Hyper-elastic, high strength dilatation balloon made from multi-block copolymers

Abstract

A self-wrapping dilatation balloon comprising a multiblock copolymer having high elasticity and elastic recovery from nominal strains greater than about 30% is described. Also described herein, is a polymeric extrudate for making a dilatation balloon comprising a multiblock copolymer having tensile strength in the range of about 50 MPa to about 450 MPa, strain at break in the range of about 50% to about 600% and substantially complete elastic recovery from nominal strains of at least about 30%. The extrudate has phase-separated microdomains that are macroscopically aligned in parallel, perpendicular, transverse or a combination thereof. Also described herein is a process for producing a polymeric extrudate for use as a dilatation balloon. The process comprises extruding a multiblock copolymer mixture or composition to form an extrudate. The extruding is done such that the extrudate has phase-separated microdomains that are macroscopically aligned in parallel, perpendicular, transverse or a combination thereof. After extrusion, the process optionally comprises the steps of drawing and coagulating the extrudate.

1 . A zero fold dilatation balloon comprising a multiblock copolymer having elasticity at nominal strains greater than about 30%.  
     
     
         2 . The balloon of  claim 1 , wherein said multiblock copolymer has elastic recovery from nominal strains greater than about 30%.  
     
     
         3 . The balloon of  claim 2 , wherein said nominal strain is [(balloon outer diameter at nominal pressure−preform outer diameter)/preform outer diameter]×100.  
     
     
         4 . The balloon of  claim 2  having elastic recovery from nominal strains greater than about 50%.  
     
     
         5 . The balloon of  claim 1  having hoop strength of at least about 14,000 p.s.i.  
     
     
         6 . The balloon of  claim 1  having radial growth of about 5-20%.  
     
     
         7 . The balloon of  claim 1 , further comprising a plasticizer.  
     
     
         8 . The balloon of  claim 7 , wherein the solubility parameter of said plasticizer and at least one block of said multiblock copolymer are about equal.  
     
     
         9 . The balloon of  claim 8 , wherein said plasticizer is a carbonamide, sulfonamide, phenylic compound, cyclic ketone, mixture of phenyls and esters, sulfonated ester, sulfonated amide, N-alkylolarylsulfonamide, phthalate ester, amine, aliphatic diol or phosphite ester of an alcohol.  
     
     
         10 . The balloon of  claim 1 , further comprising at least one of a filler, antioxidant, colorant, crosslinking agent, impact strength modifier, drug or biologically active material.  
     
     
         11 . The balloon of  claim 1 , wherein said multiblock copolymer is a diblock, triblock, butablock, pentablock, hexablock, heptablock, octablock, nonablock, decablock, undecablock or dodecablock copolymer.  
     
     
         12 . The balloon of  claim 11 , wherein at least one block of said multiblock copolymer is polyethylene, polypropylene, poly(cylohexylethylene), polyisoprene, poly(1,3-butadiene), poly(vinyl chloride), poly(vinyl fluoride), poly(chloroprene), poly(methyl acrylate), poly(methyl methacrylate), poly(acyrlonitrile), polystyrene or poly(4-vinylpyridine).  
     
     
         13 . The balloon of  claim 1 , wherein said multiblock copolymer is a blend of two or more multiblock copolymers.  
     
     
         14 . The balloon of  claim 1 , further comprising a homopolymer.  
     
     
         15 . The balloon of  claim 1 , further comprising a viscosity modifier.  
     
     
         16 . The balloon of  claim 1 , wherein said multiblock copolymer has microdomains macroscopically aligned parallel, perpendicular, transverse or a combination thereof.  
     
     
         17 . A balloon dilatation catheter, comprising: 
 a) a tubular elongated catheter shaft; and    b) the dilatation balloon disposed on said shaft comprising the multiblock copolymer of  claim 1 .    
     
     
         18 . The catheter of  claim 17 , wherein: 
 (1) said shaft has proximal and distal portions; and    (2) said balloon is self-wrapped over said distal portion such that it has a low profile.    
     
     
         19 . The catheter of  claim 18 , wherein said distal portion has substantially same low profile after one or more expansions of said balloon with rated pressures that result in about 5% to about 20% radial growth of said balloon.  
     
     
         20 . The catheter of  claim 19 , wherein said low profile is in the range of about 0.025 mm to about 13.0 mm when said balloon is deflated.  
     
     
         21 . The catheter of  claim 19 , wherein said low profile is in the range of about 0.25 mm to about 2.5 mm when said balloon is deflated.  
     
     
         22 . The balloon of  claim 1 , having a non-linear compliance curve comprising initial, secondary and final segments, the initial segment having a radial growth higher than the secondary segment, and the secondary segment having a radial growth higher than the final segment.  
     
     
         23 . The balloon of  claim 22 , wherein said initial segment has modulus in the range of about 0.05 GPa to about 2 GPa.  
     
     
         24 . The balloon of  claim 22 , wherein said initial segment has modulus less than about 1 GPa.  
     
     
         25 . The balloon of  claim 22 , having a radial growth in mm/p.s.i. of 0.39 for said initial segment, 0.025 for said secondary segment, and 0.017 for said final segment.  
     
     
         26 . The balloon of  claim 1  comprising two or more layers of polymeric material comprising a multiblock copolymer.  
     
     
         27 . The balloon of  claim 1  having a Young's Modulus less than about 5 GPa.  
     
     
         28 . A polymeric extrudate for making a dilatation balloon comprising a multiblock copolymer having tensile strength in the range of about 50 MPa to about 450 MPa, strain at break in the range of about 50% to about 600% and elasticity at nominal strains of at least about 30%.  
     
     
         29 . The extrudate of  claim 28 , wherein said multiblock copolymer has substantially complete elastic recovery from nominal strains of at least about 30%.  
     
     
         30 . The extrudate of  claim 29 , wherein said extrudate has tensile strength in the range of about 150 MPa to about 250 MPa, strain at break in the range of about 300% to about 500% and substantially complete elastic recovery from strains of at least about 30%.  
     
     
         31 . The extrudate of  claim 29 , wherein said extrudate has tensile strength in the range of about 50 MPa to about 150 MPa, strain at break in the range of about 50% to about 300% and substantially complete elastic recovery from strains of at least about 30%.  
     
     
         32 . The extrudate of  claim 29 , wherein said extrudate has tensile strength in the range of about 250 MPa to about 450 MPa, strain at break in the range of about 500% to about 600% and substantially complete elastic recovery from strains of at least about 30%.  
     
     
         33 . The extrudate of  claim 29 , wherein said extrudate has tensile strength of at least 150 MPa, strain at break at least 120% and substantially complete elastic recovery from strains of at least about 40%.  
     
     
         34 . The extrudate of  claim 29 , wherein said multiblock copolymer is a diblock, triblock, butablock, pentablock, hexablock, heptablock, octablock, nonablock, decablock, undecablock or dodecablock copolymer.  
     
     
         35 . The extrudate of  claim 34 , wherein at least one block of said multiblock copolymer is polyethylene, polypropylene, poly(cylohexylethylene), polyisoprene, poly(1,3-butadiene), poly(vinyl chloride), poly(vinyl fluoride), poly(chloroprene), poly(methyl acrylate), poly(methyl methacrylate), poly(acyrlonitrile), polystyrene or poly(4-vinylpyridine).  
     
     
         36 . The extrudate of  claim 35 , wherein said triblock copolymer is an alternating triblock copolymer having a structure (A-B-A).  
     
     
         37 . The extrudate of  claim 35 , wherein said pentablock copolymer is an alternating pentablock copolymer having a structure (A-B-A-B-A).  
     
     
         38 . The extrudate of  claim 34 , wherein said multiblock copolymer is a blend of two or more multiblock copolymers.  
     
     
         39 . The extrudate of  claim 28 , further comprising a plasticizer.  
     
     
         40 . The extrudate of  claim 39 , wherein the solubility parameter of said plasticizer and at least one block of said multiblock copolymer are about equal.  
     
     
         41 . The extrudate of  claim 40 , wherein said plasticizer is a carbonamide, sulfonamide, phenylic compound, cyclic ketone, mixture of phenyls and esters, sulfonated ester, sulfonated amide, N-alkylolarylsulfonamide, phthalate ester, amine, aliphatic diol or phosphite ester of an alcohol.  
     
     
         42 . The extrudate of  claim 28 , further comprising at least one of a filler, antioxidant, colorant, crosslinking agent, impact strength modifier, drug or biologically active material.  
     
     
         43 . The extrudate of  claim 28 , further comprising a viscosity modifier.  
     
     
         44 . The extrudate of  claim 28 , further comprising a homopolymer.  
     
     
         45 . The extrudate of  claim 28  having a tubular shape, wherein said tubular shape has outer diameter of about 0.025 mm to about 13 mm and inner diameter of about 0.013 mm to about 12 mm.  
     
     
         46 . The extrudate of  claim 28  having a tubular shape, wherein said tubular shape has an outer diameter of about 0.25 mm to about 2.5 mm and an inner diameter of about 0.15 mm to about 1.5 mm.  
     
     
         47 . The extrudate of  claim 28 , having phase-separated microdomains that are macroscopically aligned in parallel, perpendicular, transverse, or a combination thereof.  
     
     
         48 . The extrudate of  claim 47 , having two or more regions with different macroscopic microdomain alignment.  
     
     
         49 . A self-wrapping dilatation balloon comprising a multiblock copolymer having high elasticity and elastic recovery from nominal strains greater than about 30%.  
     
     
         50 . A polymeric extrudate for making a dilatation balloon comprising a multiblock copolymer having tensile strength in the range of about 50 MPa to about 450 MPa, strain at break in the range of about 50% to about 600% and substantially complete elastic recovery from strains of at least about 30%.