Polymer blends for use in making medical devices including catheters and balloons for dilatation catheters

• US 5,554,120 A
• Filed: 07/25/1994
• Issued: 09/10/1996
• Est. Priority Date: 07/25/1994
• Status: Expired due to Term

• Current Assignee: Advanced Cardiovascular Systems Incorporated
• Original Assignee: Advanced Cardiovascular Systems Incorporated
• Inventors: Patel, Udayan, Muni, Ketan, Chen, Ziyun, Cheng, Tai, Saltman, Robert
• Primary Examiner(s): Short, Patricia A.
• Application Number:
  US08/280,764
• Time in Patent Office: 778 Days
• Field of Search: 604/93, 604/96, 525/166, 525/179
• US Class Current: 604/96.01
• CPC Class Codes: A61L 29/049 Mixtures of macromolecular compounds
• CPC Class Codes: A61M 2025/1031 Surface processing of balloon members, e.g. coating or deposition; Mounting additional parts onto the balloon member's surface
• CPC Class Codes: A61M 25/0009 Making of catheters or other medical or surgical tubes
• CPC Class Codes: A61M 25/1029 Production methods of the balloon members, e.g. blow-moulding, extruding, deposition or by wrapping a plurality of layers of balloon material around a mandril
• CPC Class Codes: C08L 23/00 Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 67/02 Polyesters derived from dicarboxylic acids and dihydroxy compounds C08L67/06 takes precedence
• CPC Class Codes: 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

Abstract

A combination of polymeric components provides desired characteristics in forming medical instruments such as catheters and balloons for dilatation catheters. For example, a balloon material is formed from a blend of polymeric components, including a first crystalline polymeric component and a second softening polymeric component. Where the first two components are generally incompatible, the balloon material can also include a third compatibilizing agent to facilitate blending the first two polymeric components together. The first polymeric component can be a branched or straight chain polyamide having a molecular weight of at least about 5000, or a polyester prepared from aromatic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic dicarboxylic acids having from 2 to 12 carbon atoms, and at least one glycol having the formula HO(CH₂)_n OH, where n is an integer from 2 to 10, neopentyl glycol and cyclohexane dimethanol. The second polymeric component can be a polyolefin, an ethylene copolymer, a polyester block copolymer, or a polyamide block copolymer. The third polymeric component is preferably an ethylene copolymer having the formula E/X/Y where E is ethylene; X is an α, β-ethylenically unsaturated monomer derived from at least one of alkylacrylate, alkylmethacrylate, alkyl vinyl ether, carbon monoxide, sulfur dioxide, or mixtures thereof, where the alkyl groups contain 1-12 carbon atoms; and Y is an α, β-ethylenically unsaturated monomer containing a reactive group that forms a covalent bond with the first polymeric component. The polymeric blend can be irradiated to enhance the properties of the balloon material, including significantly increasing burst pressures.

Claims

1. A catheter material formed from polymeric components, comprising:

about 60-77% by weight of the total blend composition of a first polymeric component selected from the group consisting of polyesters and polyamides, said polyesters being prepared from the group of dicarboxylic acids selected from aromatic dicarboxylic acids having from 8 to 14 carbon atoms and aliphatic dicarboxylic acids having from 2 to 12 carbon atoms, and at least one glycol selected from the group consisting of glycols having the formula HO(CH₂)_n OH, where n is an integer from 2 to 10, neopentyl glycol and cyclohexane dimethanol, and said polyamides being branched or straight chain polyamides having a molecular weight of at least 5000;

about 23-40% by weight of the total blend composition of a second polymer component having a Shore hardness less than 75 D, wherein said second polymeric component is a softening ethylene copolymer, the ethylene copolymer having the formula E'"'"'X'"'"' or E'"'"'X'"'"'Y'"'"', where E'"'"' is ethylene, and is about 60-85% by weight of the ethylene copolymer, where X'"'"' is about 15-40% by weight of the ethylene copolymer, and is selected from the group consisting of methylacrylate, ethylacrylate, propylacrylate, butylacrylate and mixtures thereof, and Y'"'"' is selected from the group consisting of α

, β

-ethylenically unsaturated monocarboxylic acids, α

, β

-ethylenically unsaturated dicarboxylic acids, and anhydrides comprising about 0.5-15% by weight of the ethylene copolymer; and

less than about 2.5% by weight of the total blend composition of a compatibilizing ethylene copolymer having the formula E/X/Y where

E is ethylene,

X is an α

, β

-ethylenically unsaturated monomer derived from at least one of alkylacrylate, alkylmethacrylate, alkyl vinyl ether, carbon monoxide, sulfur dioxide, or mixtures thereof, where the alkyl groups contain 1-12 carbon atoms, and

Y is an α

, β

-ethylenically unsaturated monomer containing a reactive group that forms a covalent bond with said first polymeric component.

2. The catheter material of claim 1, wherein said first polymeric component comprises about 60-77% of the total blend composition, and is selected from the group consisting of polyethylene-terephthalate, polybutylene-terephthalate, glycol modified polyethylene-terephthalate, 1,4-cyclohexylene dimethylene terephthalate/isophthalate copolymer, linear homopolymer esters derived from aromatic dicarboxylic acids and glycols of the general formula HO(CH₂)_n OH where n is an integer from 2 to 10.

3. The catheter material of claim 1, wherein said first polymeric component is a polyester having glycol segments selected from the group consisting of ethylene glycol;

1,3-trimethylene glycol;

1,4-tetramethylene glycol;

1,6-hexamethylene glycol;

1,8-octamethylene glycol;

1,10-decamethylene glycol;

2,2-dimethyl-1,3-propane diol;

1,3-propylene glycol;

1,4-butylene glycol;

neopentyl glycol and cyclohexane dimethanol.

4. The catheter material of claim 1, wherein X is selected from the group consisting of vinyl acetate, methylacrylate, butylacrylate, and methyl vinyl ether.

5. The catheter material of claim 1, wherein Y is an α

, β

-ethylenically unsaturated monomer containing a reactive group selected from the group consisting of epoxide, maleic anhydride, isocyanate, or oxazoline.

6. The catheter material of claim 1, wherein X is a moiety derived from at least one of alkyl acrylate, alkyl methacrylate, alkyl vinyl ether, carbon monoxide, sulfur dioxide, or mixtures thereof.

7. The catheter material of claim 1, wherein Y is selected from the group consisting of glycidyl methacrylate, glycidyl acrylate, maleic anhydride, and isocyanato-ethylmethacrylate.

8. The catheter material of claim 1, wherein Y is a moiety derived from at least one alkyl acrylate, alkyl methacrylate, or mixtures thereof, where the alkyl groups contain 1-8 carbon atoms.

9. The catheter material of claim 1, wherein Y is selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, and epoxide containing copolymerizable monomers.

10. The catheter material of claim 1, wherein the α

, β

-ethylenically unsaturated mono-carboxylic acid is neutralized at least partially by at least one metal ion selected from the group consisting of sodium, zinc, magnesium, calcium, potassium, and lithium.

11. The catheter material of claim 1, wherein E is ethylene, and is 67% by weight of the compatibilizing ethylene copolymer;

X is selected from the group of methylacrylate, ethylacrylate and butylacrylate, and is about 15-30% by weight of the compatibilizing ethylene copolymer; and

Y is selected from the group consisting of glycidyl acrylate and glycidyl methacrylate, and is about 8% by weight of the compatibilizing ethylene copolymer.

12. The catheter material of claim 1, wherein said polymeric blend is irradiated.

13. The catheter material of claim 12, wherein said polymeric blend is irradiated using ionizing radiation generated by any of an electron beam, gamma rays, ultraviolet light, or a molecular beam.

14. The catheter material of claim 12, wherein said polymeric blend is irradiated by an electron beam in the range of about 10-100 Mrads.

15. A balloon material formed from a blend composition of polymeric components, comprising:

about 60-77% by weight of the total blend composition of a first polymeric component selected from the group consisting of polyesters and polyamides, said polyesters being prepared from the group of dicarboxylic acids selected from aromatic dicarboxylic acids having from 8 to 14 carbon atoms and aliphatic dicarboxylic acids having from 2 to 12 carbon atoms, and at least one glycol selected from the group consisting of glycols having the formula HO(CH₂)_n OH, where n is an integer from 2 to 10, neopentyl glycol and cyclohexane dimethanol, and said polyamides being branched or straight chain polyamides having a molecular weight of at least 5000;

about 23-40% by weight of the total blend composition of a second polymer component having a Shore hardness less than 75 D, wherein said second polymeric component is a softening ethylene copolymer, and the ethylene copolymer has the formula E'"'"'X'"'"' or E'"'"'X'"'"'Y'"'"', where E'"'"' is ethylene, and is about 60-85% by weight of the ethylene copolymer, where X'"'"' is about 15-40% by weight of the ethylene copolymer, and is selected from the group consisting of methylacrylate, ethylacrylate, propylacrylate, butylacrylate and mixtures thereof, and Y'"'"' is selected from the group consisting of α

, β

-ethylenically unsaturated monocarboxylic acids, α

, β

-ethylenically unsaturated dicarboxylic acids, and anhydrides comprising about 0.5-15% by weight of the ethylene copolymer; and

less than about 2.5% by weight of the total blend composition of a compatibilizing ethylene copolymer having the formula E/X/Y where

E is ethylene,

X is an α

, β

-ethylenically unsaturated monomer derived from at least one of alkylacrylate, alkylmethacrylate, alkyl vinyl ether, carbon monoxide, sulfur dioxide, or mixtures thereof, where the alkyl groups contain 1-12 carbon atoms, and

Y is an α

, β

-ethylenically unsaturated monomer containing a reactive group that forms a covalent bond with said first polymeric component.

16. The balloon material of claim 15, wherein said first polymeric component comprises about 60-77% of the total blend composition, and is selected from the group consisting of polyethylene-terephthalate, polybutylene-terephthalate, glycol modified polyethylene-terephthalate, 1,4-cyclohexylene dimethylene terephthalate/isophthalate copolymer, linear homopolymer esters derived from aromatic dicarboxylic acids and glycols of the general formula HO(CH₂)_n OH where n is an integer from 2 to 10.

17. The balloon material of claim 15, wherein said first polymeric component is a glycol selected from the group consisting of ethylene glycol;

1,3-trimethylene glycol;

1,4-tetramethylene glycol;

1,6-hexamethylene glycol;

1,8-octamethylene glycol;

1,10-decamethylene glycol;

2,2-dimethyl-1,3-propane diol;

1,3-propylene glycol;

1,4-butylene glycol;

neopentyl glycol and cyclohexane dimethanol.

18. The balloon material of claim 15, wherein X is selected from the group consisting of vinyl acetate, methylacrylate, butylacrylate, and methyl vinyl ether.

19. The balloon material of claim 15, wherein Y is an α

, β

-ethylenically unsaturated monomer containing a reactive group selected from the group consisting of epoxide, maleic anhydride, isocyanate, or oxazoline.

20. The balloon material of claim 15, wherein X is a moiety derived from at least one of alkyl acrylate, alkyl methacrylate, alkyl vinyl ether, carbon monoxide, sulfur dioxide, or mixtures thereof.

21. The balloon material of claim 15, wherein Y is selected from the group consisting of glycidyl methacrylate, glycidyl acrylate, maleic anhydride, and isocyanato-ethylmethacrylate.

22. The balloon material of claim 15, wherein X is a moiety derived from at least one alkyl acrylate, alkyl methacrylate, or mixtures thereof, where the alkyl groups contain 1-8 carbon atoms.

23. The balloon material of claim 15, wherein Y is selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, and epoxide containing copolymerizable monomers.

24. The balloon material of claim 15, wherein the α

, β

-ethylenically unsaturated mono-carboxylic acid is neutralized at least partially by at least one metal ion selected from the group consisting of sodium, zinc, magnesium, calcium, potassium, and lithium.

25. The balloon material of claim 15, wherein E is ethylene, and is 67% by weight of the compatibilizing ethylene copolymer;

X is selected from the group of methylacrylate, ethylacrylate and butylacrylate, and is about 15-30% by weight of the compatibilizing ethylene copolymer; and

Y is selected from the group consisting of glycidyl acrylate and glycidyl methacrylate, and is about 8% by weight of the compatibilizing ethylene copolymer.

26. The balloon material of claim 15, wherein said polymeric blend is irradiated.

27. The balloon material of claim 26, wherein said polymeric blend is irradiated using ionizing radiation generated by any of an electron beam, gamma rays, ultraviolet light, or a molecular beam.

28. The balloon material of claim 26, wherein said polymeric blend is irradiated by an electron beam in the range of about 10-100 Mrads.

29. A dilatation catheter balloon material formed from a blend composition of polymeric components, comprising:

about 60-77% by weight of the total blend composition of a first polymeric component selected from the group consisting of polyethylene-terephthalate, polybutylene-terephthalate, glycol modified polyethylene-terephthalate, 1,4-cyclohexylene dimethylene terephthalate/isophthalate copolymer, linear homopolymer esters derived from aromatic dicarboxylic acids and glycols of the general formula HO(CH₂)_n OH where n is an integer from 2 to 10;

about 23-40% by weight of the total blend composition of a second polymeric component comprising an ethylene copolymer containing ethylene and at least one other monomer selected from the group consisting of α

, β

-ethylenically unsaturated monomers, carbon monoxide, and sulfur dioxide, said ethylene copolymer having the formula E'"'"'X'"'"' or E'"'"'X'"'"'Y'"'"', where E'"'"' is ethylene, and is about 60-85% by weight of the ethylene copolymer, where X'"'"' is about 15-40% by weight of the ethylene copolymer, and is selected from the group consisting of alkylacrylate, where the alkyl group contains 1-4 carbon atoms, and mixtures thereof, and Y'"'"' is selected from the group consisting of α

, β

-ethylenically unsaturated monocarboxylic acids, α

, β

-ethylenically unsaturated dicarboxylic acids, and anhydrides comprising about 0.5-15% by weight of the ethylene copolymer; and

from about 0.25% to about 2.5% by weight of the total blend composition of a compatibilizing ethylene copolymer having the formula E/X/Y where

E is ethylene,

X is an α

, β

-ethylenically unsaturated monomer derived from at least one of alkylacrylate, alkylmethacrylate, alkyl vinyl ether, carbon monoxide, sulfur dioxide, or mixtures thereof, where the alkyl groups contain 1-12 carbon atoms, and

Y is an α

, β

-ethylenically unsaturated monomer containing a reactive group that forms a covalent bond with said first polymeric component.

30. The dilatation catheter balloon material of claim 29, wherein Y is selected from the group consisting of glycidyl methacrylate, glycidyl acrylate, maleic anhydride, and isocyanato-ethylmethacrylate.

31. The dilatation catheter balloon material of claim 29, wherein E is ethylene, and is 67% by weight of the compatibilizing ethylene copolymer;

X is selected from the group of methylacrylate, ethylacrylate and butylacrylate, and is about 15-30% by weight of the compatibilizing ethylene copolymer; and

Y is selected from the group consisting of glycidyl acrylate and glycidyl methacrylate, and is about 8% by weight of the compatibilizing ethylene copolymer.

32. A catheter material formed from a radiation cross-linked polymeric blend, comprising:

about 60-77% by weight of the total blend composition of a first polymeric component selected from the group consisting of polyesters, said polyesters being prepared from the group of dicarboxylic acids selected from aromatic dicarboxylic acids having from 8 to 14 carbon atoms and aliphatic dicarboxylic acids having from 2 to 12 carbon atoms, and at least one glycol selected from the group consisting of glycols having the formula HO(CH₂)_n OH, where n is an integer from 2 to 10, neopentyl glycol and cyclohexane dimethanol;

about 23-40% by weight of the total blend composition of a second polymer component having a Shore hardness less than 75 D, said second polymeric component comprising a softening ethylene copolymer, the ethylene copolymer having the formula E'"'"'X'"'"' or E'"'"'X'"'"'Y'"'"', where E'"'"' is ethylene and is about 60-85% by weight of the ethylene copolymer, where X'"'"' is about 15-40% by weight of the ethylene copolymer, and is selected from the group consisting of methylacrylate, ethylacrylate, propylacrylate, butylacrylate and mixtures thereof, and Y'"'"' is selected from the group consisting of α

, β

-ethylenically unsaturated monocarboxylic acids, α

, β

-ethylenically unsaturated dicarboxylic acids, and anhydrides comprising about 0.5-15% by weight of the ethylene copolymer; and

less than about 2.5% by weight of the total blend composition of a compatibilizing ethylene copolymer having the formula E/X/Y where

E is ethylene,

X is an α

, β

-ethylenically unsaturated monomer derived from at least one of alkylacrylate, alkylmethacrylate, alkyl vinyl ether, carbon monoxide, sulfur dioxide, or mixtures thereof, where the alkyl groups contain 1-12 carbon atoms, and

Y is an α

, β

-ethylenically unsaturated monomer containing a reactive group that forms a covalent bond with said first polymeric component.

33. A balloon material formed from a radiation cross-linked polymeric blend, comprising:

about 60-77% by weight of the total blend composition of a first polymeric component selected from the group consisting of polyesters, said polyesters being prepared from the group of dicarboxylic acids selected from aromatic dicarboxylic acids having from 8 to 14 carbon atoms and aliphatic dicarboxylic acids having from 2 to 12 carbon atoms, and at least one glycol selected from the group consisting of glycols having the formula HO(CH₂)_n OH, where n is an integer from 2 to 10, neopentyl glycol and cyclohexane dimethanol;

about 23-40% by weight of the total blend composition of a second polymer component having a Shore hardness less than 75 D, said second polymeric component comprising a softening ethylene copolymer, the ethylene copolymer having the formula E'"'"'X'"'"' or E'"'"'X'"'"'Y'"'"', where E'"'"' is ethylene and is about 60-85% by weight of the ethylene copolymer, where X'"'"' is about 15-40% by weight of the ethylene copolymer, and is selected from the group consisting of methylacrylate, ethylacrylate, propylacrylate, butylacrylate and mixtures thereof, and Y'"'"' is selected from the group consisting of α

, β

-ethylenically unsaturated monocarboxylic acids, α

, β

-ethylenically unsaturated dicarboxylic acids, and anhydrides comprising about 0.5-15% by weight of the ethylene copolymer; and

less than about 2.5% by weight of the total blend composition of a compatibilizing ethylene copolymer having the formula E/X/Y where

E is ethylene,

X is an α

, β

-ethylenically unsaturated monomer derived from at least one of alkylacrylate, alkylmethacrylate, alkyl vinyl ether, carbon monoxide, sulfur dioxide, or mixtures thereof, where the alkyl groups contain 1-12 carbon atoms, and

Y is an α

, β

-ethylenically unsaturated monomer containing a reactive group that forms a covalent bond with said first polymeric component.

34. A catheter material formed from polymeric components, comprising:

about 60-77% by weight of the total blend composition of a first polymeric component selected from the group consisting of polyesters and polyamides, said polyesters being prepared from the group of dicarboxylic acids selected from aromatic dicarboxylic acids having from 8 to 14 carbon atoms and aliphatic dicarboxylic acids having from 2 to 12 carbon atoms, and at least one glycol selected from the group consisting of glycols having the formula HO(CH₂)_n OH, where n is an integer from 2 to 10, neopentyl glycol and cyclohexane dimethanol, and said polyamides being branched or straight chain polyamides having a molecular weight of at least 5000;

about 23-40% by weight of the total blend composition of a second polymer component having a Shore hardness less than 75 D, wherein said second polymeric component is a softening ethylene copolymer, and said softening ethylene copolymer contains ethylene and at least one other monomer selected from the group consisting of α

, β

-ethylenically unsaturated monomers, carbon monoxide, and sulfur dioxide, and wherein when said at least one other monomer comprises an α

, β

-ethylenically unsaturated monomer and is an acid containing moiety, said α

, β

-ethylenically unsaturated monomer is partially neutralized with an ion selected from the group of sodium, potassium, zinc, lithium, calcium, and ammonium; and

less than about 2.5% by weight of the total blend composition of a compatibilizing ethylene copolymer having the formula E/X/Y where

E is ethylene,

X is an α

, β

-ethylenically unsaturated monomer derived from at least one of alkylacrylate, alkylmethacrylate, alkyl vinyl ether, carbon monoxide, sulfur dioxide, or mixtures thereof, where the alkyl groups contain 1-12 carbon atoms, and

Y is an α

, β

-ethylenically unsaturated monomer containing a reactive group that forms a covalent bond with said first polymeric component.

35. A balloon material formed from a blend composition of polymeric components, comprising:

about 60-70% by weight of the total blend composition of a first polymeric component selected from the group consisting of polyesters and polyamides, said polyesters being prepared from the group of dicarboxylic acids selected from aromatic dicarboxylic acids having from 8 to 14 carbon atoms and aliphatic dicarboxylic acids having from 2 to 12 carbon atoms, and at least one glycol selected from the group consisting of glycols having the formula HO(CH₂)_n OH, where n is an integer from 2 to 10, neopentyl glycol and cyclohexane dimethanol, and said polyamides being branched or straight chain polyamides having a molecular weight of at least 5000;

about 23-40% by weight of the total blend composition of a second polymer component having a Shore hardness less than 75 D, said second polymeric component comprising a softening ethylene copolymer, and said softening ethylene copolymer contains ethylene and at least one other monomer selected from the group consisting of α

, β

-ethylenically unsaturated monomers, carbon monoxide, and sulfur dioxide, and wherein when said at least one other monomer comprises an α

, β

-ethylenically unsaturated monomer and is an acid containing moiety, said α

, β

-ethylenically unsaturated monomer is partially neutralized with an ion selected from the group of sodium, potassium, zinc, lithium, calcium, and ammonium; and

less than about 2.5% by weight of the total blend composition of a compatibilizing ethylene copolymer having the formula E/X/Y where

E is ethylene,

X is an α

, β

-ethylenically unsaturated monomer derived from at least one of alkylacrylate, alkylmethacrylate, alkyl vinyl ether, carbon monoxide, sulfur dioxide, or mixtures thereof, where the alkyl groups contain 1-12 carbon atoms, and

Y is an α

, β

-ethylenically unsaturated monomer containing a reactive group that forms a covalent bond with said first polymeric component.

36. A dilatation catheter balloon material formed from a blend composition of polymeric components, comprising:

about 60-77% by weight of the total blend composition of a first polymeric component selected from the group consisting of polyethylene-terephthalate, polybutylene-terephthalate, glycol modified polyethylene-terephthalate, 1,4-cyclohexylene dimethylene terephthalate/isophthalate copolymer, linear homopolymer esters derived from aromatic dicarboxylic acids and glycols of the general formula HO(CH₂)_n OH where n is an integer from 2 to 10;

about 23-40% by weight of the total blend composition of a second polymeric component comprising an ethylene copolymer containing ethylene and at least one other monomer selected from the group consisting of α

, β

-ethylenically unsaturated monomers, carbon monoxide, and sulfur dioxide, and wherein when said at least one other monomer comprises an α

, β

-ethylenically unsaturated monomer and is an acid containing moiety, said α

, β

-ethylenically unsaturated monomer is partially neutralized with an ion selected from the group of sodium, potassium, zinc, lithium, calcium, and ammonium; and

from about 0.25% to about 2.5% by weight of the total blend composition of a compatibilizing ethylene copolymer having the formula E/X/Y where

E is ethylene,

X is an α

, β

-ethylenically unsaturated monomer derived from at least one of alkylacrylate, alkylmethacrylate, alkyl vinyl ether, carbon monoxide, sulfur dioxide, or mixtures thereof, where the alkyl groups contain 1-12 carbon atoms, and

Y is an α

, β

-ethylenically unsaturated monomer containing a reactive group that forms a covalent bond with said first polymeric component.