# US 8,772,429 B2 · Biomaterial

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- Number: US 8,772,429 B2
- Document ID: US8772429B2
- Status: Granted
- Kind: B2
- Application number: 12/971,384
- Filed: 2010-12-17
- Published: 2011-06-23
- Granted: 2014-07-08
- Earliest claimed: 2009-12-18
- Assignees: Vysera Biomedical Limited
- Applicants: Niall Behan
- Inventors: Niall Behan
- Web page: https://patentgrep.com/patent/US8772429B2

## CPC

- C08G 77/42: Block-or graft-polymers containing polysiloxane sequences (polymerising aliphatic unsaturated monomers on to a polysiloxane C08F283/12)
- A61L 27/18: obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- A61L 27/34: Macromolecular materials
- A61L 29/06: obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- A61L 29/085: {Macromolecular materials}
- C08G 18/10: Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G 18/61: Polysiloxanes
- C08G 18/69: Polymers of conjugated dienes {(hydrogenated polymers of conjugated dienes C08G18/6208)}
- C08G 77/458: containing polyurethane sequences
- C08G 2110/0008: flexible
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- A61L: METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES (preservation of bodies or disinfecting characterised by the agents employed A01N; preserving, e.g. sterilising, food or foodstuffs A23; preparations for medical, dental or toiletry purposes A61K)

## Abstract

The present invention provides a triblock copolymer and a viscoelastic biostable foam comprising the same.

## Claims

### Claim 1

A block copolymer of the formula [polybutadiene][polyalkyl ether][polysiloxane][polyalkylether][polybutadiene].

### Claim 2

A block copolymer of formula I
wherein:
each represents a point of attachment to a urethane or urea linkage;
each of R1, R2, R3, and R4 is independently selected from one or more of halogen, R, OR, —CO2R, a fluorinated hydrocarbon, a polyether, a polyester or a fluoropolymer;
each R is independently hydrogen, an optionally substituted C1-20 aliphatic group, or an optionally substituted group selected from phenyl, 8-10 membered bicyclic aryl, a 4-8 membered monocyclic saturated or partially unsaturated heterocyclic ring having 1-2 heteroatoms independently selected from nitrogen, oxygen, or sulphur, or 5-6 membered monocyclic or 8-10 membered bicycle heteroaryl group having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
each of m n and p is independently 2 to 100; and
each of L1 and L2 is independently a bivalent C1-20 hydrocarbon chain wherein 1-4 methylene units of the hydrocarbon chain are optionally and independently replaced by —O—, —S—, —N(R)C(O)O—, —N(R)C(O)N(R)—, —OC(O)N(R)—, —N(R)—, —C(O)—, —C(O)N(R)—, —N(R)C(O)—, —SO2—, —SO2N(R)—, —N(R)SO2—, —OC(O)—, —C(O)O—, or a bivalent cycloalkylene, arylene, heterocyclene, or heteroarylene.

### Claim 3 (depends on 2)

The copolymer according to claim 2, wherein R1 and R2 are methyl, one or both of R3 and R4 is independently a C1-20 hydrocarbon chain wherein 1-4 methylene units of the hydrocarbon chain are optionally and independently substituted by halogen, and L1 and L2 are independently a bivalent C1-20 hydrocarbon chain wherein 1-4 methylene units of the hydrocarbon chain are optionally and independently replaced by —NHC(O)O— or —NHC(O)NH—.

### Claim 4 (depends on 2)

The copolymer according to claim 2, wherein R1 and R2 are methyl, one or both of R3 and R4 is independently a C1-20 hydrocarbon chain wherein 1-4 methylene units of the hydrocarbon chain are optionally and independently substituted by halogen, L1 is —NHC(O)O— or —NHC(O)NH—, and L2 is a C1-20 hydrocarbon chain.

### Claim 5 (depends on 2)

The copolymer according to claim 2, wherein R1 and R2 are methyl, one or both of R3 and R4 is independently a C1-20 hydrocarbon chain, L1 is —NHC(O)O— or —NHC(O)NH—, and L2 is a C1-20 hydrocarbon chain.

### Claim 6 (depends on 2)

The copolymer according to claim 2, wherein m and p are each independently between 2 and 50 and n is between 2 and 20.

### Claim 7 (depends on 6)

The copolymer according to claim 6, wherein m and p are each independently between 2 and 30 and n is between 2 and 20.

### Claim 8 (depends on 6)

The copolymer according to claim 6, wherein each of m, n, and p are 8-16.

### Claim 9 (depends on 2)

The copolymer according to claim 2, wherein one or more of R1, R2, R3, and R4 is independently an optionally substituted C1-6 alkyl.

### Claim 10 (depends on 9)

The copolymer according to claim 9, wherein each of R1, R2, R3, and R4 is independently methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, or cyclobutyl.

### Claim 11 (depends on 10)

The copolymer according to claim 10, wherein each of R1, R2, R3, and R4 is independently mono-, di-, tri, or perfluorinated methyl, ethyl, propyl, butyl, or phenyl.

### Claim 12 (depends on 9)

The copolymer according to claim 9, wherein each of R1, R2, R3, and R4 is independently methyl, ethyl, propyl, trifluoromethyl, trifluoroethyl, or trifluoropropyl.

### Claim 13 (depends on 2)

The copolymer according to claim 2 wherein each of L1 and L2 is independently a bivalent C1-20 alkylene chain.

### Claim 14 (depends on 13)

The copolymer according to claim 13 wherein each of L1 and L2 is independently a bivalent C1-10 alkylene chain.

### Claim 15 (depends on 13)

The copolymer according to claim 13 wherein each of L1 and L2 is independently a bivalent methylene, ethylene, propylene, or butylene chain.

### Claim 16 (depends on 2)

The copolymer according to claim 2 wherein each of L1 and L2 is independently —OCH2—, —OCH2CH2—, —OCH2CH2CH2—, or —OCH2CH2CH2CH2—.

### Claim 17 (depends on 2)

The copolymer according to claim 2 wherein each of L1 and L2 is independently a bivalent C1-6 alkylene chain wherein at least one methylene unit of the chain is replaced by —O— and at least one methylene unit of the chain is replaced by a bivalent arylene.

### Claim 18 (depends on 17)

The copolymer according to claim 17 wherein each of L1 and L2 is independently —OCH2-phenylene-, —OCH2CH2-phenylene-, —OCH2CH2-phenylene-CH2—, or —OCH2CH2CH2CH2-phenylene-.

### Claim 19 (depends on 2)

The copolymer according to claim 2, wherein at least one of L1 and L2 is a bivalent C1-20 hydrocarbon chain wherein 1-4 methylene units of the hydrocarbon chain are optionally and independently replaced by: —N(H)C(O)N(H)—, —N(H)C(O)O—, or —OC(O)N(H)—.

### Claim 20 (depends on 2)

The copolymer according to claim 2, wherein L1 is a urethane.

### Claim 21 (depends on 2)

The copolymer according to claim 2, wherein L2 is —CH2CH2—.

### Claim 22

A block copolymer of formula II:
wherein:
each of Rx and Ry is independently —OH, —NH2, a protected hydroxyl or a protected amine;
each of R1, R2, R3, and R4 is independently selected from one or more of halogen, R, OR, —CO2R, a fluorinated hydrocarbon, a polyether, a polyester or a fluoropolymer;
each R is independently hydrogen, an optionally substituted C1-20 aliphatic group, or an optionally substituted group selected from phenyl, 8-10 membered bicyclic aryl, a 4-8 membered monocyclic saturated or partially unsaturated heterocyclic ring having 1-2 heteroatoms independently selected from nitrogen, oxygen, or sulphur, or 5-6 membered monocyclic or 8-10 membered bicyclic heteroaryl group having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
each of m, n, and p is independently 2 to 100; and
each of L1 and L2 is independently a bivalent C1-20 hydrocarbon chain wherein 1-4 methylene units of the hydrocarbon chain are optionally and independently replaced by —O—, —S—, —N(R)C(O)O—, —N(R)C(O)N(R)—, —OC(O)N(R)—, —N(R)—, —C(O)—, —C(O)N(R)—, —N(R)C(O)—, —SO2—, —SO2N(R)—, —N(R)SO2—, —OC(O)—, —C(O)O—, or a bivalent cycloalkylene, arylene, heterocyclene, or heteroarylene.

### Claim 23 (depends on 22)

The copolymer according to claim 22, wherein both of Rx and Ry are —OH.

### Claim 24 (depends on 22)

The copolymer according to claim 22, selected from any of formulae II-a, II-b, II-c, and II-d:

### Claim 25 (depends on 2)

The copolymer according to claim 2, selected from:

### Claim 26 (depends on 2)

A biomaterial comprising the block copolymer according to claim 2.

### Claim 27 (depends on 2)

A medical device comprising the block copolymer according to claim 2.

### Claim 28

A viscoelastic biostable foam comprising the block copolymer of formula I
wherein:
each represents a point of attachment to a urethane or urea linkage;
each of R1, R2, R3, and R4 is independently selected from one or more of halogen, R, OR, —CO2R, a fluorinated hydrocarbon, a polyether, a polyester or a fluoropolymer;
each R is independently hydrogen, an optionally substituted C1-20 aliphatic group, or an optionally substituted group selected from phenyl, 8-10 membered bicyclic aryl, a 4-8 membered monocyclic saturated or partially unsaturated heterocyclic ring having 1-2 heteroatoms independently selected from nitrogen, oxygen, or sulphur, or 5-6 membered monocyclic or 8-10 membered bicyclic heteroaryl group having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
each of m n and p is independently 2 to 100; and
each of L1 and L2 is independently a bivalent C1-20 hydrocarbon chain wherein 1-4 methylene units of the hydrocarbon chain are optionally and independently replaced by —O—, —S—, —N(R)C(O)O—, —N(R)C(O)N(R)—, —OC(O)N(R)—, —N(R)—, —C(O)—, —C(O)N(R)—, —N(R)C(O)—, —SO2—, —SO2N(R)—, —N(R)SO2—, —OC(O)—, —C(O)O—, or a bivalent cycloalkylene, arylene, heterocyclene, or heteroarylene.

### Claim 29 (depends on 28)

The viscoelastic biostable foam according to claim 28, comprising the triblock copolymer selected from

### Claim 30 (depends on 28)

The viscoelastic biostable foam according to claim 28, wherein said foam is stable to gastric fluid for at least 3 months, for at least 4 months, for at least 5 months, for at least 6 months, for at least 7 months, for at least 8 months, for at least 9 months, for at least 10 months, for at least 11 months, or for at least one year.

### Claim 31 (depends on 28)

The viscoelastic biostable foam according to claim 28, wherein said foam takes up less than about 5%, less than about 10%, less than about 15%, less than about 20%, less than about 25%, or less than about 30% by weight of water at equilibrium.

### Claim 32 (depends on 28)

The viscoelastic biostable foam according to claim 28, wherein said foam has an elongation capacity of about 200-1200%.

### Claim 33 (depends on 28)

The viscoelastic biostable foam according to claim 28, wherein said foam has a tensile strength of about 0.1 to about 1.0 MPa.

### Claim 34 (depends on 28)

The viscoelastic biostable foam according to claim 28, wherein said foam has a density of 0.1 to 1.5 g/cm3.

### Claim 35 (depends on 28)

The viscoelastic biostable foam according to claim 28, wherein R1 is hydrogen, methyl, chloro or fluoro.

### Claim 36 (depends on 28)

The viscoelastic biostable foam according to claim 28, wherein R2 is hydrogen or methyl.

### Claim 37 (depends on 28)

The viscoelastic biostable foam according to claim 28, wherein R3 is methyl, phenyl, fluoro, or —CH2CH2F.

### Claim 38 (depends on 28)

The viscoelastic biostable foam according to claim 28, wherein R4 is methyl, phenyl, fluoro, or —CH2CH2F.

### Claim 39 (depends on 1)

A biomaterial comprising the block copolymer of claim 1.

### Claim 40 (depends on 1)

A medical device comprising the block copolymer according to claim 1.

### Claim 41 (depends on 1)

A viscoelastic biostable foam comprising the block copolymer of claim 1.

### Claim 42 (depends on 41)

The viscoelastic biostable foam according to claim 41, wherein said foam is stable to gastric fluid for at least 3 months, for at least 4 months, for at least 5 months, for at least 6 months, for at least 7 months, for at least 8 months, for at least 9 months, for at least 10 months, for at least 11 months, or for at least one year.

### Claim 43 (depends on 41)

The viscoelastic biostable foam according to claim 41, wherein said foam takes up less than about 5%, less than about 10%, less than about 15%, less than about 20%, less than about 25%, or less than about 30% by weight of water at equilibrium.

### Claim 44 (depends on 41)

The viscoelastic biostable foam according to claim 41, wherein said foam has an elongation capacity of about 200-1200%.

### Claim 45 (depends on 41)

The viscoelastic biostable foam according to claim 41, wherein said foam has a tensile strength of about 0.1 to about 1.0 MPa.

### Claim 46 (depends on 41)

The viscoelastic biostable foam according to claim 41, wherein said foam has a density of 0.1 to 1.5 g/cm3.