# US 11,439,495 B2 · Self-healing graft material and method of use thereof

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- Number: US 11,439,495 B2
- Document ID: US11439495B2
- Status: Granted
- Kind: B2
- Application number: 16/545,311
- Filed: 2019-08-20
- Published: 2020-02-27
- Granted: 2022-09-13
- Earliest claimed: 2018-08-22
- Assignees: Cook Medical Technologies LLC
- Applicants: Cook Medical Technologies LLC
- Inventors: Ralf Spindler; Davorin Kevin Skender
- Web page: https://patentgrep.com/patent/US11439495B2

## CPC

- A61F 2/07: Stent-grafts
- A61F 2/90: characterised by a net-like or mesh-like structure
- C08G 18/10: Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G 18/246: {containing also tin-carbon bonds}
- C08G 18/3855: {having sulfur}
- C08G 18/4854: {Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group}
- C08G 18/735: {containing one isocyanate or isothiocyanate group linked to a primary carbon atom and at least one isocyanate or isothiocyanate group linked to a tertiary carbon atom}
- C08G 18/755: {and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate}
- C08L 75/04: Polyurethanes
- C08L 77/00: Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain (of polyhydrazides C08L79/06; of polyamideimides or polyamide acids C08L79/08); Compositions of derivatives of such polymers
- C09D 175/04: Polyurethanes
- A61F 2002/072: {Encapsulated stents, e.g. wire or whole stent embedded in lining}
- A61F 2210/0076: multilayered, e.g. laminated structures
- C08G 18/283: {Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds}
- C08G 64/081: {containing sulfur}
- A61F: FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS (dental prosthetics A61C)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)

## Abstract

The present disclosure relates to a graft material including a self-healing polymer layer and to implantable medical devices including such a graft material. The invention also relates to methods of using and manufacturing such graft materials and devices. In one embodiment, the implantable medical device is a stent graft.

## Claims

### Claim 1

A stent graft comprising:
an expandable stent having a luminal and an abluminal surface; and
a graft disposed on at least one of the luminal and the abluminal surface;
wherein the graft comprises a first layer comprising a self-healing polymer material; and wherein the self-healing polymer is a cross-linked co-polymer of a diamine and acrylic acid having a mixture of reversible hydrogen bonds and permanent covalent crosslinks.

### Claim 2 (depends on 1)

The stent-graft of claim 1, wherein the diamine is 1,12 diaminododecane.

### Claim 3 (depends on 1)

The stent-graft of claim 1 further comprising a second self-healing polymer layer, wherein the second self-healing polymer is a thermoplastic polyurethane comprising a hard segment component, a soft segment component and a chain extender component.

### Claim 4 (depends on 3)

The stent-graft of claim 3, wherein the hard segment component comprises a polymerized diisocyanate unit, wherein the diisocyanate is selected from the group consisting of isophorone diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), 4,4′ methylenebis(phenyl isocyanate) and hexamethylene diisocyanate.

### Claim 5 (depends on 3)

The stent-graft of claim 3, wherein the soft segment component comprises polymerized polytetramethylene ether glycol.

### Claim 6 (depends on 3)

The stent-graft of claim 3, wherein the chain extender component comprises polymerized bis(4-hydroxyphenyl) disulphide.

### Claim 7 (depends on 1)

The stent graft of claim 1, wherein the graft further comprises a second layer comprising a polymer selected from the group consisting of polytetrafluoroethylene, electro-spun polytetrafluoroethylene, expanded polytetrafluoroethylene, polyethylene terephthalate, polyester, polyurethane and Fluorinated ethylene propylene, and wherein the second layer is disposed on the first layer.

### Claim 8 (depends on 7)

The stent graft of claim 7, wherein the graft further comprises a third layer comprising a polymer selected from the group consisting of polytetrafluoroethylene, electro-spun polytetrafluoroethylene, expanded polytetrafluoroethylene, polyethylene terephthalate, polyester, polyurethane and fluorinated ethylene propylene, wherein the first layer is disposed between the second layer and the third layer.

### Claim 9 (depends on 1)

The stent-graft of claim 1, wherein the self-healing polymer material is woven, knitted or braided, and, wherein the self-healing polymer material imbedded in a polyurethane.

### Claim 10 (depends on 1)

The stent graft of claim 1, wherein the expandable stent comprises a plurality of interconnected struts at least partially imbedded within the first layer.

### Claim 11 (depends on 1)

The stent graft of claim 1, wherein the graft comprises a plurality of stacked layers the self-healing polymer material, wherein at least one of the plurality of stacked layers is separated from another of the plurality of stacked layers by a layer comprising a polymer selected from the group consisting of polytetrafluoroethylene, electro-spun polytetrafluoroethylene, expanded polytetrafluoroethylene, polyethylene terephthalate, polyester, polyurethane and fluorinated ethylene propylene.

### Claim 12

A stent graft comprising a stent and graft material, the graft material comprising a first layer comprising a self-healing polymer material and a second layer comprising a polymer selected from the group consisting of polytetrafluoroethylene, electro-spun polytetrafluoroethylene, expanded polytetrafluoroethylene, polyethylene terephthalate, polyester, polyurethane and fluorinated ethylene propylene, wherein the second layer is disposed on the first layer; and wherein the self-healing polymer is a cross-linked co-polymer of a diamine and acrylic acid having a mixture of reversible hydrogen bonds and permanent covalent crosslinks.

### Claim 13 (depends on 12)

The stent-graft of claim 12, wherein the diamine is 1,12 diaminododecane.

### Claim 14 (depends on 12)

The stent-graft of claim 12 further comprising a second self-healing polymer layer, wherein the second self-healing polymer is a thermoplastic polyurethane comprising a hard segment component, a soft segment component and a chain extender component.

### Claim 15 (depends on 14)

The stent-graft of claim 14, wherein the hard segment component comprises a polymerized diisocyanate unit, wherein the diisocyanate is selected from the group consisting of isophorone diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), 4,4′ methylenebis(phenyl isocyanate) and hexamethylene diisocyanate.

### Claim 16 (depends on 14)

The stent-graft of claim 14, wherein the soft segment component comprises polymerized polytetramethylene ether glycol.

### Claim 17 (depends on 14)

The stent-graft of claim 14, wherein the chain extender component comprises polymerized bis(4-hydroxyphenyl) disulphide.

### Claim 18 (depends on 12)

The stent graft of claim 12, wherein the graft further comprises a third layer comprising a polymer selected from the group consisting of polytetrafluoroethylene, electro-spun polytetrafluoroethylene, expanded polytetrafluoroethylene, polyethylene terephthalate, polyester, polyurethane and fluorinated ethylene propylene, wherein the first layer is disposed between the second layer and the third layer.

### Claim 19

A stent graft comprising:
an expandable stent comprising a tubular body with a lumen extending therethrough and having a luminal and an abluminal surface; and
a graft disposed on at least one of the luminal and the abluminal surface;
wherein the graft comprises:
a first layer comprising self-healing polymer, wherein the self-healing polymer is a cross-linked co-polymer of a diamine and acrylic acid having a mixture of reversible hydrogen bonds and permanent covalent crosslinks;
a second layer comprising electro-spun polytetrafluoroethylene or expanded polytetrafluoroethylene; and
a third layer comprising electro-spun polytetrafluoroethylene or expanded polytetrafluoroethylene,
wherein the first layer is disposed between the second layer and the third layer.
