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WO2024249005A1 - Copolymère aba à trois blocs et implants biorésorbables fabriqués avec celui-ci - Google Patents

Copolymère aba à trois blocs et implants biorésorbables fabriqués avec celui-ci Download PDF

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Publication number
WO2024249005A1
WO2024249005A1 PCT/US2024/026979 US2024026979W WO2024249005A1 WO 2024249005 A1 WO2024249005 A1 WO 2024249005A1 US 2024026979 W US2024026979 W US 2024026979W WO 2024249005 A1 WO2024249005 A1 WO 2024249005A1
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WIPO (PCT)
Prior art keywords
block copolymer
block
tmc
weight
stent
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Pending
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PCT/US2024/026979
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English (en)
Inventor
Xinhua Zong
Ni Ding
Mary Beth Kossuth
Erik David ELI
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Abbott Cardiovascular Systems Inc
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Abbott Cardiovascular Systems Inc
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Publication date
Priority claimed from US18/643,271 external-priority patent/US20240400756A1/en
Application filed by Abbott Cardiovascular Systems Inc filed Critical Abbott Cardiovascular Systems Inc
Priority to CN202480029843.6A priority Critical patent/CN121039196A/zh
Publication of WO2024249005A1 publication Critical patent/WO2024249005A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/08—Materials for coatings
    • A61L31/10—Macromolecular materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F5/00—Orthopaedic methods or devices for non-surgical treatment of bones or joints; Nursing devices ; Anti-rape devices
    • A61F5/0003—Apparatus for the treatment of obesity; Anti-eating devices
    • A61F5/0013—Implantable devices or invasive measures

Definitions

  • the present disclosure relates to polymer compositions and bioresorbable implants made therewith.
  • embodiments of the invention relate to a polymeric material which is an ABA tri -block copolymer and implantable devices made from and/or coated with the copolymer.
  • percutaneous vascular procedures include a mechanical approach for thrombus disruption or removal, also known as thrombectomy.
  • thrombectomy a mechanical approach for thrombus disruption or removal
  • the medical device is removed from the vessel. Once the medical device is removed from the vessel, an opening in the vessel wall remains, leading to hemorrhage into surrounding tissues.
  • conventional vessel closure techniques include applying manual compression and sutures. However, if the patient utilizes anticoagulants, requires longterm bed rest (e.g., 24 or more hours), or the vessel wall opening is large, these conventional techniques may no longer be adequate.
  • An alternative hemostasis method is to use various vessel closure devices. Examples of closure devices include the Abbott Vascular Perclose family of mechanical based vessel closure devices. Alternative hemostasis methods include other vessel closure devices. One example is a plug-based closure device where the plug may be formed of a bioabsorbable and bioresorbable polymer.
  • interventional vascular procedures may include the use of vascular stents.
  • self-expanding and balloon expandable stents are often used in the iliac and coronary vasculature to reduce blood loss in the instances of (or anticipated) vessel dissection or perforation.
  • Self-expanding and balloon expandable stents are often covered for the treatment of restenotic and in-stent restentoic lesions in arteries, thrombotic occlusion, aneurysms, and traumatic or iatrogenic vessel injuries.
  • the nonwoven matrix cover is commonly formed of nano- or submicron fibers which resemble the native extracellular matrix.
  • stent restenosis may occur, especially at the distal and proximal end of the covered stent, due to smooth muscle cell (SMC) migration and proliferation across the internal elastic lamina (IEL) to luminal surface.
  • SMC smooth muscle cell
  • IEL internal elastic lamina
  • the specific placement of the stent acts as a scaffold to the vessel, which supports the vessel’s walls and helps prevent the reoccurrence of the blockage inside the vessel.
  • Placement of the stent may occur utilizing a catheter as a stent deployment mechanism to deliver and position the stent at the targeted area.
  • a typical coronary stent delivery system uses a balloon expandable release method by which the mounted stent is expanded to the vessel diameter with the assistance of a balloon. Once the stent is deployed to the target area, the balloon is deflated and withdrawn with the catheter and other delivery system elements.
  • a stent graft or a covered stent is used.
  • the covered stent’s functions depend on the stent design, the graft material properties, the stent/graft construction, and design of the hybrid stent graft system.
  • the stent functions to provide a scaffold to the impaired vessel while the graft material becomes a conduit for the blood flow.
  • the covered stent facilitates reopening of the vessel lumen while also providing a barrier against restenosis.
  • Another example includes treating aneurisms to provide a bypass and partially, or in some cases completely, exclude the sac of the aneurism from the circulatory system.
  • the covered stent is used in the emergency treatment of vascular injuries such as dissections or used to prevent prophylactically in the case of an accidental tear of the vessel, where the stent plays a role in scaffolding the vessel and maintaining the patency of the vessel lumen while the graft material seals tears and reestablishes blood flow distally.
  • the device When the tear occurs in the blood vessel during a percutaneous intervention, the device must be fully positioned against the vessel wall to prevent or minimize blood leakage between the outer surface of the device and the vessel inner wall until coagulation may occur.
  • the covered stent may fail to provide its intended functionality.
  • the covered stent may fail to reach the target area in order to deploy the covered stent.
  • stent dislodgement from the catheter delivery system may occur or there may be difficulties inflating or deflating the balloon or even deploying a self-expanding stent from the sheath. Difficulties withdrawing the delivery system may occur.
  • the stent may fracture, migrate, cause restenotic occlusion, or be in malapposition to the arterial wall and a source of thrombus build up.
  • Another potential problem is that the covering may tear or become separated from the remainder of the stent
  • the most common failure mechanisms of covered stents are due to failure of delivery to the target lesion, stent dislodgment, and failure to seal the perforation, which can be due to inadequacies in the polymer materials used in the device.
  • Stent dislodgment may occur during stent delivery due to poor retention, high profile, or high advancement push force may lead to poor securement of the crimped stent onto the balloon.
  • the retention process must secure the covered stent onto the balloon; however, the process must not damage the stent, cover, or balloon.
  • the retention of the covered stent onto the balloon is more challenging due to the thickness from the cover material on the stent.
  • the covering may make deployment more difficult in a self-expanding stent or lead to high deployment forces (or inability to deploy).
  • polymeric materials that may be used in medical implants, including vessel closure devices, and covered medical devices, such as stents.
  • the polymeric material should be flexible, strong and bioresorbable in months instead of year(s).
  • One example application of the polymeric material is covered stents for use in many vascular procedures.
  • the polymer compositions are ABA tri-block copolymers with an A block that is crystalline and advantageously provides mechanical strength and a B block that is amorphous and advantageously provides elasticity, flexibility, and an overall relatively fast degradation rate.
  • the ABA tri-block copolymers are biodegradable, biocompatible, and bioabsorbable and therefore suitable for use in making a variety of medical devices.
  • the techniques described herein relate to an implantable device which includes an implantable device body and a polymeric material applied to and/or that forms the implantable device body.
  • the implantable device may be a vessel closure device that provides rapid hemostasis at a puncture site in a wall of a blood vessel.
  • the implantable device may be a stent which is covered with the polymeric material.
  • all or portions of digestive tract devices, medical patches and films, valves, clotting devices, atrial appendages, transplants, septal occluders, abdominal aortic aneurysm (AAA) repair devices, and combinations or modifications thereof can be formed of and/or coated with the polymeric material.
  • the A block of an example ABA tri-block copolymer is a polyglycolide (PGA), also known as polyglycolic acid.
  • the B block of the example ABA tri-block copolymer includes an amorphous random copolymer of glycolic acid (GA), trimethylene carbonate (TMC), and s-caprolactone (CL).
  • the A block of an example ABA tri-block copolymer may also include poly- L-Lactic Acid (PLLA), also known as poly-L-Lactide, in place of or in addition to PGA.
  • PLLA poly- L-Lactic Acid
  • the B block of the example ABA tri-block copolymer includes an amorphous random copolymer of glycolic acid (GA) and/or lactic acid (LA), where LA can be LLA and/or DLLA.
  • LA glycolic acid
  • LA lactic acid
  • trimethylene carbonate (TMC), and e-caprolactone (CL) can also be present. Due to its crystallinity, the A block provides mechanical strength, and the B block, being amorphous, provides elasticity. However, because it was found that TMC and CL degrade slowly, including GA/LA in the B block advantageously make more tunable degradation profiles of implantable device based on needs of targeted therapeutic applications.
  • each A block in the ABA tri-block copolymers can have a weight percent ranging from about 10% to about 35% of the copolymer, or about 15% to about 25%, with the two A blocks together making up about 20% to about 70%, or about 30% to about 50% by weight of the copolymer.
  • the B block in the ABA tri-block copolymers can have a weight percent ranging from about 30% to about 80%, or about 50% to about 70%, by weight of the copolymer.
  • the ABA tri-block copolymer can include the three or more monomers (i.e., GA, LA, TMC and CL) in a weight ratio of about 50/25/25 (GA/LLA:TMC:CL), where GA/LLA stands for either GA or LLA (or combination thereof).
  • the three monomers in the ABA tri-block copolymer can have a weight ratio of about 60/20/20 (GA/LLA: TMC: CL). The weight ratio can be in one or more ranges that include the foregoing weight ratios.
  • the B block can include three or more monomers (i.e., GA, LLA, DLLA, TMC and CL) in a weight ratio of about 15/20/25 (GA/LA:TMC:CL), or about 10/20/20 (GA/LA: TMC: CL), or about 15/25/25 (GA/LA: TMC: CL), or about 30/20/20 (GA/LA:TMC:CL), GA/LA stands for either GA or LA (LLA or DLLA), or a combination thereof.
  • the weight ratio can be in one or more ranges that include the foregoing weight ratios.
  • the soft segment contains no or is substantially free of LLA and/or DLLA, but contains or consists of or consists essentially of the three monomers of GA, TMC and CL. In another embodiment, the soft segment contains no or is substantially free of GA, but contains or consists of or consists essentially of LLA and/or DLLA, TMC and CL.
  • the ABA tri-block copolymer can have first and second glass transition temperatures (Tg-1 and Tg-2) for the amorphous phase and a melting temperature (Tm) and enthalpy of fusion (AH) for the crystalline phase.
  • Tg-1 can be in a range of about -30°C to about 0°C, or about -20°C to about -5°C
  • Tg-2 can be in a range of about 30°C to about 55°C, or about 30°C to about 40°C.
  • Tm can be in a range of about 110°C to about 200°C, or about 145°C to about 200°C
  • AH can be in a range of about 5 J/g to about 50 J/g, or about 10 J/g to about 35 J/g.
  • Figures 1A and IB illustrate examples of medical devices made from an ABA polymeric material according to an embodiment of the present invention.
  • Figures 2A through 2F illustrate an exemplary covered medical device made with an ABA polymeric material according to an embodiment of the present invention.
  • Figure 3 illustrates an attachment of a graft to a stent or scaffold according to an embodiment of the present invention.
  • Figure 4 illustrates an attachment of a graft to a stent or scaffold according to an embodiment of the present invention.
  • Figure 5 illustrates an attachment of a graft to a stent or scaffold according to an embodiment of the present invention.
  • FIGS. 6A through 6C illustrate thermograms of various exemplary triblock copolymers by differential scanning calorimetry (DSC) at a first heat.
  • Figures 7A through 7C illustrate DSC thermograms of the same triblock copolymers as Figures 6A-6C, at a second heat.
  • Figure 8 illustrates a stress strain measurement of an exemplary triblock copolymer.
  • Figure 9 illustrates molar mass change over time for various exemplary triblock copolymers.
  • Figure 10 illustrates mass loss change over time for various exemplary triblock copolymers.
  • One or more embodiments of the present disclosure generally relate to ABA triblock copolymers
  • the ABA tri-block copolymers disclosed herein includes an A block, which is selected to primarily provide or contribute to mechanical strength, and a B block which is selected to primarily provide or contribute flexibility and elasticity.
  • the polymer compositions may be bioabsorbable, biocompatible, and biodegradable.
  • One or more embodiments of the present disclosure may generally relate to apparatuses, systems, and methods of making and using an implantable medical device including a polymeric material (e.g., a closure device or covered stent), that uses an ABA tri-block copolymer.
  • the implantable medical device may be used to provide immediate or substantially immediate hemostasis at a vessel wall opening.
  • the implantable medical device may be used as a covered stent where the stent provides scaffolding to the vessel and the polymeric material is used as a covering and/or coating.
  • the polymeric material is both bioabsorbable and biocompatible and degrades and/or is reabsorbed after the stent has been properly placed and secured.
  • the disclosed polymeric material in the implantable medical device provides a balance of crystalline hard segment to withstand force from the medical procedure and an amorphous soft segment providing delivery, expandability, and conformity with vessel walls. Therefore, the implantable medical device is appropriate to use in many interventional vascular procedures.
  • any of the systems, apparatuses, and methods described herein may be applicable to other uses, including and not limited to digestive tract devices, medical patches and films, valves, clotting devices, atrial appendages, occluders, AAA repair, AV fistulas, tissue transplants and/or a coronary sinus reducer for use in angina treatment. Additionally, elements described in relation to any embodiment depicted and/or described herein may be combinable with elements described in relation to any other embodiment depicted and/or described herein.
  • the polymeric material can be moldable to be appropriately shaped.
  • the polymeric material in the case of a balloon expandable covered stent, the polymeric material is a woven or non-woven mesh which is incorporated around the stent and should be sufficiently flexible to allow the balloon expandable covered stent to expand.
  • the polymeric material may be molded and allow moldability.
  • the polymeric material can be compressible for appropriate delivery.
  • the polymeric material is advantageously able to push through the vessel wall prior to the implantable device being used. Therefore, the polymeric material will desirably have compression properties.
  • the polymeric material may be soluble for spray coating or dip-coating on the stent or other devices. Roller-coating and/or ink-jetting are also possible.
  • Such coating may contain one or more anti-proliferative drugs, such as sirolimus (Rapamycin), everolimus, zotarolimus, deforolimus, umirolimus, temsirolimus, and its analog or antimicrotubule agents such as paclitaxel.
  • the polymeric material may be electrospun to create a filament like structure.
  • the polymeric material can be elastic.
  • the elastic properties allow the polymeric material to fit the particular vessel’s geometry, such as in the use of a vessel closure device or around a stent used as vessel scaffolding, or a stent coating which can tolerate the stent crimping and expansion.
  • the polymeric material should be able to undergo low deformation during the deployment. In other embodiments, the polymeric material should be able to undergo low deformation after the deployment. In even other embodiments, the polymeric material should be able to undergo low deformation both during and after deployment.
  • the polymeric material can have low deformation while the covered stent is being inserted and continue to have low deformation until the polymeric material begins to degrade, leaving the stent in the appropriate position.
  • the polymeric material can have a low deployment force.
  • the polymeric material can have relatively fast degradation following implantation.
  • the polymeric material may degrade in less than 1 month, within 2 months, within 3 months, within 4 months, within 5 months, within 6 months, within 7 months, within 8 months, within 1 year, or more than 1 year following implantation. In some procedures, it may be preferable for the polymeric material degrade within about 1 month to about 6 months following implantation.
  • the polymeric material should be biocompatible, or bioabsorbable, or bioresorbable, or biodegradable, or a combination thereof.
  • the polymeric material when used in a covered stent, the polymeric material should be biocompatible with the vessel into which the stent is being inserted. As the polymeric material degrades, the degraded material is advantageously bioabsorbable by the vessel or removed through body’s excretory system.
  • the polymeric material is advantageously biocompatible with the vessel walls and bioabsorbable by the body as the vessel walls close without the polymeric material.
  • the polymers include an A block and a B block.
  • the A block is selected primarily to provide or contribute mechanical strength, while the B block is selected primarily to provide or contribute elasticity and flexibility, to the polymeric material.
  • the monomeric constituents of the ABA tri-block copolymer typically include glycolic acid (GA), which is often provided as condensed glycolide dimer, lactic acid (LA), which can also be provided as condensed lactide dimer, trimethylene carbonate (TMC), and s-caprolactone (CL).
  • Glycolic acid, glycolide dimer, and polyglycolide have the following chemical structures: glycolic acid (GA) glycolide polyglycolide (PGA)
  • Lactic acid, lactide dimer, and polylactide (aka polylactic acid) have the following chemical structures: polylactic acid (PLA)
  • PGA When used to form the A block, PGA will typically have n glycolide units joined to each other to form a crystalline polymer, with a terminal hydroxyl or terminal carboxylate being condensed with and forming a covalent bond with a corresponding terminal monomer of the B block.
  • a diol initiator may be used to create the glycolic acid/glycolide (GA)/lactic acid (LA), trimethylene carbonate (TMC), or e-caprolactone (CL) polymer through anionic living polymerization.
  • the B block is synthesized first by using a diol as an initiator and a catalyst, which yields a B block terminated with two hydroxyl groups — one at each end.
  • the catalyst may be a tin catalyst such as stannous octanoate.
  • the A block may be synthesized after the B block using the same tin catalyst.
  • Trimethylene carbonate (TMC) and its monomeric unit in poly(trimethylene carbonate) after ring opening and polymerization have the following chemical structures: trimethylene carbonate (TMC) poly(trimethylene carbonate)
  • s-caprolactone (CL) and its monomeric unit in polycaprolactone after ring opening and polymerization have the following chemical structures: s-caprolactone (CL) polycaprolactone
  • the A block is formed of a crystalline polyglycolide (PGA) and/or poly(l-lactic acid) (PLLA).
  • Polyglycolide may also be referred to as poly(glycolic acid)/polyglycolic acid (PGA).
  • PGA is a biodegradable, thermoplastic polymer and is a linear aliphatic polyester.
  • the B block is formed of an amorphous random copolymer.
  • the amorphous random copolymer includes glycolic acid/glycolide (GA) and/or lactic acid (LA), tri-methylene carbonate (TMC), and s-caprolactone (CL) monomeric units.
  • Glycolide and lactide are each typically provided in dimer form.
  • TMC is also referred to as 1,3 -propylene carbonate and is initially a 6-membered cyclic carbonate ester before ring opening and polymerization.
  • CL is also referred to as caprolactone and is a lactone (e g., a cyclic ester), which includes a seven-member ring initially.
  • the polymeric materials used to make medical implants are tri-block copolymers with an ABA symmetric triblock copolymer pattern.
  • the copolymers exhibit a blend of mechanical strength and elasticity.
  • the A units comprised of PGA and/or PLLA provide or contribute mainly to mechanical strength and, therefore, the A blocks play the majority role in the polymeric material’s mechanical strength.
  • the TMC and CL monomeric units in the B block provide or contribute mainly to elasticity and therefore the B block plays the majority role in the polymeric material’s elasticity and flexibility.
  • the GA and/or LA units in the B block are more hydrophilic than TMC and CL and promote faster biodegradation and resorption by the body.
  • the polymeric material have a relatively fast degradation time.
  • the TMC and CL in the B block degrade relatively slowly.
  • embodiments may advantageously include GA and/or LA in the B block to accelerate degradation of the random copolymer.
  • Example embodiments may include two A blocks where each A block is less than about 10% weight, about 10% weight, about 15% weight, about 20% weight, about 25% weight, about 30% weight, or more than about 30% weight.
  • the A block may be formed of GA, LLA.
  • example embodiments may include a B block that contains less than about 15% weight, about 15% weight, about 17.5% weight, about 20% weight, about 22.5% weight, about 25% weight, about 30% weight, or more than about 30% weight of GA, LA, or a combination of GA and LA, less than about 5% weight, about 5% weight, about 10% weight, about 20% weight, about 25% weight, or more than about 25% weight of TMC, and less than about 20% weight, about 20% weight, about 25% weight, or more than about 25% weight of CL.
  • the A block may contain only PGA and the B block may contain GA rather than LA, in addition to the TMC and CL, as monomeric units.
  • the A block may contain only PLLA rather than PGA and the B block may contain LA rather than GA, in addition to the TMC and CL, as monomeric units.
  • the A block may contain only PGA and the B block may only contain LA, in addition to the TMC and CL, as monomeric units.
  • the A block may contain only PLLA and the B block may only contain GA, in addition to the TMC and CL, as monomeric units.
  • the A block may contain a copolymer of PGA and PLLA, which may impact (e.g., decrease) the crystallinity of the A block
  • the B block may include only GA, only LLA, only DLLA, both GA and LLA, both DLLA and LLA, both GA and LLA, or GA, LLA, and DLLA, in addition to TMC and CL, as monomeric units.
  • the A block may contain only PGA, only PLLA, or both PGA and PLLA, while the B block contains a mixture of GA, LLA, and DLLA, in addition to the TMC and CL, as monomeric units.
  • Example #13 appears to be a favorable formulation for use in making the anchor seal and cap seal for closing perforated vessels due to its physical characteristics, while having good bioabsorption.
  • each A block in the ABA tri-block copolymer can have a weight percent ranging from about 10% to about 30% of the copolymer, or about 15% to about 25%, with the two A blocks together making up about 20% to about 60%, or about 30% to about 50% by weight of the copolymer.
  • the B block in the ABA tri-block copolymer can have weight percent ranging from about 40% to about 80%, or about 50% to about 70%, by weight of the copolymer.
  • the ABA tri-block copolymer can include the monomers (i.e., GA and/or LA, TMC and CL) in a weight ratio of about 50/25/25 (GA/LA:TMC:CL). In other embodiments, the monomers in the ABA tri-block copolymer can have a weight ratio of about 60/20/20 (GA/LA:TMC:CL). In yet other embodiments, the monomers in the ABA tri-block copolymer can have a weight ratio of 50-60 parts GA/LA: 10-40 parts TMC: 10-40 parts CL, with the proviso that the block copolymer includes 100 parts of combined GA/LA, TMC and CL.
  • the monomers in the ABA tri-block copolymer can have a weight ratio of 50-60 parts GA/LA: 10-40 parts TMC: 10-40 parts CL, with the proviso that the block copolymer includes 100 parts of combined GA/LA, TMC and CL.
  • the monomers in the ABA tri-block copolymer can have a weight ratio of 50-60 parts GA/LA:20-25 parts TMC:20- 25 parts CL, with the proviso that the block copolymer includes 100 parts of combined GA/LA, TMC and CL.
  • the B block can include the monomers (i.e., GA/LA, TMC and CL) in a weight ratio of about 15/20/25 (GA/LA: TMC: CL), or about 10/20/20 (GA/LA: TMC: CL), or about 15/25/25 (GA/LA:TMC:CL), or about 30/20/20 (GA/LA: TMC: CL), or in a weight ratio of about 15-30 parts GA: 20-25 parts TMC: 20- 25 parts CL, or in a weight ratio of about 15-30 parts GA: 10-40 parts TMC: 10-40 parts CL.
  • the monomers i.e., GA/LA, TMC and CL
  • the ABA tri-block copolymer can have first and second glass transition temperatures (Tg-1 and Tg-2) for the amorphous phase and a melting temperature (Tm) and enthalpy of fusion (AH) for the crystalline phase.
  • Tg-1 can be in a range of about -10°C to about -40°C, or about -15°C to about -30°C
  • Tg-2 can be in a range of about 40°C to about 55°C, or about 45°C to about 50°C.
  • Tm can be in a range of about 105°C to about 220°C, or about 145°C to about 210°C
  • AH can be in a range of about 10 J/g to about 35 J/g, or about 13 J/g to about 30 J/g.
  • the block copolymer can have a tensile strength in a range of about 5 MPa to about 100 MPa, preferably about 10 MPa to about 40 MPa, and more preferably about 10 MPa to about 30 MPa.
  • the block copolymer can have a first glass transition temperature Tg in a range of about -30°C to about 0°C, preferably about -20°C to about - 5°C, and more preferably about -15°C to about -10°C.
  • the block copolymer can have an elongation at break in a range of about 50% to about 1000%, preferably about 100% to about 800%, and more preferably about 200% to about 400%.
  • the block copolymer can have an inherent viscosity in a range of about 0.5 to about 1.8 dL/g, preferably about 0.7 to about 1.5 dL/g, and more preferably about 0.9 to about 1. IdL/g.
  • the block copolymer can have an elastic modulus in a range of about 20 MPa to about 500 MPa, preferably about 40 MPa to about 400 MPa, and more preferably about 40 MPa to about 200 MPa.
  • the block copolymer can have a percent crystallinity in a range of about 5% to about 25%, preferably about 5% to about 20%, and more preferably about 7% to about 15%.
  • Embodiments of the invention also generally include an implantable device, which includes an implantable device body.
  • the implantable device body may vary considerably depending on the intended application. Some example implantable device bodies will now be discussed.
  • the implantable device body relates to a vessel closure delivery device.
  • the vessel closure delivery device may include an actuator, an anchor, a cap, a closure element, a delivery sheath, a fluid-blocking component, and/or a suture element.
  • Examples of the implantable device body can be found in co-pending U.S. Provisional Patent Application No. 63/495,360, filed April 11, 2023, and entitled “Vessel Closure Device with Improved Safety and Tract Hemostasis” and U.S. Patent Application Publication No. 2022/0110617, entitled “Vessel Closure Device with Improved Safety and Tract Hemostasis”, the disclosures of which are incorporated herein in their entireties by reference.
  • the implantable device body is a stent.
  • the stent may include a balloon-expandable stent, self-expanding stent, coronary stent, peripheral stent, carotid stent, neurological stent, vascular stent, ureteral stent, prostatic stent, colon stent, esophageal stent, pancreatic stent, biliary stent, glaucoma drainage stent, stent for AV fistula, coronary sinus reducer, or other appropriate stent types.
  • the balloon expandable stent is the Omnilink EliteTM Vascular Balloon-Expandable Stent.
  • the stent may be formed of a variety of metals including cobalt chromium, stainless steel, nitinol, or other appropriate metals.
  • the stent (e.g., not including the covering or coating) has a thickness ranging from about 50 pm to about 250 pm, preferably from about 90 pm to about 210 pm, more preferably from about 110 pm to about 160 pm.
  • the implantable device body can be digestive tract devices, medical patches and films, valves, clotting devices, atrial appendages, AAA repair devices, and/or tissue transplants.
  • the covering may be on the outside, inside, some combination thereof, or encapsulating the stent.
  • the covering may be for the entire stent or a portion of the stent, e.g., which portion requires sealing specifically due to the purpose of that particular stent graft. Applying Polymeric Material Onto Implantable Device
  • the polymeric material is applied to the implantable device body by the use of an electrospinning process.
  • electrospinning is a fiber production method based on using electric force to attract charged polymer solution threads to create a polymer fiber.
  • the polymer fiber may differ in fiber diameter based on the electrospinning process.
  • an ABA copolymer solution is provided and utilizes an electrospinning process to produce ABA copolymer fibers.
  • the ABA copolymer solution flows out of a needle and is electrostatically attracted to an opposite charge on a mandrel.
  • the polymer is wrapped around the mandrel to create nonwoven 3D web with individual ABA copolymer fibers.
  • the final individual ABA copolymer fibers may have a spider web like consistency and appearance after the electrospinning process.
  • the ABA copolymer fibers may be drawn out into long filaments during the electrospinning process.
  • the electrospun polymeric material is used to create the implantable device body as well as the polymeric coating. Since the polymeric material advantageously has a rubber like form and is biodegradable, the polymeric material may be used to create some portion, most or all the product’s structure. For example, the extent and location of the covering may depend on the purpose of such device. By way of further example, for anchoring one might want the covering in a middle portion of the device, but the edges may anchor in the vessel or perhaps even limit risk for edge thrombus build-up.
  • the polymeric material can be used to cover an implantable medical device, such as a stent.
  • the polymeric material can be used to form a cap and/or anchor for a vessel closure device.
  • the electrospun filaments may be directly overlayed onto the implantable device body.
  • the electrospun polymeric filaments are initially deposited into a rope-like structure.
  • the rope-like polymeric material is then overlayed onto the implantable device body.
  • the polymeric material may have a durable, highly elastic, tear resistant, and biodegradable structure with a consistency similar to Teflon tape (e.g., stretchy with recoverability).
  • the polymeric material may be dissolved in a solution.
  • the solvent may be hexafluoro isopropanol or other appropriate solvent(s).
  • the active pharmaceutical ingredient such as everolimus may be co-dissolved with the polymer and applied on the stent as an anti-restenotic coating through spraying, roller-coating, and/or ink-jetting.
  • the polymeric material may be melted and then be electronically sprayed as a coating onto a medical device and/or drug delivery device.
  • FIG. 1 A and IB illustrate an example of an anchor 102 and a cap 104 made from the ABA polymer.
  • the anchor 102 may be passed through an opening (e g., puncture) defined in a wall of a blood vessel and deployed into the vessel lumen.
  • the anchor 102 can then be drawn proximally to draw the anchor into contact with an inner surface of the blood vessel wall.
  • the cap 104 can then be deployed on the outside surface of the blood vessel wall to close the puncture by advancing the cap 104 along the suture element 106.
  • the suture element 106 can optionally be formed of or coated in the ABA polymer.
  • the anchor 102 includes a keel 120 (discussed more fully below) and a surface.
  • the suture 106 can be threaded through holes or eyelets within the anchor 102 to thereby secure the suture 106 to the anchor 102, such as illustrated in FIG. IB.
  • Such a configuration also allows for any forces applied to the suture 106 (i.e., pulling or tensioning the suture 106) to be transferred to the anchor 102. For example, when a physician or other practitioner exerts a proximal pulling or tugging force on the suture 106, a proximal pulling or tugging force will be exerted on the anchor 102, moving the anchor 102 in a proximal direction.
  • the extravascular cap 104 can be made from ABA polymer and be of sufficient size and geometry to prevent it from passing through the puncture access site at the surface of the blood vessel.
  • the size and geometry of the cap 104 can significantly increase patient safety by preventing extravascular components from passing through the access site during and/or after deployment.
  • the cap 104 can have a diameter ranging from about 1 mm to about 10 mm, from about 3 mm to about 8 mm, from about 4 mm to about 5 mm, or a range defined by any two of the foregoing values.
  • the cap 104 can have another size and shape based upon the specific dimensions of the access site, so that the cap 104 does not pass through the puncture/access site and into the vessel lumen.
  • the cap 104 can have a low-profile and be made from a biodegradable material.
  • the cap 104 can also have a desired flexibility to conform to the anatomy at the access site (especially in vessels with significant calcification present) and provide more effective sealing than would rigid materials.
  • the cap 104 can be deployed through an access tissue tract and placed on top of the vessel, acting as the primary extravascular seal with the vessel wall or other tissue disposed between the anchor 102 and the cap 104.
  • FIGS. 2A through 2F illustrate an example of a covered stent or scaffold made from the ABA polymer.
  • Figures 2A and 2B are SEM images of a polymer coating 204, such as formed by the ABA polymer, on a stent or scaffold body 222 of a stent or scaffold 220 to form a covered stent or scaffold 200.
  • Figure 2C illustrates the covered stent or scaffold 200 with a lumen 206.
  • Figure 2D illustrates a profile view of the covered stent or scaffold 200
  • Figure 2E illustrates an example of the flexibility of the covered stent or scaffold 200 where the body or frame 222 and the polymer coating 204 are both formed of the ABA polymer
  • Figure 2F illustrates a zoomed or more detailed view of the body or frame 222 illustrating the stent or scaffold rings 228 and connectors 229.
  • covered stent or scaffold 200 of Figures 2A through 2F illustrate a self-expandable stent or scaffold
  • other stents or scaffolds are possible, including balloon expandable stents or scaffolds that are coated with the polymer coating 204, while the underlying stent body or scaffold body is formed of a metal alloy, such as nitinol, elgiloy, 316 stainless steel, L605 Co-Cr, MP35N cobalt alloy, ternary nickel titanium platinum, platinum cobalt, tantalum alloys, and combinations or modifications thereof.
  • a metal alloy such as nitinol, elgiloy, 316 stainless steel, L605 Co-Cr, MP35N cobalt alloy, ternary nickel titanium platinum, platinum cobalt, tantalum alloys, and combinations or modifications thereof.
  • attachment or coupling of the graft 300 to the crimped stent or scaffold 320 can be performed using circular flat rings or ribbons 330a surrounding the ends of the graft 300 and maintaining attachment or coupling of the graft body to the body or frame at both ends.
  • the circular flat rings or ribbons (such as O-rings) 330a may be made from the ABA polymer or other polymer such as shape memory polymer (SMP).
  • shape memory polymer SMP
  • the shape memory polymer can be programmed such that the diameter of the circular flat rings or ribbons 330a at room temperature will be small and will subsequently enlarge to the expanded stent diameter once thermally activated.
  • Assembly of the graft 300 and crimped stent or scaffold 320 can include positioning of the graft body onto the crimped body or frame.
  • the circular rings or ribbons 330a can then be loaded at both the proximal and distal ends, which secures the graft 300 in place.
  • attachment or coupling of the graft 300 to the crimped stent or scaffold 320 can be accomplished using circular wire rings 330b at both ends.
  • the wire 330b may be constructed from a shape memory alloy such a nitinol (nickel -titanium alloy).
  • the wire 330b may have a sinusoidal shape which can be deformed at room temperature when placed onto the graft 300 mounted or disposed over the body or frame 320.
  • the recovered pre-deformed shape of the ring 330b may allow full extension of the stent or scaffold 320 during deployment at nominal pressure upon temperature activation.
  • Such rings or ribbons 330a/330b may be of any desired cross-sectional shape.
  • attachment or coupling of the graft 300 to the crimped stent or scaffold 320 can be performed by spot gluing or welding 330c the graft 300 to the proximal and distal ends of the stent or scaffold 320.
  • securement of the graft 300 to the crimped stent or scaffold 320 can be performed by using an adhesive, thermal bonding, solvent bonding, laser welding technology, and combinations or modifications thereof.
  • spot gluing or laser welding can be performed at both ends or done at specified internal locations. The welding, gluing, etc. may be fully circular or at a number of discreet non-continuous positions.
  • Figures 6A-6C and Figure 7A-7C illustrate thermal properties of three example embodiments of an A-B-A block copolymer.
  • Glass transition temperatures (Tg) for the amorphous phase of B-block, melting temperature (Tm) and enthalpy of fusion (AH) for the crystalline phase of A-block were measured by differential scanning calorimetry (DSC) at a heating rate of 10 °C/min in a temperature range of -50-230 °C. The samples were scanned using two heating cycles.
  • Figure 6 shows the first heating cycle while Figure 7 shows the second heating cycle.
  • Glass transition temperatures (Tg) of amorphous B-block (soft segment) in three example embodiments of an A-B-A copolymer is in the range of -30 °C to 0 °C.
  • the melting peak of crystalline A-block (hard segment) in the three example embodiments of an A-B-A copolymer is in the range of 108 °C to 183 °C.
  • the block copolymer in Figures 6A and 7A shows the highest Tm at about 176-183 °C, and AH of 26-30J/g.
  • the block copolymer in Figures 6B and 7B exhibits a Tm at about 151-155 °C, and AH of 11-16 J/g.
  • the block copolymer in Figure 6C exhibits a Tm at about 108 °C, and AH of 21 J/g.
  • Figure 7C illustrates no melting peak due to a slow crystallization process with the lowest content of crystalline A-block in an example embodiment of an A-B-A copolymer.
  • Figure 8 illustrates mechanical properties of an example embodiment of an A-B-A block copolymer carried out using the INSTRON. The tensile strength and the maximum elongation depend on the weight ratio of the A-block as well as monomer ratios within the B-block. Sample 4 has mechanical properties with elongation up to 900% and elastomeric properties due to the absence of a measurable yield stress in the stress-strain curve.
  • Figure 9 and Figure 10 illustrate in-vitro degradation properties of three example embodiments of an A-B-A block copolymer.
  • sample-3 shows the fastest degradation rate with the steepest molecular weight drop and the fastest mass loss.
  • the degradation of A-B-A block copolymers depends on A-block constituent type (GA/LA), and the overall weight ratio of the A-block constituent, including its ratio in the B-block.
  • a stated value should therefore be interpreted broadly enough to encompass values that are at least close enough to the stated value to perform a desired function or achieve a desired result.
  • the stated values include at least the variation to be expected in a suitable manufacturing or production process, and may include values that are within 5%, within 1%, within 0.1%, or within 0.01% of a stated value.
  • any references to “up” and “down” or “above” or “below” are merely descriptive of the relative position or movement of the related elements.
  • Embodiment 1 A block copolymer comprising polyglycolide (PGA) or poly-L- lactide, forming an A block and a random copolymer of glycolide (GA), L-lactide, DL- lactide, trimethylene carbonate (TMC), and s-caprolactone (CL) forming a B block.
  • PGA polyglycolide
  • PLA poly-L- lactide
  • Embodiment 2 The block copolymer of embodiment 1, wherein the block copolymer is an ABA tri -block copolymer with A blocks and an intervening B block.
  • Embodiment 3 The block copolymer of any of embodiment 1-2, wherein each A block has a weight % ranging from about 10% to about 35%, or about 15% to about 25%, by weight of the block copolymer and, in the case of the ABA tri-block copolymer, the A blocks together have a weight % ranging from about 20% to about 70%, or about 30% to about 50%, by weight of the block copolymer.
  • Embodiment 4 The block copolymer of any of embodiment 1-3, wherein the B block has a weight % ranging from about 30% to about 80%, or about 50% to about 70%, by weight of the block copolymer.
  • Embodiment 5 The block copolymer of any of embodiment 1-4, wherein the block copolymer comprises glycolide (GA), trimethylene carbonate (TMC), and s-caprolactone (CL) monomers in a weight ratio of about 50/25/25 (GA:TMC:CL), in a weight ratio of about 60/20/20 (GA:TMC:CL), or in a weight ratio of about 50-60 parts GA: 10-40 parts TMC: 10-40 parts CL, with the proviso that the block copolymer includes 100 parts of combined GA, TMC and CL
  • Embodiment 6 The block copolymer of any of embodiment 1-5, wherein the B block comprises glycolide (GA), trimethylene carbonate (TMC), and e-caprolactone (CL) monomers in a weight ratio of about 15/20/20 (GA:TMC:CL), a weight ratio of about 10/20/20 (GA:TMC:CL), a weight ratio of about 15/25/25 (GA:TMC:CL), a weight ratio of about 30/20/20 (GA:TMC:CL), or in a weight ratio of about 15-30 parts GA: 10-40 parts TMC: 10-40 parts CL.
  • G glycolide
  • TMC trimethylene carbonate
  • CL e-caprolactone
  • Embodiment 7 The block copolymer of any of embodiment 1-6, wherein the block copolymer can have an inherent viscosity in a range of about 0.5 to about 1.8 dL/g, about 0.7 to about 1.5 dL/g, or about 0.9 to about 1 1 dL/g.
  • Embodiment 8 The block copolymer of any of embodiment 1-7, wherein the block copolymer has a first glass transition temperature (Tg-1) of an amorphous phase in a range of about -30°C to about 0°C, or about -20°C to about -5°C, and a second glass transition temperature (Tg-2) of the amorphous phase in a range of about 30°C to about 55°C, or about 30°C to about 40°C.
  • Tg-1 first glass transition temperature
  • Tg-2 second glass transition temperature
  • Embodiment 9 The block copolymer of any of embodiment 1-8, wherein the Tm can be in a range of about 110°C to about 200°C, or about 145°C to about 200°C, and AH can be in a range of about 5 J/g to about 50 J/g, or about 10 J/g to about 35 J/g.
  • Embodiment 10 The block copolymer of any of embodiment 1-9, wherein, the block copolymer has an enthalpy of fusion (AH) in a range of about 5 J/g to about 35 J/g, or about 13 J/g to about 30 J/g.
  • AH enthalpy of fusion
  • Embodiment 11 The block copolymer of any of embodiment 1-10, wherein the block copolymer can have a percent crystallinity in a range of about 5% to about 25%, about 5% to about 20%, or about 7% to about 15%.
  • Embodiment 12 The block copolymer of any of embodiment 1-11, wherein the block copolymer has a tensile strength in a range of about 5 MPa to about 100 MPa, or about 10 MPa to about 40 MPa, or about 10 MPa to about 30 MPa.
  • Embodiment 13 The block copolymer of any of embodiment 1-12, wherein the block copolymer has an elongation at break in a range of about 50% to about 1000%, about 100% to about 800%, or about 200% to about 400%.
  • Embodiment 14 The block copolymer of any of embodiment 1-13, wherein the block copolymer can have an elastic modulus in a range of about 20 MPa to about 500 MPa, preferably about 40 MPa to about 400 MPa, and more preferably about 40 MPa to about 200 MPa.
  • Embodiment 15 An implantable device comprising an implantable device body; and a block copolymer as in any of embodiments 1-14 on and/or forming the implantable device body.
  • Embodiment 16 The implantable device of embodiment 15, wherein the implantable device body comprises a stent having a stent thickness ranging from about 50 pm to about 200 pm.
  • Embodiment 17 The implantable device of embodiment 15, wherein the stent comprises a plurality of interstices and a thickness of the polymeric material within each interstice is about 50 microns when in an expanded state.
  • Embodiment 18 The implantable device of any of embodiments 15-17, wherein the implantable device body comprises a vessel closure device.
  • Embodiment 19 The implantable device of any of embodiments 15-18, wherein one or more layers of the block copolymer is configured to be electrospun onto the implantable device body.
  • Embodiment 20 The implantable device of any of claims 15-19, wherein the block copolymer is an ABA tri-block copolymer with A blocks and an intervening B block, wherein each A block has a weight % ranging from about 10% to about 35%, or about 15% to about 25%, by weight of the block copolymer and the A blocks together have a weight % ranging from about 20% to about 70%, or about 30% to about 50%, by weight of the block copolymer.
  • the block copolymer is an ABA tri-block copolymer with A blocks and an intervening B block, wherein each A block has a weight % ranging from about 10% to about 35%, or about 15% to about 25%, by weight of the block copolymer and the A blocks together have a weight % ranging from about 20% to about 70%, or about 30% to about 50%, by weight of the block copolymer.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Surgery (AREA)
  • Vascular Medicine (AREA)
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Abstract

L'invention concerne un copolymère séquencé comprenant un bloc A et un bloc B. Le bloc A fournit une résistance mécanique tandis que le bloc B fournit une élasticité au matériau polymère. Le copolymère séquencé peut être un copolymère ABA à trois blocs. Le bloc A peut comprendre un ou plusieurs éléments parmi le polyglycolide (PGA), le poly(acide lactique) (PLA) ou un copolymère correspondant. Le bloc B peut comprendre un copolymère aléatoire de (i) glycolide (GA) et/ou lactide (LA), (ii) carbonate de triméthylène (TMC) et (iii) ε-caprolactone (CL). Le copolymère séquencé peut recouvrir un dispositif implantable qui peut être utilisé pour administrer une hémostase immédiate au niveau d'un site de ponction dans une paroi d'un vaisseau sanguin.
PCT/US2024/026979 2023-05-31 2024-04-30 Copolymère aba à trois blocs et implants biorésorbables fabriqués avec celui-ci Pending WO2024249005A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6048947A (en) * 1996-08-10 2000-04-11 Deutsche Institute Fuer Textil- Und Faserforschung Stuttgart Stiftung Des Oeffentlichen Rechts Triblock terpolymer, its use for surgical suture material and process for its production
US6794485B2 (en) * 2000-10-27 2004-09-21 Poly-Med, Inc. Amorphous polymeric polyaxial initiators and compliant crystalline copolymers therefrom
US9468707B2 (en) * 2007-06-29 2016-10-18 Abbott Cardiovascular Systems Inc. Biodegradable triblock copolymers for implantable devices
US20220110617A1 (en) 2020-10-12 2022-04-14 Abbott Cardiovascular Systems, Inc. Vessel closure device with improved safety and tract hemostasis

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6048947A (en) * 1996-08-10 2000-04-11 Deutsche Institute Fuer Textil- Und Faserforschung Stuttgart Stiftung Des Oeffentlichen Rechts Triblock terpolymer, its use for surgical suture material and process for its production
US6794485B2 (en) * 2000-10-27 2004-09-21 Poly-Med, Inc. Amorphous polymeric polyaxial initiators and compliant crystalline copolymers therefrom
US9468707B2 (en) * 2007-06-29 2016-10-18 Abbott Cardiovascular Systems Inc. Biodegradable triblock copolymers for implantable devices
US20220110617A1 (en) 2020-10-12 2022-04-14 Abbott Cardiovascular Systems, Inc. Vessel closure device with improved safety and tract hemostasis

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Title
LINTI ET AL.: "Development, preclinical evaluation, and validation of a novel quick vascular closure device for transluminal, cardiac and radiological arterial catherization", J. MAT. SCI. MAT. IN MEDICINE, vol. 29, 2018, pages 83
WIDJAJA ET AL.: "Triblock copolymers of ε-caprolactone, L-lactide, and trimethylene carbonate: biodegradability and elastomeric behavior", J. BIOMED. MAT. RES, vol. 99, no. 1, 2011, pages 38 - 46

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