Method of device having biostable elastomeric polymers having quaternary carbons

• US 6,197,240 B1
• Filed: 05/10/1999
• Issued: 03/06/2001
• Est. Priority Date: 07/29/1996
• Status: Expired due to Term

• Current Assignee: Lifeshield Sciences LLC (Acacia Research Corporation)
• Original Assignee: Corvita Corporation (Boston Scientific Corporation)
• Inventors: Pinchuk, Leonard
• Primary Examiner(s): Silbaugh, Jan H.
• Assistant Examiner(s): JONES, KENNETH MITCHELL
• Application Number:
  US09/309,007
• Time in Patent Office: 666 Days
• Field of Search: 264/309, 264/310, 264/330, 264/331.11, 264/331.15, 264/331.17, 264/331.18, 427/2.1, 427/2.24, 427/2.25
• US Class Current: 264/309
• CPC Class Codes: A61L 27/16 obtained by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: B29C 41/08 Coating a former, core or other substrate by spraying or fluidisation, e.g. spraying powder spray-up of reinforcing fibres B29C70/305
• CPC Class Codes: B29L 2031/7532 Artificial members, protheses
• CPC Class Codes: C08L 53/00 Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• CPC Class Codes: Y10S 623/901 Method of manufacturing prosthetic device

Abstract

An article of manufacture and method of making and implanting the article made of a polyolefin star or linear copolymer are disclosed in which the polyolefin copolymer is biostable and crack-resistant when implanted in vivo. The polyolefin copolymer is the reaction product of a rubbery component which when homopolymerized produces a polymer having a low level of hardness, and a hardening component which when homopolymerized produces a polymer having a high level of hardness. The polyolefin copolymer is elastomeric, has a hardness intermediate the low and high levels of hardness, and has a backbone in which the majority of polymer linkages along the copolymer chain are alternating quaternary and secondary carbon atoms.

Claims

1. A method of making an endoluminal or vascular device for in vivo implant and which is formed of a polymer which is resistant to degradation and cracking when in vivo implanted, comprising the steps of:

applying the polymer when in fluid form on a surface;

solidifying the polymer from its fluid form on the surface to form a non-woven membrane mat; and

removing the non-woven membrane mat from the surface,

wherein said polymer is a polyolefin copolymer;

said polyolefin copolymer having a backbone in which the majority of polymer linkages along the copolymer chain are alternating quaternary and secondary carbon atoms;

said polyolefin copolymer being a reaction product of a first rubbery component having a quaternary carbon atom which when homopolymerized produces a polymer having a low level of hardness, and a second hardening component which when homopolymerized produces a polymer having a high level of hardness; and

said polyolefin copolymer reaction product of said first and second components is elastomeric and having a hardness intermediate said low and high levels of hardness.

2. The method of claim 1, wherein said surface is rotated as the polymer is sprayed thereon.

3. The method of claim 1, wherein the polymer is dissolved in a solvent, and is applied to said surface while in fluid form by spraying thereon, and the solvent is evaporated while spraying to form said non-woven membrane mat on the surface.

4. The method of claim 1, wherein the solidified polymer is an elastic copolymer.

5. The method of claim 1, wherein the non-woven membrane mat is porous.

6. The method of claim 1, wherein said polyolefin copolymer reaction product is a star or linear copolymer.

7. The method of claim 1, wherein said first rubbery component is polyisobutylene.

8. The method of claim 7, wherein said second hardening component is selected from the group consisting of styrene, α

-methylstyrene, methylmethacrylate, ethylmethacrylate and hydroxyethyl methacrylate.

9. The method of claim 1, wherein said second hardening component is selected from the group consisting of styrene, α

-methylstyrene, methylmethacrylate, ethylmethacrylate and hydroxyethyl methacrylate.

10. The method of claim 1, wherein said surface if rotated and the polymer is dissolved in a solvent and applied to said rotating surface while in fluid form by spraying thereon, and the solvent is evaporated while spraying to form said non-woven membrane mat on the surface;

the solidified polymer is an elastic copolymer; and

the non-woven membrane mat is porous.

11. The method of claim 1, wherein said polymer is applied to said surface by spraying.

12. A method of making an endoluminal or vascular device for in vivo implant and which is formed of a polymer which is resistant to degradation and cracking when in vivo implanted, comprising the steps of:

applying the polymer when in fluid form on a surface;

solidifying the polymer from its fluid form on the surface to form a non-woven membrane mat; and

removing the non-woven membrane mat from the surface,

wherein the reaction product has the formulation;

where R and R′

are non-cyclic or cyclic aliphatic moieties having from 1 to about 8 carbon atoms, R″

is a hydrogen, hydroxyl, methyl or ethyl group, and R′

″

is an aromatic phenyl, benzyl or substituted benzyl group, COOCH₃, methoxy, ethoxy, aliphatic, cycloaliphatic, or substituted aliphatic, and such that homopolymers of

have a high level of hardness, n and m are from about 250 to about 5000, and p is about 1-10.

13. A method of making an endoluminal or vascular device for in vivo implant and which is formed of a polymer which is resistant to degradation and cracking when in vivo implanted, comprising the steps of:

applying the polymer when in fluid form on a surface;

solidifying the polymer from its fluid form on the surface to form a non-woven membrane mat; and

removing the non-woven membrane mat from the surface,

wherein the reaction product has the formulation;

where R and R′

are non-cyclic or cyclic aliphatic moieties having from 1 to about 8 carbon atoms, R″

is a hydrogen, hydroxyl, methyl or ethyl group, and R′

″

is an aromatic phenyl, benzyl or substituted benzyl group, COOCH₃, methoxy, ethoxy, aliphatic, cycloaliphatic, or substituted aliphatic, and such that homopolymers of

have a high level of hardness, n and m are from about 250 to about 5000, and p is about 1-10.

14. A method of making an endoluminal or vascular device for in vivo implant and which is formed of a polymer which is resistant to degradation and cracking when in vivo implanted, comprising the steps of:

applying the polymer when in fluid form on a surface;

solidifying the polymer from its fluid form on the surface to form a non-woven membrane mat; and

removing the non-woven membrane mat from the surface,

wherein said surface is rotated as the polymer is sprayed thereon;

the polymer which is sprayed while in fluid form is dissolved in a solvent, and the solvent is evaporated while spraying to form said non-woven membrane mat on the surface;

the solidified polymer is an elastic copolymer; and

the non-woven membrane mat is porous,

wherein said polymer is a polyolefin copolymer;

said polyolefin copolymer having a backbone in which the majority of polymer linkages along the copolymer chain are alternating quaternary and secondary carbon atoms;

said polyolefin copolymer being a reaction product of a first rubbery component having a quaternary carbon atom which when homopolymerized produces a polymer having a low level of hardness, and a second hardening component which when homopolymerized produces a polymer having a high level of hardness; and

said polyolefin copolymer reaction product of said first and second components is elastomeric and having a hardness intermediate said low and high levels of hardness.

15. The method of claim 14, wherein said polyolefin copolymer reaction product is a star or linear copolymer.

16. The method of claim 14, wherein said first rubbery component is polyisobutylene.

17. The method of claim 16, wherein said second hardening component is selected from the group consisting of styrene, α

-methylstyrene, methylmethacrylate, ethylmethacrylate and hydroxyethyl methacrylate.

18. The method of claim 14, wherein said second hardening component is selected from the group consisting of styrene, α

-methylstyrene, methylmethacrylate, ethylmethacrylate and hydroxyethyl methacrylate.

19. A method of making an endoluminal or vascular device for in vivo implant and which is formed of a polymer which is resistant to degradation and cracking when in vivo implanted, comprising the steps of:

applying the polymer when in fluid form on a surface;

solidifying the polymer from its fluid form on the surface to form a non-woven membrane mat; and

removing the non-woven membrane mat from the surface,

wherein said surface is rotated as the polymer is sprayed thereon;

the polymer which is sprayed while in fluid form is dissolved in a solvent, and the solvent is evaporated while spraying to form said non-woven membrane mat on the surface;

the solidified polymer is an elastic copolymer; and

the non-woven membrane mat is porous,

wherein the reaction product has the formulation;

where R and R′

are non-cyclic or cyclic aliphatic moieties having from 1 to about 8 carbon atoms, R″

is a hydrogen, hydroxyl, methyl or ethyl group, and R′

″

is an aromatic phenyl, benzyl or substituted benzyl group, COOCH₃, methoxy, ethoxy, aliphatic, cycloaliphatic, or substituted aliphatic, and such that homopolymers of

have a high level of hardness, n and m are from about 250 to about 5000, and p is about 1-10.

20. A method of making an endoluminal or vascular device for in vivo implant and which is formed of a polymer which is resistant to degradation and cracking when in vivo implanted, comprising the steps of:

applying the polymer when in fluid form on a surface;

solidifying the polymer from its fluid form on the surface to form a non-woven membrane mat; and

removing the non-woven membrane mat from the surface,

wherein said surface is rotated as the polymer is sprayed thereon;

the polymer which is sprayed while in fluid form is dissolved in a solvent, and the solvent is evaporated while spraying to form said non-woven membrane mat on the surface;

the solidified polymer is an elastic copolymer; and

the non-woven membrane mat is porous,

wherein the reaction product has the formulation;

where R and R′

are non-cyclic or cyclic aliphatic moieties having from 1 to about 8 carbon atoms, R″

is a hydrogen, hydroxyl, methyl or ethyl group, and R′

″

is an aromatic phenyl, benzyl or substituted benzyl group, COOCH₃, methoxy, ethoxy, aliphatic, cycloaliphatic, or substituted aliphatic, and such that homopolymers of

have a high level of hardness, n and m are from about 250 to about 5000, and p is about 1-10.