Class Codes: B01D 71/68 Polysulfones; Polyethersulfones
• 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: C08G 18/5072 containing sulfur
• CPC Class Codes: C08G 18/7657 containing two or more aromatic rings
• CPC Class Codes: C08G 81/00 Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers involving only carbon-to-carbon unsaturated bond reactions C08F299/00 ; polyester-amides C08G69/44; polyester-imides C08G73/16; polyamides-imides C08G73/14; block- or graft polymers containing polysiloxane sequences C08G77/42
• CPC Class Codes: C08J 2375/04 Polyurethanes
• CPC Class Codes: C08J 2381/08 Polysulfonates
• CPC Class Codes: C08J 2439/06 Homopolymers or copolymers of N-vinyl-pyrrolidones
• CPC Class Codes: C08J 5/18 Manufacture of films or sheets
• CPC Class Codes: C08L 75/04 Polyurethanes
• CPC Class Codes: C08L 81/06 : Polysulfones; Polyethersulfones

Abstract

A polysulfone-urethane copolymer is disclosed, which can be used as a membrane polymer, e.g., a matrix polymer, a pore forming agent, or both, while enhancing a membrane'"'"'s blood compatibility. Methods are disclosed for forming the copolymer and incorporating the copolymer in membranes (e.g., spun hollow fibers, flat membranes) and other products.

Claims

1. A polysulfone-urethane copolymer comprising formula (I) or formula (II):

-[D-E]_a1-[D-G-D]_a2-[E-D]_a3- 

 

(I)

[D-(E-D)_b1-(G)_b2-(D-E)_b3]_b4- 

 

(II)

wherein G is a urethane block, D is a divalent residue of an aromatic dihydroxyl compound, E is an aromatic sulfone group, and wherein i) a1, a2 and a3 are independently from 1-100 which randomly or non-randomly repeat in formula (I), and ii) b1, b2, b3, and b4 are independently from 1-100 which randomly or non-randomly repeat in formula (II), and wherein the urethane block is a urethane from a reaction of a diisocyanate and a polyol and wherein the polyol consists of the formula;

HO—

(—

CH(Z)—

CH₂—

O)_n1—

H, where Z is CH₃ or H and n1 is from 1 to 100.

2. The polysulfone-urethane copolymer of claim 1, having formula (I):

-[D-E]_a1-[D-G-D]_a2-[E-D]_a3-

wherein a1 and a3 are independently from 10-100 and a2 is from 1-10 units which randomly or non-randomly repeat in formula (I).

3. The polysulfone-urethane copolymer of claim 1, having formula (II):

[D-(E-D)_b1-(G)_b2-(D-E)_b3]_b4-

wherein b1 and b3 are independently from 10-100 and b2 and b4 are independently from 1-10 units which randomly or non-randomly repeat in formula (II).

4. The polysulfone-urethane copolymer of claim 1, having formula

J-D----[X]_g-[D-G-D]_y-[X]_i----D-J

wherein J is an end group of the polymer, X is a polysulfone block comprised of aromatic dihydroxyl compound and dihalodiphenyl sulfone, wherein g and i are independently from 1-100 units.

5. The polysulfone-urethane copolymer of claim 4, wherein each J is a mono-reacted residue of a dihalodiphenyl sulfone or a polysulfone block containing an aromatic dihydroxyl compound and a dihalodiphenyl sulfone end unit.

6. The polysulfone-urethane copolymer of claim 1, wherein D is a di-reacted residue of a dihydroxydiphenyl sulfone or a dihydroxybiphenyl.

7. The polysulfone-urethane copolymer of claim 1, which has a weight average molecular weight of from about 10,000 to about 750,000 g/mol.

8. A membrane comprising the polysulfone-urethane copolymer of claim 1.

9. The membrane of claim 8, wherein the membrane is a hollow fiber or a flat sheet.

10. The membrane of claim 8, wherein said membrane contains from 0 to less than 50 wt % total polyvinylpyrrolidone or polyethylene glycol.

11. A method for preparing the polysulfone-urethane copolymer of claim 1, comprising:

1) reacting at least one oligo- or polyurethane block with an aromatic dihydroxyl compound which end caps the at least one oligo- or polyurethane block to form an end-capped oligo- or polyurethane block; and

2) reacting the end-capped oligo- or polyurethane block with an aromatic diol and a dihalodiphenyl sulfone to form a polysulfone-urethane copolymer with control of stoichiometry so that the polysulfone-urethane copolymer has dihalodiphenyl sulfone end groups.

12. The method of claim 11, further comprising 3) adding a dihalodiphenyl sulfone and/or an aromatic diol to complete the polymerization or build molecular weight of the copolymer.

13. The method of claim 11, further comprising preparing the at least one oligo- or polyurethane block by reacting diisocyanate and an organic polyol compound to form the at least one oligo- or polyurethane block.

14. The method of claim 11, wherein the reacting the at least one oligo- or polyurethane block with the aromatic dihydroxyl compound is performed in the presence of metal carbonate, aprotic polar solvent, and excess of the aromatic dihydroxyl compound.

15. The method of claim 11, wherein the aromatic dihydroxyl compound is a bisphenol and the dihalodiphenyl sulfone is a 4,4′

-dihalodiphenyl sulfone.

16. A method for preparing the polysulfone-urethane copolymer of claim 1, comprising:

1) reacting an aromatic diol and a dihalodiphenyl sulfone to form a polysulfone block, and control the stoichiometry so that the polysulfone block is end-capped with residue of an aromatic diol; and

2) reacting at least one oligo- or polyurethane block, an aromatic dihydroxyl compound, and the polysulfone block to form a polysulfone-urethane copolymer.

17. The method of claim 16, further comprising 3) adding a dihalodiphenyl sulfone and/or an aromatic diol to complete the polymerization or build molecular weight of the copolymer.

18. The method of claim 16, further comprising preparing the at least one oligo- or polyurethane block by reacting diisocyanate and an organic polyol compound to form the at least one oligo- or polyurethane block.

19. A process of making a membrane comprising preparing a dope solution containing the polysulfone-urethane copolymer of claim 1, and forming a hollow fiber or flat sheet with the dope solution.

20. The polysulfone-urethane copolymer of claim 1, wherein G is a series of urethane blocks.