ABA triblock copolymer and bioreabsorbable implants made therefrom

Abstract

The block copolymer comprises A block and B block. Block A provides mechanical strength, and block B provides elasticity to the polymer material. The block copolymer may also be an ABA triblock copolymer. Block A may contain one or more of polyglycolide (PGA), polylactic acid (PLA), or copolymers thereof. Block B may contain a random copolymer of (i) glycoside (GA) and / or lactide (LA), (ii) trimethylene carbonate (TMC), and (iii) ε-caprolactone (CL). The block copolymer can coat implantable devices that can be used to provide immediate hemostasis at puncture sites in the blood vessel wall.

Description

Technical Field

[0001] This application claims the benefit of and priority to U.S. Provisional Patent Application No. 63 / 505,290, filed May 31, 2023, and U.S. Patent Application No. 18 / 643,271, filed Apr. 23, 2024, both entitled "ABA TRI-BLOCK COPOLYMER AND BIORESORBABLE IMPLANTS MADE THEREWITH," which are hereby incorporated by reference in their entirety.

[0002] The present disclosure relates to polymer compositions and bioresorbable implants made therefrom. More particularly, embodiments of the present invention relate to a polymeric material that is an ABA triblock copolymer, as well as implantable devices made of the copolymer and / or implantable devices coated with the copolymer.

Background Art

[0003] Several diagnostic procedures and interventional vascular procedures are currently performed translumenally. As an example, percutaneous vascular procedures include mechanical approaches for thrombolysis or thrombectomy, also known as thrombectomy. After a percutaneous vascular procedure, the medical device is removed from the blood vessel. When the medical device is removed from the blood vessel, an opening in the vessel wall remains, resulting in bleeding into the surrounding tissue.

[0004] Generally, conventional vascular closure procedures involve applying manual compression and suturing. However, these conventional techniques may no longer be appropriate if the patient is using anticoagulants, requires prolonged bed rest (e.g., more than 24 hours), or has a large opening in the vessel wall. Alternative hemostasis methods include the use of various vascular closure devices. Examples of closure devices include the Abbott Vascular Perclose series, which are mechanically based vascular closure devices. Alternative hemostasis methods include other vascular closure devices. One example is a plug-based closure device in which the plug can be formed from a bioabsorbable and bioreabsorbable polymer.

[0005] Furthermore, vascular interventions may include the use of vascular stents. For example, self-expanding stents and balloon-expanding stents are often used in the iliac and coronary vascular systems to reduce blood loss in cases of (anticipated) vascular dissection or perforation. Self-expanding stents and balloon-expanding stents are often included in the treatment of restenotic lesions and in-stent restenotic lesions in arteries, thrombotic occlusion, aneurysms, and traumatic or iatrogenic vascular injuries. Nonwoven matrix covers are generally formed of nanofibers or submicron fibers that resemble the natural extracellular matrix. Permanent covered stents are commonly used, but stent restenosis can occur, particularly at the distal and proximal ends of covered stents, due to smooth muscle cell (SMC) migration and proliferation from the internal elastic lamina (IEL) to the lumen surface.

[0006] The specific placement of a stent acts as a scaffold for the blood vessel, supporting the vessel wall and helping to prevent recurrence of occlusion within the vessel. Stent placement can occur using a catheter as a stent deployment mechanism to deliver and position the stent in the target area. As an example, a typical coronary artery stent delivery system uses a balloon-expandable release method, in which the implemented stent is expanded to the vessel diameter using a balloon. Once the stent is deployed in the target area, the balloon is deflated and withdrawn using a catheter and other delivery system elements. In some cases, stent grafts or covered stents are used. The function of a covered stent depends on the stent design, graft material properties, stent / graft structure, and the design of the hybrid stent-graft system.

[0007] In hybrid stent and graft systems, the stent functions to provide a scaffold to the impaired vessel, while the graft material becomes a conduit for blood flow. In more detailed examples, in peripheral artery disease and aortic occlusion, covered stents facilitate the reopening of the vascular lumen and also provide a barrier against restenosis. Another example is the treatment of aneurysms, providing a bypass and, in some cases, completely removing the aneurysmal sac from the circulatory system. In yet another example, covered stents are used in the emergency treatment of vascular injury such as dissection, or prophylactically in cases of accidental vascular tears, where the stent provides a scaffold to the vessel and maintains patency of the vascular lumen, while the graft material seals the tear and restores peripheral blood flow. When a laceration occurs in a blood vessel during 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 inner wall of the vessel until coagulation occurs.

[0008] Stent grafting is a minimally invasive procedure, but complexity and risks still exist. Rarely, covered stents may fail to perform their intended function. For example, a covered stent may not reach the target area for deployment. In other cases, the stent may detach from the catheter delivery system, or there may be difficulties in inflating or deflating the balloon, or even deploying the self-expanding stent from the sheath. Withdrawing the delivery system may be difficult. In other cases, the stent may fragment, migrate, cause restenosis or occlusion, or be malappositioned to the arterial wall, potentially becoming a source of thrombus growth. Another potential problem is that the covering may tear or separate from the rest of the stent.

[0009] The most common failure mechanisms of covered stents are failure to deliver the target lesion, failure to remove the stent, and failure to seal the perforation, which may be due to incompatibility of the polymer material used in the device. Stent removal may occur during stent delivery due to insufficient retention, high profile, or high forward pushing force, which can result in insufficient fixation of the stent to the balloon. The retention method must securely fix the covered stent to the balloon, but the method must not damage the stent, coating, or balloon. Retaining a covered stent in a balloon is more difficult due to the thickness of the stent's coating material. Furthermore, the coating can make deployment in self-expanding stents more difficult, or lead to high deployment forces (or make deployment impossible).

[0010] 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, 2018, 29:83, disclosed a GA-TMC-CL block copolymer for vascular closure applications. However, the authors did not disclose whether the copolymer was ABA-type or AB-type. They also did not disclose whether the amorphous block was a GA-TMC-CL polymer or a TMC-CL polymer.

[0011] Widjaja et al., "Triblock copolymers of ε-caprolactone, L-lactide, and trimethylene carbonate: biodegradability and elastomeric behavior," J.Biomed.Mat.Res:Part A, 2011; 99(1) pp. 38-46, disclosed an ABA block copolymer in which A is crystalline poly(L-lactide) and B is an amorphous random copolymer of TMC and CL. This copolymer exhibits thermoplastic elastomer properties. However, the entire polymer degrades slowly due to the presence of LA in the polymer. The soft segments of TMC and CL also degrade slowly due to the relatively hydrophobic nature of the monomers. When the molar ratio of LLA to the intermediate block (CL-TMC) is higher than 1, the triblock polymer is too brittle. [Prior art documents] [Non-patent literature]

[0012] [Non-Patent Document 1] 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, 2018, 29:83. [Non-Patent Document 2] Widjaja et al., "Triblock copolymers of ε-caprolactone, L-lactide, and trimethylene carbonate: biodegradability and elastomeric behavior", J. Biomed. Mat. Res: Part A, 2011; 99(1), pp. 38-46. [Overview of the project] [Problems that the invention aims to solve]

[0013] Therefore, there is a continuing need for improved polymer materials that can be used in vascular occlusion devices and covered medical devices, such as medical implants including stents. Polymer materials should be flexible, strong, and bioresorbable for periods of months, not years. One example of a polymer material application is covered stents for use in many vascular procedures. [Means for solving the problem]

[0014] (Summary of the invention) This specification discloses polymer compositions and implantable devices manufactured therefrom. The polymer composition is an ABA triblock copolymer comprising a crystalline A block, which advantageously provides mechanical strength, and an amorphous B block, which advantageously provides elasticity, flexibility, and a relatively fast overall degradation rate. Thus, the ABA triblock copolymer is biodegradable, biocompatible, and bioabsorbable, and therefore suitable for use in the manufacture of a variety of medical devices.

[0015] In some embodiments, the technology described herein relates to an implantable device comprising an implantable device body, a polymer material applied to the implantable device body, and / or a polymer material forming the implantable device body. In some embodiments, the implantable device may be a vascular occluder that provides rapid hemostasis at the puncture site of a blood vessel wall. In other embodiments, the implantable device may be a stent coated with the polymer material. In other embodiments, gastrointestinal devices, medical patches and thin films, valves, coagulation devices, atrial appendages, implants, septal occluders, abdominal aortic aneurysm (AAA) treatment devices, and all or part of combinations or modifications thereof may be formed from and / or coated with the polymer material.

[0016] In some embodiments, block A of the example ABA triblock copolymer is polyglycolide (PGA), also known as polyglycolic acid. In some embodiments, block B of the example ABA triblock copolymer comprises an amorphous random copolymer of glycolic acid (GA), trimethylene carbonate (TMC), and ε-caprolactone (CL). In some embodiments, block A of the example ABA triblock copolymer may also contain poly-L-lactic acid (PLLA), also known as poly-L-lactide, instead of or in addition to PGA. In some embodiments, block B of the example ABA triblock copolymer comprises an amorphous random copolymer of glycolic acid (GA) and / or lactic acid (LA), where LA may be LLA and / or DLLA. As described above, trimethylene carbonate (TMC) and ε-caprolactone (CL) may also be present. Due to their degree of crystallinity, block A provides mechanical strength, while the amorphous block B provides elasticity. However, since TMC and CL are known to degrade slowly, including GA / LA in block B is advantageous in that it allows for a more tunable degradation profile of the implantable device based on the needs of targeted therapeutic applications.

[0017] In some embodiments, each A block of the ABA triblock copolymer may have a weight percentage ranging from about 10% to about 35% or about 15% to about 25% of the copolymer, and two A blocks together constitute about 20% to about 70% or about 30% to about 50% of the copolymer. In some embodiments, the B block of the ABA triblock copolymer may have a weight percentage ranging from about 30% to about 80% or about 50% to about 70% of the copolymer.

[0018] In some embodiments, the ABA triblock copolymer may contain 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 represents either GA or LLA (or a combination thereof). In other embodiments, the three monomers in the ABA triblock copolymer may have a weight ratio of about 60 / 20 / 20 (GA / LLA:TMC:CL). The weight ratio may be one or more ranges, including the weight ratios described above.

[0019] In some embodiments, block B may contain 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), where GA / LA represents either GA or LA (LLA or DLLA) or a combination thereof. The weight ratio may be one or more ranges, including the weight ratios described above. In some embodiments, the soft segment does not contain or substantially does not contain LLA and / or DLLA, but contains or is composed of or essentially composed of the three monomers GA, TMC, and CL. In another embodiment, the soft segment does not contain or substantially does not contain GA, but contains or is composed of or essentially composed of LLA and / or DLLA, TMC, and CL.

[0020] ABA triblock copolymers may have a first glass transition temperature and a second glass transition temperature (Tg-1 and Tg-2) for the amorphous phase, and a melting point (Tm) and enthalpy of fusion (ΔH) for the crystalline phase.

[0021] In some embodiments, Tg-1 may be in the range of approximately -30°C to approximately 0°C, or approximately -20°C to approximately -5°C, and Tg-2 may be in the range of approximately 30°C to approximately 55°C, or approximately 30°C to approximately 40°C.

[0022] In some embodiments, Tm may be in the range of about 110°C to about 200°C, or about 145°C to about 200°C, and ΔH may be in the range of about 5 J / g to about 50 J / g, or about 10 J / g to about 35 J / g.

[0023] This summary is provided to introduce an example of a concept in a simplified form that will be further described below in the detailed description. This summary is not intended to identify the key features or essential features of the claimed subject matter, nor is it intended to be used as an indication of the scope of the claimed subject matter.

[0024] The description of various aspects and features of the present invention is given with reference to various representative embodiments thereof, which are illustrated in the accompanying drawings. It is recognized that these drawings illustrate only typical embodiments of the present invention and are not to be considered as limiting the scope of the present invention.

Brief Description of the Drawings

[0025] [Figure 1A] FIG. showing an example of a medical device manufactured from an ABA polymer material according to an embodiment of the present invention. [Figure 1B] FIG. showing an example of a medical device manufactured from an ABA polymer material according to an embodiment of the present invention. [Figure 2A] FIG. showing an exemplary coated medical device manufactured from an ABA polymer material according to an embodiment of the present invention. [Figure 2B] FIG. showing an exemplary coated medical device manufactured from an ABA polymer material according to an embodiment of the present invention. [Figure 2C] FIG. showing an exemplary coated medical device manufactured from an ABA polymer material according to an embodiment of the present invention. [Figure 2D] FIG. showing an exemplary coated medical device manufactured from an ABA polymer material according to an embodiment of the present invention. [Figure 2E] FIG. showing an exemplary coated medical device manufactured from an ABA polymer material according to an embodiment of the present invention. [Figure 2F] FIG. showing an exemplary coated medical device manufactured from an ABA polymer material according to an embodiment of the present invention. [Figure 3] FIG. showing attachment of a graft to a stent or scaffold according to an embodiment of the present invention. [Figure 4] This figure shows the attachment of a graft to a stent or scaffolding material according to one embodiment of the present invention. [Figure 5] This figure shows the attachment of a graft to a stent or scaffolding material according to one embodiment of the present invention. [Figure 6A] This figure shows thermograms of various exemplary triblock copolymers obtained by differential scanning calorimetry (DSC) during the first heating stage. [Figure 6B] This figure shows thermograms of various exemplary triblock copolymers obtained by differential scanning calorimetry (DSC) during the first heating stage. [Figure 6C] This figure shows thermograms of various exemplary triblock copolymers obtained by differential scanning calorimetry (DSC) during the first heating stage. [Figure 7A] This figure shows the DSC thermogram of the same triblock copolymer as in Figures 6A-6C, after the second heating. [Figure 7B] This figure shows the DSC thermogram of the same triblock copolymer as in Figures 6A-6C, after the second heating. [Figure 7C] This figure shows the DSC thermogram of the same triblock copolymer as in Figures 6A-6C, after the second heating. [Figure 8] This figure shows the stress-strain measurement of an example triblock copolymer. [Figure 9] This figure shows the change in molar mass over time for various example triblock copolymers. [Figure 10] This figure shows the change in mass loss over time for various example triblock copolymers. [Modes for carrying out the invention]

[0026] One or more specific embodiments of this disclosure are described below. To accurately describe these embodiments, some features of the actual embodiments may be described herein. It should be recognized that in the progress of any such actual embodiments, such as any engineering or design project, numerous individual decisions of the embodiments, such as compliance with system-related constraints and business-related constraints, which may vary from one embodiment to another, are made to achieve the developer's specific objectives. It should be further recognized that such development efforts are complex and time-consuming, but are still routine tasks of design, fabrication, and production for those skilled in the art who benefit from this disclosure.

[0027] One or more embodiments of this disclosure generally relate to ABA triblock copolymers. The ABA triblock copolymers disclosed herein comprise an A block, selected to primarily provide or contribute to mechanical strength, and a B block, selected to primarily provide or contribute to flexibility and elasticity. The polymer compositions may be bioabsorbable, biocompatible, and biodegradable.

[0028] One or more embodiments of this disclosure may relate to apparatus, systems, and methods for manufacturing and using implantable medical devices (e.g., occluders or covered stents) comprising polymer materials using ABA triblock copolymers. Implantable medical devices can be used to achieve immediate or substantially immediate hemostasis at openings in the vessel wall. Furthermore, the implantable medical device may be used as a covered stent, where the stent provides a scaffold to the vessel, and the polymer material is used as a covering and / or coating. In this case, the polymer material is both bioabsorbable and biocompatible, and decomposes and / or is absorbed after the stent is properly placed and fixed. The disclosed polymer material for implantable medical devices provides a balance between crystalline hard segments for withstanding forces from medical procedures and amorphous soft segments for delivery, expandability, and integration with the vessel wall. Therefore, implantable medical devices are suitable for use in many vascular interventional procedures.

[0029] This disclosure describes specific implementations of implantable medical devices, apparatus and systems, and related methods for use in vascular interventional procedures. However, it should be understood that any of the systems, apparatus and methods described herein, but not limited to them, are applicable to other uses, including gastrointestinal devices, medical patches and thin films, valves, coagulation devices, atrial appendages, occluders, AAA treatment, arteriovenous fistulas, tissue transplantation, and / or coronary sinus decompression devices used in the treatment of angina. Furthermore, elements described herein in relation to any embodiment described and / or referred to herein can be combined with elements described in relation to any other embodiment described and / or referred to herein.

[0030] Polymer materials Some embodiments of the polymer material are desirable to provide the following features. In some embodiments, the polymer material is moldable and can be appropriately shaped. For example, in the case of a balloon-expandable covered stent, the polymer material is a woven or nonwoven mesh that is incorporated around the stent and should have sufficient flexibility to expand the balloon-expandable covered stent. In some embodiments, the polymer material is moldable and allows for moldability. In some embodiments, the polymer material is compressible for proper delivery. In the particular case of a plug-based occluder, the polymer material can advantageously be pushed into the vascular wall before the implantable device is used. Therefore, the polymer material preferably has compressible properties. In some embodiments, the polymer material may be soluble for spray or immersion coating on stents or other devices. Roller coating and / or inkjet coating are also possible. Such coatings may contain one or more antiproliferative drugs, such as sirolimus (rapamycin), everolimus, zotarolimus, defololimus, umilolimus, temsirolimus, and their analogues, or microtubule inhibitors such as paclitaxel. In yet another embodiment, the polymer material may be electrospun to produce a filamentous structure.

[0031] In some embodiments, the polymer material may be elastic. For example, in the use of vascular occlusion devices, or around stents used as vascular scaffolds, or in stent coatings that can withstand compression and expansion of stents, the elastic properties allow the polymer material to conform to the external shape of a particular vessel. In some embodiments, the polymer material should undergo low deformation during deployment. In other embodiments, the polymer material should undergo low deformation after deployment. In yet another embodiment, the polymer material should undergo low deformation both during and after deployment. In the case of covered stents, the polymer material may undergo low deformation while the covered stent is being inserted and may continue to deform until the polymer material begins to decompose, leaving the stent in the correct position. In some embodiments, the polymer material may have a low deployment force.

[0032] In some embodiments, polymer materials can decompose relatively quickly after implantation. For example, polymer materials may decompose in less than one month, within two months, within three months, within four months, within five months, within six months, within seven months, within eight months, within one year, or more than one year after implantation. In some procedures, it may be preferable for polymer materials to decompose within about one to six months after implantation. In some embodiments, polymer materials should be biocompatible, or bioabsorbable, or bioreabsorbable, or biodegradable, or a combination thereof. For example, when polymer materials are used in covered stents, the polymer materials should be biocompatible with the blood vessel into which the stent is inserted. When polymer materials decompose, the decomposed material is advantageously bioabsorbable by the blood vessel or removed by the body's elimination system. As another example, when polymer materials are used in vascular occlusion devices, the polymer materials are advantageously biocompatible with the blood vessel wall and bioabsorbable by the body because the blood vessel wall closes without the polymer material.

[0033] Herein, in a particular embodiment of the ABA triblock copolymer, the polymer comprises an A block and a B block. The A block is selected primarily to provide or contribute to mechanical strength, and the B block is selected primarily to provide or contribute to elasticity and flexibility to the polymer material.

[0034] The monomer components of ABA triblock copolymers typically include glycolic acid (GA), often provided as a condensed glycolide dimer; lactic acid (LA), which may also be provided as a condensed lactide dimer; trimethylene carbonate (TMC); and ε-caprolactone (CL). Glycolic acid, glycolide dimers, and polyglycolides have the following chemical structures.

[0035] [ka]

[0036] Lactic acid, lactide dimers, and polylactides (also known as polylactic acid) have the following chemical structures.

[0037] [ka]

[0038] When used to form block A, PGA typically forms a crystalline polymer having n glycoside units bonded to each other, and terminal hydroxyls or terminal carboxylates condense with the corresponding terminal monomers of block B to form covalent bonds. When used in block B, a diol initiator can be used to produce polymers of glycolic acid / glycolide (GA) / lactic acid (LA), trimethylene carbonate (TMC), or ε-caprolactone (CL) by anionic living polymerization.

[0039] In some embodiments, block B is first synthesized using a diol as an initiator and catalyst, thereby producing block B having two hydroxyl groups at each end. In some embodiments, the catalyst may be a tin catalyst, such as stannous octanoate. In these embodiments, block A may be synthesized after block B using the same tin catalyst.

[0040] The monomer units of trimethylene carbonate (TMC) and poly(trimethylene carbonate) after ring opening and polymerization have the following chemical structures.

[0041] [ka]

[0042] The monomer units of ε-caprolactone (CL) and polycaprolactone after ring-opening and polymerization have the following chemical structures.

[0043] [ka]

[0044] In some embodiments, Block A is formed of 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 a linear aliphatic polyester.

[0045] In some embodiments, block B is formed of an amorphous random copolymer. The amorphous random copolymer comprises monomer units of glycolic acid / glycolide (GA) and / or lactic acid (LA), trimethylene carbonate (TMC), and ε-caprolactone (CL). Glycolide and lactide are typically provided in dimer form, respectively. TMC, also known as 1,3-propylene carbonate, is initially a six-membered ring carbonate ester before ring-opening and polymerization. CL, also known as caprolactone, is a lactone (e.g., a cyclic ester) that initially contains a seven-membered ring.

[0046] The polymer material used to manufacture medical implants is a triblock copolymer having an ABA symmetric triblock copolymer pattern. The copolymer represents a blend of mechanical strength and elasticity. The A unit, composed of PGA and / or PLLA, primarily provides or contributes to mechanical strength, and therefore the A block plays a dominant role in the mechanical strength of the polymer material. The TMC and CL monomer units in the B block primarily provide or contribute to elasticity, and therefore the B block plays a dominant role in the elasticity and flexibility of the polymer material. The GA and / or LA units in the B block are more hydrophilic than TMC and CL, promoting faster biodegradation and absorption by the body.

[0047] As described above, in some embodiments, it is desirable that the polymer material has a relatively fast degradation time. Generally, TMC and CL in block B degrade relatively slowly. To compensate for this, embodiments may advantageously include GA and / or LA in block B to accelerate the degradation of the random copolymer.

[0048] To identify one or more ABA triblock copolymers suitable for the intended purpose of implantable devices, numerous compositions of ABA triblock polymers (also known as terpolymers) were generated and tested to determine the optimal composition with desirable properties for the application. The following table summarizes these example copolymer compositions.

[0049] [Table 1]

[0050] Table 1 shows some examples of the disclosed embodiments. Exemplary embodiments may include two A blocks, each A block containing less than about 10% by weight, about 10% by weight, about 15% by weight, about 20% by weight, about 25% by weight, about 30% by weight, or more than about 30% by weight. In some embodiments, A blocks may be formed of GA, LLA. Furthermore, exemplary embodiments may include B blocks containing less than about 15% by weight, about 15% by weight, about 17.5% by weight, about 20% by weight, about 22.5% by weight, about 25% by weight, about 30% by weight, or more than about 30% by weight of GA, LA, or a combination of GA and LA, and containing less than about 5% by weight, about 5% by weight, about 10% by weight, about 20% by weight, about 25% by weight, or more than about 25% by weight of TMC, and containing less than about 20% by weight, about 20% by weight, about 25% by weight, or more than about 25% by weight of CL.

[0051] In some embodiments, as monomer units, block A may contain only PGA, and block B may contain GA rather than LA in addition to TMC and CL. In other embodiments, as monomer units, block A may contain only PLLA rather than PGA, and block B may contain LA rather than GA in addition to TMC and CL. In yet another embodiment, as monomer units, block A may contain only PGA, and block B may contain LA rather than LA in addition to TMC and CL. Or, in yet another embodiment, as monomer units, block A may contain only PLLA, and block B may contain GA rather than GA in addition to TMC and CL. In further embodiments, as monomer units, block A may contain copolymers of PGA and PLLA, which may affect (e.g., decrease) the crystallinity of block A, and block B may contain GA alone, LLA alone, DLLA alone, both GA and LLA, both DLLA and LLA, both GA and LLA, or GA, LLA and DLLA in addition to TMC and CL. In some embodiments, as monomer units, block A may contain PGA alone, PLLA alone, or both PGA and PLLA, and block B may contain a mixture of GA, LLA and DLLA in addition to TMC and CL.

[0052] Depending on the application and desired function of the ABA triblock polymer material, the percentages of A-block material and B-block material can be optimized to yield the best properties. For example, Example 13 is found to have good bioabsorbability and, due to its physical properties, is a preferred formulation for use in the manufacture of anchor seals and cap seals for closing perforated blood vessels.

[0053] Other properties of the ABA triblock polymer material can be optimized to provide functional characteristics. For example, in some embodiments, each A block of the ABA triblock copolymer may have a weight percentage ranging from about 10% to about 30% or about 15% to about 25% of the copolymer, and two A blocks together constitute about 20% to about 60% or about 30% to about 50% of the copolymer. In some embodiments, the B block of the ABA triblock copolymer may have a weight percentage ranging from about 40% to about 80% or about 50% to about 70% of the copolymer.

[0054] In some embodiments, the ABA triblock copolymer may contain 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 of the ABA triblock copolymer may have a weight ratio of about 60 / 20 / 20 (GA / LA:TMC:CL). In yet another embodiment, the monomers of the ABA triblock copolymer may have a weight ratio of 50-60 parts GA / LA:10-40 parts TMC:10-40 parts CL, wherein the block copolymer contains 100 parts GA / LA, TMC, and CL combined. In yet another embodiment, the monomers of the ABA triblock copolymer may have a weight ratio of 50-60 parts GA / LA:20-25 parts TMC:20-25 parts CL, wherein the block copolymer contains 100 parts GA / LA, TMC, and CL combined.

[0055] In some embodiments, block B may contain 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:about 20-25 parts TMC:about 20-25 parts CL, or in a weight ratio of about 15-30 parts GA:about 10-40 parts TMC:about 10-40 parts CL.

[0056] ABA triblock copolymers may have a first glass transition temperature and a second glass transition temperature (Tg-1 and Tg-2) for the amorphous phase, and a melting point (Tm) and enthalpy of fusion (ΔH) for the crystalline phase.

[0057] In some embodiments, Tg-1 may be in the range of about -10°C to about -40°C, or about -15°C to about -30°C, and Tg-2 may be in the range of about 40°C to about 55°C, or about 45°C to about 50°C.

[0058] In some embodiments, Tm may be in the range of about 105°C to about 220°C, or about 145°C to about 210°C, and ΔH may be in the range of about 10 J / g to about 35 J / g, or about 13 J / g to about 30 J / g.

[0059] For example, in some embodiments, the block copolymer can have a tensile strength in the 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.

[0060] In some embodiments, the block copolymer may have a first glass transition temperature Tg in the 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.

[0061] In some embodiments, the block copolymer can have an elongation at break ranging from about 50% to about 1000%, preferably about 100% to about 800%, and more preferably about 200% to about 400%.

[0062] In some embodiments, the block copolymer can have an inherent viscosity in the 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 1.1 dL / g.

[0063] In some embodiments, the block copolymer can have an elastic modulus in the 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.

[0064] In some embodiments, the block copolymer may have a crystallinity percentage in the range of about 5% to about 25%, preferably about 5% to about 20%, and more preferably about 7% to about 15%.

[0065] Embedded device body Embodiments of the present invention also generally include embedded devices, which include an embedded device body. The embedded device body can vary considerably depending on the intended application. Some examples of embedded device bodies are discussed here.

[0066] In some embodiments, the implantable device body relates to a vascular closure delivery device. The vascular closure delivery device may include an actuator, an anchor, a cap, a closure element, a delivery sheath, a fluid barrier component, and / or a suture element. Examples of implantable device bodies can be found in concurrently pending U.S. Patent Provisional Application No. 63 / 495360, filed April 11, 2023, entitled “Vessel Closure Device with Improved Safety and Tract Hemostasis,” and U.S. Patent Application No. 2022 / 0110617, entitled “Vessel Closure Device with Improved Safety and Tract Hemostasis,” the disclosures of which are incorporated herein by reference in their entirety.

[0067] In some embodiments, the implantable device body is a stent. Examples of stents include balloon-expandable stents, self-expanding stents, coronary artery stents, peripheral stents, carotid artery stents, nerve stents, vascular stents, ureteral stents, prostatic stents, colonic stents, esophageal stents, pancreatic stents, biliary stents, glaucoma drainage stents, arteriovenous fistula stents, coronary sinus decompression devices, or other suitable stent types. In some embodiments, the balloon-expandable stent is an Omnilink Elite® vascular balloon-expandable stent. In some embodiments, the stent may be formed from a variety of metals, such as cobalt-chromium, stainless steel, nitinol, or other suitable metals. In some embodiments, the stent (e.g., without covering or coating) has a thickness ranging from about 50 μm to about 250 μm, preferably about 90 μm to about 210 μm, and more preferably about 110 μm to about 160 μm.

[0068] In some embodiments, the implantable device body may be a gastrointestinal device, a medical patch and thin film, a valve, a coagulation device, an atrial appendage, an AAA treatment device, and / or a tissue graft. The covering may be on the outside of the stent, on the inside, a combination thereof, or encase the stent. The covering may be on the entire stent or on a portion of the stent, for example, a portion of which requires specific sealing due to the purpose of a particular stent graft.

[0069] Application of polymer materials to implantable devices In some embodiments, the polymer material is applied to the embedded device body using electrospinning. Generally, electrospinning is a fiber manufacturing method based on using electric force to attract charged polymer solution threads to produce polymer fibers. Polymer fibers can vary in diameter based on electrospinning.

[0070] In some embodiments, an ABA copolymer solution is prepared, and ABA copolymer fibers are produced using electrospinning. The ABA copolymer solution flows out of the needle and is electrostatically attracted to the opposite charge of the mandrel. The polymer wraps around the mandrel, forming a nonwoven 3D web together with the individual ABA copolymer fibers. The final individual ABA copolymer fibers may have a spiderweb-like homogeneity and appearance after electrospinning. Furthermore, in some embodiments, the ABA copolymer fibers may be stretched into long filaments during electrospinning.

[0071] In some embodiments, electrospun polymer materials are used to fabricate implantable device bodies and polymer coatings. Since polymer materials have a rubbery morphology and are biodegradable, they can be used to fabricate some, most, or all of the structure of a product. For example, the extent and location of the covering may depend on the purpose of such devices. As a further example, the covering may be required in the middle portion of the device for fixation, while the ends can be fixed in a blood vessel, or perhaps even limit the risk of end-to-end thrombus formation. In some embodiments, polymer materials can be used to cover implantable medical devices such as stents. In some embodiments, polymer materials can be used to form caps and / or anchors for vascular occluders.

[0072] When the polymer material is used as a covering (e.g., in a covered stent), the electrospun filaments can be directly covered over the implanted device body. In another embodiment, the electrospun polymer filaments are first deposited into a rope-like structure. The rope-like polymer material is then covered over the implanted device body. In this embodiment, the polymer material can have a durable, highly elastic, tear-resistant, and biodegradable structure with homogeneity (e.g., resilient stretchability) similar to that of Teflon tape.

[0073] In other embodiments, the polymer material may be dissolved in a solution. The solvent may be hexafluoroisopropanol or other suitable solvents. The active pharmaceutical ingredient, such as everolimus, may be dissolved together with the polymer and applied to the stent as an anti-restenosis coating by spraying, roller coating, and / or inkjet printing.

[0074] In other embodiments, the polymer material may be melted and electronically sprayed onto medical devices and / or drug delivery devices as a coating.

[0075] Example implantable device containing polymer material In the case of vascular occluders, some embodiments include anchors and occluding elements, such as caps, made of ABA polymer. Figures 1A and 1B show examples of anchors 102 and caps 104 made of ABA polymer. The anchor 102 can pass through an opening (e.g., a puncture) defined in the vessel wall and is deployed into the vessel lumen. The anchor 102 can then be retracted proximally, so that the anchor is retracted and in contact with the inner surface of the vessel wall. The cap 104 can then be positioned on the outer surface of the vessel wall and the puncture is closed by advancing the cap 104 along a suture element 106. The suture element 106 may optionally be formed of or covered with an ABA polymer.

[0076] The anchor 102 includes a keel 120 (which will be discussed in full below) and a surface. As will be discussed elsewhere, as illustrated in Figure 1B, the suture 106 can be sewn through holes or eyelets within the anchor 102, thereby securing the suture 106 to the anchor 102. This configuration also allows any force applied to the suture 106 (i.e., pulling or tugging the suture 106) to be transferred to the anchor 102. For example, if a physician or other practitioner applies a proximal pulling or traction force to the suture 106, the proximal pulling or traction force is applied to the anchor 102, moving the anchor 102 proximal.

[0077] The extravascular cap 104 can be manufactured from an ABA polymer and may be large and shaped to prevent it from passing through the puncture site on the surface of the blood vessel. The size and shape of the cap 104 can significantly enhance patient safety by preventing the extravascular device from passing through the insertion site during and / or after deployment. The cap 104 may have a diameter in the range of approximately 1 mm to 10 mm, approximately 3 mm to 8 mm, approximately 4 mm to 5 mm, or a diameter defined by any two of the aforementioned values. The cap 104 may have different sizes and shapes based on the specific width of the insertion site, so that the cap 104 does not pass through the puncture / insertion site and does not pass through the lumen of the blood vessel.

[0078] The cap 104 can be thin and may be made of a biodegradable material. The cap 104 may also have desirable flexibility to conform to the anatomical structure of the insertion site (particularly in blood vessels where significant calcification is present), which may result in a more effective seal than a rigid material. The cap 104 can be deployed through the insertion tissue pathway, positioned over the blood vessel, and act as the primary extravascular sealant between the blood vessel wall or other tissue between the anchor 102 and the cap 104.

[0079] In the case of covered stents, some embodiments include stents, grafts, or other functions made from ABA polymer. Figures 2A to 2F show examples of covered stents or scaffolding materials made from ABA polymer. Figures 2A and 2B are SEM images of the polymer coating 204 made of ABA polymer on the stent body or scaffolding body 222 of the covered stent or scaffolding material 220 for forming the covered stent or scaffolding material 200. Figure 2C shows the covered stent or scaffolding material 200 having a lumen 206. Figure 2D shows a side view of the covered stent or scaffolding material 200, and Figure 2E shows an example of the flexibility of the covered stent or scaffolding material 200 in which both the body or frame 222 and the polymer coating 204 are made of ABA polymer. Figure 2F shows an enlarged or more detailed view of the body or frame 222 showing the ring 228 and connector 229 of the stent or scaffolding material. The covered stent or scaffolding material 200 in Figures 2A to 2F represents a self-expanding stent or scaffolding material, but other stents or scaffolding materials are also possible, such as balloon-expanding stents or scaffolding materials covered with a polymer coating 204. On the other hand, it should be understood that the underlying stent or scaffolding material body is formed from metal alloys, such as Nitinol, Elgiloy, 316 stainless steel, L605Co-Cr, MP35N cobalt alloy, ternary nickel-titanium-platinum alloy, platinum-cobalt alloy, tantalum alloy, and combinations or modifications thereof.

[0080] In another configuration illustrated in Figure 3, the attachment or connection of the graft 300 to the crimped stent or scaffolding material 320 may be carried out using a circular flat ring or ribbon 330a that surrounds the ends of the graft 300 and maintains the attachment or connection of the graft body to the body or frame at both ends. For example, the circular flat ring or ribbon (e.g., an O-ring) 330a may be made of an ABA polymer or another polymer such as a shape memory polymer (SMP). In the case of a shape memory polymer, the shape memory polymer may be programmed so that the diameter of the circular flat ring or ribbon 330a is small at room temperature and then expands to the expanded stent diameter when thermally activated. The assembly of the graft 300 and the crimped stent or scaffolding material 320 may include the positioning of the graft body to the crimped body or frame. The circular ring or ribbon 330a can then be attached to both the proximal and distal ends, thereby fixing the graft 300 in place.

[0081] In another embodiment, as shown in Figure 4, the attachment or connection of the graft 300 to the crimped stent or scaffolding material 320 may be achieved using circular wire rings 330b at both ends. The wire 330b may be made of a shape memory alloy such as Nitinol (nickel-titanium alloy). When the wire 330b is installed on the graft 300 mounted or positioned on the body or frame 320, it may have a sinusoidal shape that is deformable at room temperature. Once recovered, the pre-deformation shape of the ring 330b, upon temperature activation, may allow for the full expansion of the stent or scaffolding material 320 during deployment at nominal pressure. Such rings or ribbons 330a / 330b may have any desired cross-sectional shape.

[0082] In further embodiments, as shown in Figure 5, the attachment or connection of the graft 300 to the crimped stent or scaffolding material 320 may be carried out by spot bonding or welding 330c to the proximal and distal ends of the stent or scaffolding material 320. In other embodiments, the fixation of the graft 300 to the crimped stent or scaffolding material 320 may be carried out by the use of adhesives, thermal bonding, solvent bonding, laser welding techniques, and combinations or modifications thereof. After the graft body is positioned on the crimped stent or scaffolding material 320 and mounted on the mandrel, spot bonding or laser welding may be carried out at both ends or at specific internal locations. The welding, bonding, etc. may be at a complete annular shape or at many discrete and discontinuous locations. [Examples]

[0083] Experimental results Figures 6A–6C and 7A–7C illustrate the thermal properties of three exemplary embodiments of the ABA block copolymer. The glass transition temperature (Tg) of the amorphous phase of block B, the melting point (Tm) of the crystalline phase of block A, and the enthalpy of melting (ΔH) were measured by differential scanning calorimetry (DSC) at a heating rate of 10°C / min in the temperature range of -50 to 230°C. The sample was scanned using two heating cycles. Figure 6 shows the first heating cycle, and Figure 7 shows the second heating cycle.

[0084] The glass transition temperature (Tg) of the amorphous B block (soft segment) of the ABA copolymer in the three exemplary embodiments is in the range of -30°C to 0°C. The melting peak of the crystalline A block (hard segment) of the ABA copolymer in the three exemplary embodiments is in the range of 108°C to 183°C. The block copolymer in Figures 6A and 7A shows the highest Tm and ΔH of 26 to 30 J / g at approximately 176 to 183°C. The block copolymer in Figures 6B and 7B shows a Tm of approximately 151 to 155°C and a ΔH of 11 to 16 J / g. The block copolymer in Figure 6C shows a Tm of approximately 108°C and a ΔH of 21 J / g. Figure 7C shows an example embodiment of the ABA copolymer that contains the lowest content of crystalline A block and has no melting peak due to a slow crystallization process.

[0085] Figure 8 illustrates the mechanical properties of an example embodiment of an ABA block copolymer performed using INSTRON. The tensile strength and maximum elongation depend on the weight ratio of block A and the monomer ratio in block B. Sample 4 has mechanical properties including elongation and elastomeric properties up to 900%, as there is no measurable yield stress in the stress-strain curve.

[0086] Figures 9 and 10 illustrate the in vitro degradation characteristics of three exemplary embodiments of ABA block copolymers. Of the three examples, sample 3 exhibits the fastest degradation rate, as well as the sharpest molecular weight decrease and fastest mass loss. The degradation of the ABA block copolymer depends on the total weight ratio of the A block components, including the type of A block component (GA / LA) and the ratio of A block components in the B block.

[0087] Additional terms / definitions The articles “a,” “an,” and “the” mean that there is one or more of the aforementioned elements. The terms “comprising,” “including,” and “having” are intended to be comprehensive and mean that there may be additional elements other than those listed. Furthermore, it should be understood that any reference to “one embodiment” or “one embodiment” in this disclosure is not intended to exclude the existence of additional embodiments that also incorporate the detailed features. Numbers, percentages, ratios, or other values ​​described herein are intended to include those values, and other values ​​that are described as “about” or “approximately” and that can be recognized by those skilled in the art as being included in the embodiments of this disclosure. Therefore, in order to perform the desired function or achieve the desired result, the described values ​​should be interpreted broadly enough to include values ​​at least close to the described values. The stated values ​​may include at least the expected variability in a preferred production or manufacturing method, and may include values ​​that are within 5%, 1%, 0.1%, or 0.01% of the stated values.

[0088] Those skilled in the art should, in consideration of this disclosure, recognize that equivalent configurations can be modified, replaced, and altered in various ways without departing from the spirit and scope of this disclosure to the embodiments disclosed herein. Equivalent configurations including functional “means-plus-function” items are intended to extend to structures described herein that perform the detailed function, including structural equivalents that operate in the same way and equivalent structures that provide the same function. It is clearly intended by the applicant not to seek means-plus-function or other functional claims in any claim except where the phrase “means to do something” appears together with the function to which it relates. Any additions, deletions, and alterations to the meaning and scope of the claims and to embodiments within that scope should be incorporated into the claims.

[0089] In this specification, the terms “approximately,” “about,” and “substantially” refer to quantities close to a given amount that perform a desired function or achieve a desired result. For example, the terms “approximately,” “about,” and “substantially” may refer to quantities that are less than 5%, less than 1%, less than 0.1%, and less than 0.01% of a given amount. Furthermore, it should be understood that any of the aforementioned directions or reference frames are merely relative directions or movements. For example, any reference to “up” and “down” or “above” or “below” simply describes the relative position or movement of the relevant elements.

[0090] The following are some further exemplary embodiments of the present invention. These are presented for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, any exemplary embodiment may be combined with one or more of the exemplary embodiments.

[0091] Embodiment 1 A block copolymer comprising a random copolymer of a polyglycolide (PGA) or poly-L-lactide forming block A, and a random copolymer of glycolicide (GA), L-lactide, DL-lactide, trimethylene carbonate (TMC), and ε-caprolactone (CL) forming block B.

[0092] Embodiment 2: The block copolymer of Embodiment 1, wherein the block copolymer is an ABA triblock copolymer containing an A block and an intervening B block.

[0093] Embodiment 3 The block copolymer of Embodiment 1 or 2, wherein each A block has a weight percentage in the range of about 10% to about 35% by weight of the block copolymer, or about 15% to about 25% by weight, and in the case of an ABA triblock copolymer, both A blocks have a weight percentage in the range of about 20% to about 70% by weight, or about 30% to about 50% by weight of the block copolymer.

[0094] Embodiment 4: A block copolymer of any of Embodiments 1 to 3, wherein block B has a weight percentage in the range of about 30% to about 80% by weight, or about 50% to about 70% by weight, of the block copolymer.

[0095] Embodiment 5 A block copolymer according to any of Embodiments 1 to 4, wherein the block copolymer contains monomers of glycolide (GA), trimethylene carbonate (TMC), and ε-caprolactone (CL) in a weight ratio of about 50 / 25 / 25 (GA:TMC:CL), about 60 / 20 / 20 (GA:TMC:CL), or about 50-60 parts GA: about 10-40 parts TMC: about 10-40 parts CL, provided that the block copolymer contains 100 parts of GA, TMC, and CL combined.

[0096] Embodiment 6: A block copolymer according to any of Embodiments 1 to 5, wherein Block B contains monomers of glycolide (GA), trimethylene carbonate (TMC), and ε-caprolactone (CL) in a weight ratio of approximately 15 / 20 / 20 (GA:TMC:CL), approximately 10 / 20 / 20 (GA:TMC:CL), approximately 15 / 25 / 25 (GA:TMC:CL), approximately 30 / 20 / 20 (GA:TMC:CL), or approximately 15-30 parts GA: approximately 10-40 parts TMC: approximately 10-40 parts CL.

[0097] Embodiment 7 A block copolymer of any of Embodiments 1 to 6, wherein the block copolymer can have an inherent viscosity in the 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.

[0098] Embodiment 8 A block copolymer according to any of Embodiments 1 to 7, wherein the block copolymer has a first glass transition temperature (Tg-1) in the amorphous phase in the 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) in the amorphous phase in the range of about 30°C to about 55°C or about 30°C to about 40°C.

[0099] Embodiment 9 A block copolymer according to any of Embodiments 1 to 8, wherein Tm may be in the range of about 110°C to about 200°C, or about 145°C to about 200°C, and ΔH may be in the range of about 5 J / g to about 50 J / g, or about 10 J / g to about 35 J / g.

[0100] Embodiment 10 A block copolymer according to any of Embodiments 1 to 9, wherein the block copolymer has a melting enthalpy (ΔH) in the range of about 5 J / g to about 35 J / g, or about 13 J / g to about 30 J / g.

[0101] Embodiment 11 A block copolymer of any of Embodiments 1 to 10, wherein the block copolymer may have a crystallinity percentage in the range of about 5% to about 25%, about 5% to about 20%, or about 7% to about 15%.

[0102] Embodiment 12 A block copolymer according to any of Embodiments 1 to 11, wherein the block copolymer has a tensile strength in the 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.

[0103] Embodiment 13 A block copolymer of any of Embodiments 1 to 12, wherein the block copolymer has a break elongation in the range of about 50% to about 1000%, about 100% to about 800%, or about 200% to about 400%.

[0104] Embodiment 14 A block copolymer of any of Embodiments 1 to 13, wherein the block copolymer can have an elastic modulus in the 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.

[0105] Embodiment 15: An implantable device comprising an implantable device body, and a block copolymer of any of Embodiments 1 to 14 on and / or forming the implantable device body.

[0106] Embodiment 16: An implantable device according to Embodiment 15, wherein the implantable device body includes a stent having a stent thickness in the range of approximately 50 μm to approximately 200 μm.

[0107] Embodiment 17: An implantable device according to Embodiment 15, wherein the stent includes multiple gaps, and when expanded, the thickness of the polymer material in each gap is approximately 50 microns.

[0108] Embodiment 18: An implantable device according to any of Embodiments 15 to 17, wherein the implantable device body includes a vascular occlusion device.

[0109] Embodiment 19 An implantable device according to any of Embodiments 15 to 18, wherein one or more layers of block copolymer are configured to be electrospun into the implantable device body.

[0110] Embodiment 20 An implantable device according to any one of claims 15 to 19, wherein the block copolymer is an ABA triblock copolymer comprising an A block and an interposed B block, each A block having a weight percentage in the range of about 10% to about 35% by weight or about 15% to about 25% by weight of the block copolymer, and together the A blocks have a weight percentage in the range of about 20% to about 70% by weight or about 30% to about 50% by weight of the block copolymer.

[0111] The present invention may be embodied in other specific forms without departing from the spirit and essential features of the invention. The embodiments described are for illustrative purposes only and are not limiting in all respects. Accordingly, the scope of the invention is indicated by the appended claims rather than by the foregoing description. All modifications that fall within the meaning and scope of equivalence of the claims are encompassed within that scope.

Claims

1. At least one of polyglycolide (PGA) or poly-L-lactide (PLLA) that forms block A, and A random copolymer of at least one of glycolide (GA), L-lactide (LLA), or DL-lactide (DLLA), trimethylene carbonate (TMC), and ε-caprolactone (CL), forming block B. Block copolymers containing these polymers.

2. The block copolymer according to claim 1, which is an ABA triblock copolymer comprising an A block and an interposing B block.

3. The block copolymer according to claim 1, wherein each A block has a weight percentage in the range of about 10% to about 35% by weight or about 15% to about 25% by weight of the block copolymer, and in the case of an ABA triblock copolymer, both A blocks have a weight percentage in the range of about 20% to about 70% by weight or about 30% to about 50% by weight of the block copolymer.

4. The block copolymer according to claim 1, wherein block B has a weight percentage in the range of about 30% to about 80% by weight, or about 50% to about 70% by weight, of the block copolymer.

5. The block copolymer according to claim 1, wherein the block copolymer contains monomers of glycolide (GA), trimethylene carbonate (TMC), and ε-caprolactone (CL) in a weight ratio of about 50 / 25 / 25 (GA:TMC:CL), about 60 / 20 / 20 (GA:TMC:CL), or about 50 to 60 parts GA: about 10 to 40 parts TMC: about 10 to 40 parts CL, wherein the block copolymer contains 100 parts of GA, TMC, and CL combined.

6. The block copolymer according to claim 1, wherein block B contains monomers of glycolide (GA), trimethylene carbonate (TMC), and ε-caprolactone (CL) in a weight ratio of about 15 / 20 / 20 (GA:TMC:CL), about 10 / 20 / 20 (GA:TMC:CL), about 15 / 25 / 25 (GA:TMC:CL), about 30 / 20 / 20 (GA:TMC:CL), or about 15 to 30 parts GA: about 10 to 40 parts TMC: about 10 to 40 parts CL.

7. The block copolymer according to claim 1, having an inherent viscosity in the range of approximately 0.8 dL / g to approximately 1.8 dL / g, approximately 0.9 dL / g to approximately 1.3 dL / g, or approximately 0.9 dL / g to approximately 1.1 dL / g.

8. The block copolymer according to claim 1, having a first glass transition temperature (Tg-1) of the amorphous phase in the 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 the range of about 30°C to about 55°C, or about 30°C to about 40°C.

9. The block copolymer according to claim 1, having a crystalline phase melting point (Tm) in the range of about 110°C to about 200°C, or about 145°C to about 200°C, and a melting enthalpy (ΔH) in the range of about 5 J / g to about 50 J / g, or about 10 J / g to about 35 J / g.

10. The block copolymer according to claim 1, having a melting enthalpy (ΔH) in the range of approximately 5 J / g to approximately 35 J / g, or approximately 13 J / g to approximately 30 J / g.

11. The block copolymer according to claim 1, having a crystallinity percentage in the range of approximately 5% to approximately 25%, approximately 5% to approximately 20%, or approximately 7% to approximately 15%.

12. The block copolymer according to claim 1, having a tensile strength in the range of approximately 5 MPa to approximately 100 MPa, or approximately 10 MPa to approximately 40 MPa, or approximately 10 MPa to approximately 30 MPa.

13. The block copolymer according to claim 1, having a break point elongation in the range of approximately 50% to approximately 1000%, approximately 100% to approximately 800%, or approximately 400% to approximately 600%.

14. The block copolymer according to claim 1, having an elastic modulus of approximately 20 MPa to approximately 500 MPa.

15. It is an implantable device, Embedded device body, and Block copolymer according to claim 1, which is on and / or forms an embedded device body. Implantable devices, including those mentioned above.

16. The implantable device according to claim 15, wherein the implantable device body includes a stent having a stent thickness in the range of approximately 50 μm to approximately 200 μm.

17. The implantable device according to claim 16, wherein when the stent includes multiple gaps and is in an expanded state, the thickness of the polymer material in each gap is approximately 50 microns.

18. The implantable device according to claim 15, wherein the implantable device body includes a vascular occlusion device.

19. The implantable device according to claim 15, wherein one or more layers of the block copolymer are configured to be electrospun into the implantable device body.

20. The embedded device according to claim 15, wherein one or more layers of the block copolymer are configured to be applied by spraying, roller coating, or inkjet printing.

21. The implantable device according to claim 20, wherein one or more layers of the block copolymer contain an active pharmaceutical ingredient.

22. The implantable device according to claim 15, wherein the block copolymer is an ABA triblock copolymer comprising an A block and an interposed B block, each A block having a weight percentage in the range of about 10% to about 35% or about 15% to about 25% of the block copolymer, and both A blocks together have a weight percentage in the range of about 20% to about 70% or about 30% to about 50% of the block copolymer.

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