WO2000050105A2 - Medical devices made from polymer blends containing liquid crystal polymers - Google Patents

Medical devices made from polymer blends containing liquid crystal polymers Download PDF

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Publication number
WO2000050105A2
WO2000050105A2 PCT/US2000/003821 US0003821W WO0050105A2 WO 2000050105 A2 WO2000050105 A2 WO 2000050105A2 US 0003821 W US0003821 W US 0003821W WO 0050105 A2 WO0050105 A2 WO 0050105A2
Authority
WO
WIPO (PCT)
Prior art keywords
lcp
base polymer
thermoplastic
melting point
balloon
Prior art date
Application number
PCT/US2000/003821
Other languages
French (fr)
Other versions
WO2000050105A3 (en
Inventor
Lixiao Wang
Jianhua Chen
Original Assignee
Scimed Life Systems, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Scimed Life Systems, Inc. filed Critical Scimed Life Systems, Inc.
Priority to EP00910181A priority Critical patent/EP1154808B1/en
Priority to JP2000600715A priority patent/JP4954372B2/en
Priority to CA002362607A priority patent/CA2362607C/en
Priority to DE60009866T priority patent/DE60009866T2/en
Priority to AT00910181T priority patent/ATE264122T1/en
Publication of WO2000050105A2 publication Critical patent/WO2000050105A2/en
Publication of WO2000050105A3 publication Critical patent/WO2000050105A3/en

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Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61MDEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M25/00Catheters; Hollow probes
    • A61M25/10Balloon catheters
    • A61M25/1027Making of balloon catheters
    • A61M25/1029Production methods of the balloon members, e.g. blow-moulding, extruding, deposition or by wrapping a plurality of layers of balloon material around a mandril
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L29/00Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/04Macromolecular materials
    • A61L29/049Mixtures of macromolecular compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L29/00Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/12Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L29/126Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L29/00Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/14Materials characterised by their function or physical properties, e.g. lubricating compositions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/0005Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61MDEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M25/00Catheters; Hollow probes
    • A61M25/10Balloon catheters
    • A61M25/1027Making of balloon catheters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42Component parts, details or accessories; Auxiliary operations
    • B29C49/78Measuring, controlling or regulating
    • B29C49/786Temperature
    • B29C2049/7861Temperature of the preform
    • B29C2049/7862Temperature of the preform characterised by temperature values or ranges
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42Component parts, details or accessories; Auxiliary operations
    • B29C49/78Measuring, controlling or regulating
    • B29C49/786Temperature
    • B29C2049/7864Temperature of the mould
    • B29C2049/78645Temperature of the mould characterised by temperature values or ranges
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42Component parts, details or accessories; Auxiliary operations
    • B29C49/78Measuring, controlling or regulating
    • B29C2049/7879Stretching, e.g. stretch rod
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/04Extrusion blow-moulding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/08Biaxial stretching during blow-moulding
    • B29C49/087Means for providing controlled or limited stretch ratio
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/22Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor using multilayered preforms or parisons
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29LINDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2022/00Hollow articles
    • B29L2022/02Inflatable articles
    • B29L2022/022Balloons
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29LINDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00Other particular articles
    • B29L2031/753Medical equipment; Accessories therefor
    • B29L2031/7542Catheters
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1334Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
    • Y10T428/1345Single layer [continuous layer]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1386Natural or synthetic rubber or rubber-like compound containing
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1397Single layer [continuous layer]

Definitions

  • the blends comprise polymer melt blend product of a) a thermotropic main-chain liquid crystal polymer (LCP); b) a crystallizable thermoplastic polymer; and c) at least one compatibilizer for a) and b).
  • LCP thermotropic main-chain liquid crystal polymer
  • melt blend balloons so produced have very high strength, but have relatively low compliance and flexibility .
  • thermoplastic polymer was a material with a relatively high melting temperature, such as crystallizable polyester or polyamide polymers.
  • the known LCPs had melting points above 275 °C, thus requiring that the thermoplastic polymer be stable at temperatures near or above the LCP melting temperature in order to process the melt blend.
  • thermoplastic polymers have higher flexibility and elasticity than polyesters or polyamides but their melting points have been too low to be processable in melt blends with LCPs. Recently LCPs with melting points below 250 °C have been prepared and commercialized. The inventors of the present invention have now discovered a much wider range of thermoplastic polymers can be blended with such low melting temperature LCPs to produce blend materials useful in fabricating medical devices.
  • the invention comprises a medical device at least a portion of which is composed of a polymeric material in which the polymeric material is a melt blend product of at least two different thermoplastic polymers, one of the thermoplastic polymers being a thermoplastic liquid crystal polymer having a melting point of about
  • Catheters and catheter balloons are specific medical devices to which the invention may be applied.
  • the low temperature LCP component may be used at relatively low levels to impart higher strength and resistance to shrinkage to base polymer materials of greater flexibility, softness or elasticity than had previously been usable with available LCPs.
  • Fig. 1 is a perspective fragmentary view of a balloon catheter embodiment of the present invention.
  • the blend products used in the present invention include a thermoplastic non-LCP base polymer in an amount of from about 50 to about 99.9% by weight, preferably from about 85 to about 99.5 percent.
  • the blend products also include from about 0J to about 20 weight percent, more preferably from about 0.5 to about 15 percent, of a liquid crystal polymer having a melting point of less than 275 °C, preferably less than 250°C.
  • a melt compatibilizer such as disclosed in application 08/926,905, may also be employed in an amount of from 0 to about 30 weight percent.
  • the base polymer should have a melting point within about 70°C, preferably within about 50 °C and more preferably within about 35 °C of the liquid crystal polymer component.
  • the base polymer has a melting point in the range of from about 140°C to about 265 °C, preferably about 220°C or less, and more preferably from about 150° C to about 210°C.
  • the base polymer may be for instance an acetal homopolymer or copolymer (typical mp 160-185 °C); cellulosic polymers (mp. 140-190°C); poly(chlorotrifluoroethylene) (mp.
  • poly(vinylidine fluoride) mp 155-180°C
  • nylon 6,6 mp. 250-260
  • nylon 6 mp 215-225
  • nylon 6J0 mp 210-220
  • nylon 12 mp 170-180
  • nylon 11 mp 180-190
  • polyoxymethylene mp 165-185
  • higher melting grades of poly(methyl methacrylate) e.g.
  • thermoplastic polyurethanes aromatic and/or aliphatic
  • thermoplastic elastomers such as polyester elastomers sold under the tradenames Hytrel ® and Arnitel ® , polyamide elastomers sold under the tradename Pebax ® , and thermoplastic polyurethane elastomers sold under the tradename Pellethane ® .
  • Particularly preferred base polymer materials include Pebax ® 7033 (mp 174°C ) and 7233 (mp 175°C), sold by Atochem North America, and Arnitel EM 740 (mp 221 °C), sold by DSM Engineering Plastics.
  • a dual extruder technique can still be used to obtain blends with base polymers whose melt temperature is substantially lower than that of the LCP used in the present invention. Therefore the range of usable base polymers is substantially increased in the present invention over those of prior application 08/926,905.
  • the LCP used in the invention hereof is one characterized by a melting point below 275°C, preferably below 250°C, suitably in the range of 150-249°C, and even more preferably about 230 °C or less.
  • the LCP is suitably a thermotropic liquid crystal polymer.
  • Specific such LCPs include Vectra ® LKX 1107, a polyester-type liquid crystal polymer (mp 220 ° C), and Vectra ® LKX 1111 , a polyesteramide-type liquid crystal polymer (mp. 220 °C), both sold by Ticona, a Hoechst company. Compatibilizers also may be used in the melt blend composition.
  • the compatibilizer may be for instance a block copolymer comprising a block which is structurally similar or otherwise is soluble in the base polymer and a block which is structurally similar or otherwise soluble with the LCP.
  • Compatibilizers may be necessary if phase separation of the blend in the melt phase is a problem.
  • phase separation of the solid phase melt blend product is not necessarily a reason to employ a compatibilizer.
  • Solid phase separation may enhance the reinforcing effect of the LCP component.
  • Optical clarity is lost with phase separation in the solid phase.
  • Use of a compatibilizer may be useful if optical clarity is a desired objective or where it is desired to improve adhesion between LCP fiber and the base polymer.
  • the blend materials described herein are particularly suited for use in forming dilatation and/or stent placement catheters or balloons thereon. Such catheters are used for percutaneous transluminal angioplasty and other minimally invasive procedures. Use in forming a proximal or intermediate portion of the catheter body may reduce or eliminate the need for braid or other physical reinforcement so that a reduced profile may be provided.
  • a particularly preferred use of the melt blend materials described herein is as a material for a catheter balloon.
  • the balloon diameter may be from about 1.5 to about 30 mm, depending on the application to which it is put, and are suitably formed to provide a double wall thickness, measured on the uninflated collapsed balloon, of about 0.0002" - 0.0020".
  • the balloons of the invention may be either single layer balloons, or multilayer balloons.
  • a catheter 10 comprising an elongated flexible tube 12 with a balloon 14, made of an LCP reinforced polymer blend in accordance with the invention hereof, mounted at the distal end thereof.
  • a portion of tube 12 also may be formed from an LCP reinforced polymer blend, which may be the same or different from the blend used to form the balloon.
  • Balloon formation may be begun by extruding a tube from a melt of the polymer blend material.
  • Some initial orientation of the LCP occurs as the blend material is drawn down during the extrusion process. This process is typically known as machine orientation and is in the direction of the extrusion operation. Orientation which occurs during the extrusion process is desirable as it induces formation of fiber form LCP in the ' tubing so-formed. Orientation can be enhanced by increasing extrudate puller speed. Also, if an angled fiber morphology is desired, a counter-rotating die and mandrel system can be used in the extrusion.
  • the extruded tube optionally may be conditioned at 20-30 °C at a controlled humidity in the range of 10-50% for a period of at least 24 hours. This conditioning provides a constant low moisture level in the tube which prevents hydrolysis and helps to optimize the orientation of the polymer in the subsequent blowing steps.
  • Balloon blowing may follow conventional single or multi-step techniques known in the art, for instance free blowing, mold blowing, or a combination of both, optionally with a preceding axial stretching step.
  • the axial stretch ratio if used, is suitably from about 2x to about 5x.
  • Balloon forming will typically be performed at a temperature in the range of 95 °C to 165°C, depending on the base polymer material and the amount of LCP incorporated into the blend.
  • the balloon forming step should be performed above the glass transition temperature but below the melt temperature of the base polymer material (for block copolymers the blowing temperature should be above the highest glass transition).
  • the radial expansion ratio is suitably from about 3x to about 12x. Depending on the technique, expansion pressures may range from about 200- 500 psi (1379 -3447 kPa).
  • the pressurized balloon is held for a brief time, suitably about 5-60 seconds, at a temperature above that used to form the balloon after which the mold is rapidly quenched to ambient temperature and the balloon removed from the mold.
  • the LC and base polymers will typically undergo phase separation on cooling so that an opaque article is obtained.
  • the phase separation occurs on a microscopic scale so that the LC discontinuous phase is uniformly distributed in a continuous base polymer phase.
  • the LC discontinuous phase is fibrous, and the fibers orient during the stretching and blowing steps of the balloon formation so a high level of reinforcement is provided to the base polymer.
  • reinforcement by the fibrous LC phase can be achieved without a major reduction in flexibility and without presenting huge increases in melt viscosity, both of which effects are commonly encountered when reinforcing fillers are added to thermoplastic polymer compositions.
  • the fiber size is so small that, even with the extremely thin films encountered in angioplasty balloons, film porosity is not created.
  • Pebax 7033 polymer was melt blended at a temperature of 225 °C with liquid crystal polymer Vectra LKX 1107 at the ratio of 95% to 5% respectively by weight and the mixture was extruded into tubing of 0.018 x 0.037 inch (0.48 x 0.94 mm).
  • a 3.0 mm balloon was formed from the tube at 98 °C and at 450 psi (4102 kPa) forming pressure using a 3.0 mm mold form in a single blowing step.
  • the balloon had a double wall thickness of 0.00175 inch (0.044 mm) and had an opaque appearance.
  • This reinforced composite balloon has much higher puncture resistance and more durability than a similar balloon made from 100% Pebax 7033.
  • Example 2 The same composition as shown in Example 1 was used to extrude a tube of 0.022 x 0.036 inch (0.56 x 0.91 mm).
  • the 3.0 mm balloon was made at 95 °C with a blowing pressure of 400 psi (2758 kPa).
  • the balloon with double wall thickness of 0.0014 inch (0.036 mm) was inflated from 4 atm ( 405 kPa) to 13 atm (1317 kPa) at 1 atm (101 kPa) increments and the balloon length change was 2.5% at the span of 4-13 atm.
  • Pebax 7033 tubing with dimension of 0.0192 x 0.0344 (0.49-0.87 mm) was used to form 3.0 mm balloon at 95 °C and 400 psi (2758 kPa) blowing pressure.
  • the formed balloon with double wall thickness of 0.0014 inch (0.036 mm) was inflated from 4 atm (405 kPa) to 13 atm (1317 kPa) at 1 atm (101 kPa) increments and the balloon grew 8.0% of its original length before inflation.
  • a 40 mm long 3.0 mm diameter balloon mold was used to make a 100% Pebax 7033 balloon.
  • the formed balloon had a body length of 37.0 mm after the balloon was removed from the mold.
  • the same mold and balloon forming conditions were used for a LCP reinforced Pebax 7033 balloon formed from the melt blend product described in Example 1.
  • the formed balloon had the body length of 38.5 mm, corresponding to a 50% improvement in balloon body length stability as a result of the inclusion of the 5% LCP component.

Abstract

A medical device, at least a portion of which is composed of a polymeric material in which the polymeric material is a melt blend product of at least two different thermoplastic polymers, one of the thermoplastic polymers being a thermoplastic liquid crystal polymer (LCP) having a melting point of less than 250 °C. The portion of the device made from the melt blend may be a catheter body segment or a balloon for a catheter. The LCP blends suitably also include a non-LCP base polymer having a melting point in the range of about 140 °C to about 265 °C.

Description

MEDICAL DEVICES MADE FROM POLYMER BLENDS CONTAINING LOW MELTING TEMPERATURE LIQUID CRYSTAL POLYMERS
U.S. Application No. 09/257,677 from which this application claims priority, is incorporated in its entirety herein by reference.
BACKGROUND OF THE INVENTION
In copending US application 08/926,905 (corresponding to PCT/US98/18345 filed Sept. 4, 1998) there are described medical balloons made from liquid crystal polymer blends. The blends comprise polymer melt blend product of a) a thermotropic main-chain liquid crystal polymer (LCP); b) a crystallizable thermoplastic polymer; and c) at least one compatibilizer for a) and b).
The melt blend balloons so produced have very high strength, but have relatively low compliance and flexibility .
The practice of the invention of application 08/926,905, however, has been limited in that the thermoplastic polymer was a material with a relatively high melting temperature, such as crystallizable polyester or polyamide polymers. The known LCPs had melting points above 275 °C, thus requiring that the thermoplastic polymer be stable at temperatures near or above the LCP melting temperature in order to process the melt blend.
Many thermoplastic polymers have higher flexibility and elasticity than polyesters or polyamides but their melting points have been too low to be processable in melt blends with LCPs. Recently LCPs with melting points below 250 °C have been prepared and commercialized. The inventors of the present invention have now discovered a much wider range of thermoplastic polymers can be blended with such low melting temperature LCPs to produce blend materials useful in fabricating medical devices. SUMMARY OF THE INVENTION
In one aspect the invention comprises a medical device at least a portion of which is composed of a polymeric material in which the polymeric material is a melt blend product of at least two different thermoplastic polymers, one of the thermoplastic polymers being a thermoplastic liquid crystal polymer having a melting point of about
275 °C or less, and especially 250°C or less. Catheters and catheter balloons are specific medical devices to which the invention may be applied.
The low temperature LCP component may be used at relatively low levels to impart higher strength and resistance to shrinkage to base polymer materials of greater flexibility, softness or elasticity than had previously been usable with available LCPs.
DESCRIPTION OF THE DRAWING
Fig. 1 is a perspective fragmentary view of a balloon catheter embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The blend products used in the present invention include a thermoplastic non-LCP base polymer in an amount of from about 50 to about 99.9% by weight, preferably from about 85 to about 99.5 percent. The blend products also include from about 0J to about 20 weight percent, more preferably from about 0.5 to about 15 percent, of a liquid crystal polymer having a melting point of less than 275 °C, preferably less than 250°C. A melt compatibilizer, such as disclosed in application 08/926,905, may also be employed in an amount of from 0 to about 30 weight percent.
The base polymer should have a melting point within about 70°C, preferably within about 50 °C and more preferably within about 35 °C of the liquid crystal polymer component. Suitably the base polymer has a melting point in the range of from about 140°C to about 265 °C, preferably about 220°C or less, and more preferably from about 150° C to about 210°C. Depending on the liquid crystal polymer melting temperature, the base polymer may be for instance an acetal homopolymer or copolymer (typical mp 160-185 °C); cellulosic polymers (mp. 140-190°C); poly(chlorotrifluoroethylene) (mp. 200-220); poly(vinylidine fluoride) (mp 155-180°C); nylon 6,6 (mp. 250-260); nylon 6 (mp 215-225); nylon 6J0 (mp 210-220); nylon 12 (mp 170-180); nylon 11 (mp 180-190); polyoxymethylene (mp 165-185); higher melting grades of poly(methyl methacrylate) (e.g. mp 140-160°C); polypropylene homopolymers and copolymers (mp 160-175); polycarbonate polymers and copolymers (mp 220- 230°C); poly(ethylene-vinyl alcohol) (mp 140-180); polyethylene terephthalate; polybutylene terephthalate; polytrimethylene terephthalate; thermoplastic polyurethanes (aromatic and/or aliphatic); thermoplastic elastomers such as polyester elastomers sold under the tradenames Hytrel® and Arnitel®, polyamide elastomers sold under the tradename Pebax®, and thermoplastic polyurethane elastomers sold under the tradename Pellethane®. Particularly preferred base polymer materials include Pebax® 7033 (mp 174°C ) and 7233 (mp 175°C), sold by Atochem North America, and Arnitel EM 740 (mp 221 °C), sold by DSM Engineering Plastics.
Use of some of these base polymers in LCP blends has been described in the prior application 08/926,905, for instance PET/LCP blends. However, by using lower melting temperature LCPs, as described herein, processing is made easier. For instance, where there is a large temperature difference between the base polymer and the LCP component, a dual extruder may have had to be used to allow the polymers to be separately melted before they could be mixed. With a smaller difference in melt temperatures the melt blend of LCP and base polymer can be prepared by melting a dry blend of the two polymers, or one of the two polymers in solid form may be added to a melt of the other, without substantial polymer degradation. A dual extruder technique can still be used to obtain blends with base polymers whose melt temperature is substantially lower than that of the LCP used in the present invention. Therefore the range of usable base polymers is substantially increased in the present invention over those of prior application 08/926,905.
The LCP used in the invention hereof is one characterized by a melting point below 275°C, preferably below 250°C, suitably in the range of 150-249°C, and even more preferably about 230 °C or less. The LCP is suitably a thermotropic liquid crystal polymer. Specific such LCPs include Vectra® LKX 1107, a polyester-type liquid crystal polymer (mp 220 ° C), and Vectra® LKX 1111 , a polyesteramide-type liquid crystal polymer (mp. 220 °C), both sold by Ticona, a Hoechst company. Compatibilizers also may be used in the melt blend composition. The compatibilizer may be for instance a block copolymer comprising a block which is structurally similar or otherwise is soluble in the base polymer and a block which is structurally similar or otherwise soluble with the LCP. Compatibilizers may be necessary if phase separation of the blend in the melt phase is a problem. However, phase separation of the solid phase melt blend product is not necessarily a reason to employ a compatibilizer. Solid phase separation may enhance the reinforcing effect of the LCP component. Optical clarity, however, is lost with phase separation in the solid phase. Use of a compatibilizer may be useful if optical clarity is a desired objective or where it is desired to improve adhesion between LCP fiber and the base polymer.
The blend materials described herein are particularly suited for use in forming dilatation and/or stent placement catheters or balloons thereon. Such catheters are used for percutaneous transluminal angioplasty and other minimally invasive procedures. Use in forming a proximal or intermediate portion of the catheter body may reduce or eliminate the need for braid or other physical reinforcement so that a reduced profile may be provided.
A particularly preferred use of the melt blend materials described herein is as a material for a catheter balloon. The balloon diameter may be from about 1.5 to about 30 mm, depending on the application to which it is put, and are suitably formed to provide a double wall thickness, measured on the uninflated collapsed balloon, of about 0.0002" - 0.0020".
The balloons of the invention may be either single layer balloons, or multilayer balloons.
Referring to the drawing, there is shown in Figure 1 a catheter 10 comprising an elongated flexible tube 12 with a balloon 14, made of an LCP reinforced polymer blend in accordance with the invention hereof, mounted at the distal end thereof. A portion of tube 12 also may be formed from an LCP reinforced polymer blend, which may be the same or different from the blend used to form the balloon.
Balloon formation may be begun by extruding a tube from a melt of the polymer blend material. Some initial orientation of the LCP occurs as the blend material is drawn down during the extrusion process. This process is typically known as machine orientation and is in the direction of the extrusion operation. Orientation which occurs during the extrusion process is desirable as it induces formation of fiber form LCP in the' tubing so-formed. Orientation can be enhanced by increasing extrudate puller speed. Also, if an angled fiber morphology is desired, a counter-rotating die and mandrel system can be used in the extrusion.
Following extrusion, the extruded tube optionally may be conditioned at 20-30 °C at a controlled humidity in the range of 10-50% for a period of at least 24 hours. This conditioning provides a constant low moisture level in the tube which prevents hydrolysis and helps to optimize the orientation of the polymer in the subsequent blowing steps.
Balloon blowing may follow conventional single or multi-step techniques known in the art, for instance free blowing, mold blowing, or a combination of both, optionally with a preceding axial stretching step. The axial stretch ratio, if used, is suitably from about 2x to about 5x. Balloon forming will typically be performed at a temperature in the range of 95 °C to 165°C, depending on the base polymer material and the amount of LCP incorporated into the blend. The balloon forming step should be performed above the glass transition temperature but below the melt temperature of the base polymer material (for block copolymers the blowing temperature should be above the highest glass transition). The radial expansion ratio is suitably from about 3x to about 12x. Depending on the technique, expansion pressures may range from about 200- 500 psi (1379 -3447 kPa).
In some cases it may be desirable to subject the formed balloon to a heat set step. In this step the pressurized balloon is held for a brief time, suitably about 5-60 seconds, at a temperature above that used to form the balloon after which the mold is rapidly quenched to ambient temperature and the balloon removed from the mold.
In the absence of a compatibilizer, or where the compatibilizer is only effective to compatibilize the melt, the LC and base polymers will typically undergo phase separation on cooling so that an opaque article is obtained. The phase separation, however, occurs on a microscopic scale so that the LC discontinuous phase is uniformly distributed in a continuous base polymer phase. The LC discontinuous phase is fibrous, and the fibers orient during the stretching and blowing steps of the balloon formation so a high level of reinforcement is provided to the base polymer. However, reinforcement by the fibrous LC phase can be achieved without a major reduction in flexibility and without presenting huge increases in melt viscosity, both of which effects are commonly encountered when reinforcing fillers are added to thermoplastic polymer compositions. Moreover, the fiber size is so small that, even with the extremely thin films encountered in angioplasty balloons, film porosity is not created.
The invention is illustrated by the following non-limiting examples.
EXAMPLES EXAMPLE 1
Pebax 7033 polymer was melt blended at a temperature of 225 °C with liquid crystal polymer Vectra LKX 1107 at the ratio of 95% to 5% respectively by weight and the mixture was extruded into tubing of 0.018 x 0.037 inch (0.48 x 0.94 mm). A 3.0 mm balloon was formed from the tube at 98 °C and at 450 psi (4102 kPa) forming pressure using a 3.0 mm mold form in a single blowing step. The balloon had a double wall thickness of 0.00175 inch (0.044 mm) and had an opaque appearance. The balloon burst at 265 psi (1827 kPa). This reinforced composite balloon has much higher puncture resistance and more durability than a similar balloon made from 100% Pebax 7033.
Improved length stability upon expansion is a desirable property for high strength, relatively compliant balloons used for stent deployment. The following Examples 2 and 3 demonstrate that the LCP blends used in the invention provide improvement is length stability for such balloons.
EXAMPLE 2
The same composition as shown in Example 1 was used to extrude a tube of 0.022 x 0.036 inch (0.56 x 0.91 mm). The 3.0 mm balloon was made at 95 °C with a blowing pressure of 400 psi (2758 kPa). The balloon with double wall thickness of 0.0014 inch (0.036 mm) was inflated from 4 atm ( 405 kPa) to 13 atm (1317 kPa) at 1 atm (101 kPa) increments and the balloon length change was 2.5% at the span of 4-13 atm.
For comparison 100% Pebax 7033 tubing with dimension of 0.0192 x 0.0344 (0.49-0.87 mm) was used to form 3.0 mm balloon at 95 °C and 400 psi (2758 kPa) blowing pressure. The formed balloon with double wall thickness of 0.0014 inch (0.036 mm) was inflated from 4 atm (405 kPa) to 13 atm (1317 kPa) at 1 atm (101 kPa) increments and the balloon grew 8.0% of its original length before inflation.
EXAMPLE 3
The same molding conditions as in the previous examples were used for this example. A 40 mm long 3.0 mm diameter balloon mold was used to make a 100% Pebax 7033 balloon. The formed balloon had a body length of 37.0 mm after the balloon was removed from the mold. The same mold and balloon forming conditions were used for a LCP reinforced Pebax 7033 balloon formed from the melt blend product described in Example 1. The formed balloon had the body length of 38.5 mm, corresponding to a 50% improvement in balloon body length stability as a result of the inclusion of the 5% LCP component.
The foregoing examples and disclosure are intended to be illustrative and not exhaustive. These examples and description will suggest many variations and alternatives to one of ordinary skill in this art. All these alternatives and variations are intended to be included within the scope of the attached claims. Those familiar with the art may recognize other equivalents to the specific embodiments described herein which equivalents are also intended to be encompassed by the claims attached hereto.

Claims

CLAIMSWhat is claimed is:
1. A medical device at least a portion of which is composed of a polymeric material in which the polymeric material is a melt blend product of at least two different thermoplastic polymers, one of the thermoplastic polymers being a thermoplastic liquid crystal polymer (LCP) having a melting point of less than 250°C.
2. A device as in claim 1 wherein the medical device is a catheter.
3. A device as in claim 2 wherein said device portion is a balloon mounted on the catheter.
4. A device as in claim 1 wherein the melt blend product includes said LCP in an amount of about 0J to about 20 weight percent and a thermoplastic non-LCP base polymer in an amount of from about 50 to about 99.9% by weight, the base polymer having a melting point in the range of about 140°C to about 265°C.
5. A device as in claim 4 wherein the base polymer has a melting point of about 220 °C or less.
6. A device as in claim 5 wherein the melting point of the base polymer is from about 150° to about 210°C and the melting point of the LCP is about 150°C to about 230 °C.
7. A device as in claim 4 wherein the base polymer is selected from the group consisting of acetal homopolymers and copolymers, cellulosic polymers, poly(chlorotrifluoroethylene), poly(vinylidine fluoride), nylon 6,6, nylon 6, nylon 6,10, nylon 12, nylon 11, polyoxymethylene, poly(methyl methacrylate) having a melting point in the range of above 140°C, polypropylene homopolymers and copolymers, polycarbonate polymers and copolymers, poly(ethylene-vinyl alcohol), polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, thermoplastic polyurethanes (aromatic and/or aliphatic) and thermoplastic elastomers.
8. A device as in claim 7 wherein said base polymer is a thermoplastic polyamide elastomer or a thermoplastic polyester elastomer.
9. A device as in claim 8 wherein said base polymer is present in said melt blend in an amount of from about 85 to about 99.5 weight percent and said LCP is present in an amount of 0.5 to about 8 percent.
10. A balloon for a medical device, the balloon being prepared by radial expansion of a tubular parison of polymeric material, wherein the polymeric material is a melt blend product of at least two different thermoplastic polymers, one of the thermoplastic polymers being a thermoplastic liquid crystal polymer (LCP) having a melting point of less than 250 °C
11. A balloon as in claim 10 wherein the melt blend product includes said
LCP in an amount of about 0J to about 20 weight percent and a thermoplastic non-LCP base polymer in an amount of from about 50 to about 99.9% by weight, the base polymer having a melting point in the range of about 140°C to about 265 °C.
12. A medical device, at least a portion of which is composed of a polymeric material, in which the polymeric material comprises at least two different thermoplastic polymers, one of the thermoplastic polymers being a thermoplastic liquid crystal polymer (LCP) and a second of the thermoplastic polymers being a non-LCP base polymer, the polymeric material being a two-phase system of LCP fibers distributed in the non-LCP base polymer.
13. A medical device as in claim 12 wherein said medical device portion is an elongated structure, and the fibers are oriented in the longitudinal direction of the structure.
14. A medical device as in claim 12 wherein said medical device portion is an elongated structure, and the fibers are oriented at an angle to the longitudinal direction of the structure.
15. A medical device as in claim 12 wherein the LCP has a melting point of less than 275 °C and the base polymer has a melting point in the range of about 140°C to about 265 °C.
16. A medical device as in claim 12 wherein the base polymer is a thermoplastic elastomer.
17. A medical device as in claim 12 wherein said medical device portion is a catheter balloon.
18. A method of forming a balloon by radial expansion of an extruded tubular parison of a polymer material comprising a thermoplastic non-LCP base polymer, the method comprising: melt blending said non-LCP base polymer with 0J to 20 weight % of an LCP prior to formation of said parision; extruding the parison in a manner so that the LCP phase separates during solidification of the melt blend product and forms longitudinally oriented fibers in a matrix of said base polymer; and then radially expanding the parison to form said balloon.
19. A method as in claim 18 wherein the LCP has a melting point of less than
275°C and the base polymer has a melting point in the range of about 140°C to about 265 °C.
20. A method as in claim 19 wherein the LCP melting point is in the range of 150°C to 249°C.
PCT/US2000/003821 1999-02-25 2000-02-15 Medical devices made from polymer blends containing liquid crystal polymers WO2000050105A2 (en)

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EP00910181A EP1154808B1 (en) 1999-02-25 2000-02-15 A balloon for medical devices made from polymer blends containing low melting temperature liquid crystal polymers
JP2000600715A JP4954372B2 (en) 1999-02-25 2000-02-15 Medical devices formed from polymer blends containing low melting temperature liquid crystal polymers
CA002362607A CA2362607C (en) 1999-02-25 2000-02-15 Medical devices made from polymer blends containing low melting temperature liquid crystal polymers
DE60009866T DE60009866T2 (en) 1999-02-25 2000-02-15 A BALLOON FOR MEDICAL ARTICLES OF LOW-MELTING LIQUID CRYSTAL POLYMERS CONTAINING POLYMER MIXTURES
AT00910181T ATE264122T1 (en) 1999-02-25 2000-02-15 A BALLOON FOR MEDICAL PRODUCTS MADE OF POLYMER BLENDS CONTAINING LOW-MELTING LIQUID CRYSTAL POLYMERS

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US6284333B1 (en) 2001-09-04
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JP2014076369A (en) 2014-05-01
WO2000050105A3 (en) 2000-12-14
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EP1331016A2 (en) 2003-07-30

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