Compositions and methods for nonwoven fabric materials

Abstract

This specification discloses nonwoven materials, such as electrospun materials, having one or more properties such as softness, bulkiness, specific pore size, little to no solvent retention, and mechanical and dimensional stability for use in implantable medical devices.

Description

[Background technology]

[0001] Cross-reference of related applications This application is a PCT application claiming the benefit and priority of U.S. Provisional Patent Application No. 63 / 461,631, filed on 25 April 2023, which is incorporated herein by reference in its entirety.

[0002] Synthetic absorbable polymers are routinely used as medical grafts, scaffolds for tissue engineering, and drug delivery devices. Since the introduction and widespread use of VICRYL absorbable sutures, sold by Ethicon, a subsidiary of Johnson & Johnson, absorbable polyesters have been the subject of significant research due to their long history of industrial use, well-known degradation mechanisms, non-toxic by-products, and potential use in multiple FDA-approved medical devices.

[0003] In recent years, electrospinning, a method that uses electric charge to extract extremely thin, typically micro or nanoscale, fibers from liquids, has attracted considerable interest in medical device applications. This process allows for the production of microfibrous materials with topography similar to that of the natural extracellular matrix. Absorbable and non-absorbable electrospinned materials not only mimic the topography of the extracellular matrix through their fibrous shape, but also serve as ideal substrates for biological interactions due to their high surface-to-volume ratio.

[0004] In the electrospinning process, a polymer is dissolved in a solution and metered through a capillary or orifice at a controlled flow rate. By applying a critical voltage that overcomes the surface tension of the polymer solution (and provided the molecular chains are sufficiently entangled in the solution), fiber formation is possible. When a critical voltage is applied, a high charge density is induced, forming a Taylor cone at the tip of the orifice. A Taylor cone is a cone observed in electrospinning, electro-spraying, and hydrodynamic spraying processes, from which a jet of charged material is ejected when the threshold voltage is exceeded.

[0005] The rapid whipping instability ejected from the Taylor cone, or fiber jet, travels from the orifice to the collector or substrate at a speed of approximately 10 m / s. Because the fiber jet is so fast, fiber formation occurs on a millisecond scale due to the rapid evaporation of the solvent, suppressing polymer crystallization. Typically, the jet ejected from the polymer solution elongates by more than 10,000 times in 0.05 seconds. This high elongation ratio is caused by electrically induced whipping instability, and this high elongation, along with the confinement of chains within micron-sized fibers, allows the polymer chains to maintain their elongated state even after fiber solidification.

[0006] In semi-crystalline polymers, delayed crystallization is typically observed. This is because the rapid solidification of the elongated polymer chains leaves insufficient time for the formation of appropriate crystalline regions, and the small fiber diameter inhibits formation. Furthermore, this formation process can generate considerable internal stress in the resulting fibers. Because the polymer chains within the fibers are highly elongated in the amorphous state, these materials can undergo both morphological and mechanical property changes due to cold crystallization and stress relaxation due to heating when exposed to heat.

[0007] Electrospun materials offer advantages in a wide range of applications in the medical device field, including tissue replacement, augmentation, and drug delivery. However, due to their amorphous nature and the highly elongated polymer chains present within the polymer fibers, electrospun materials are relatively unstable and prone to crystallization. Furthermore, the dynamic "whipping" process used to produce small-diameter fibers generates residual stress. Common electrospun materials can undergo polymer crystallization upon heat treatment / exposure, distorting the fiber topography and pore size, inducing shrinkage, and altering mechanical properties. For example, poly(lactic acid-glycolic acid) copolymers (PGLAs) such as VICRYL 90 / 10 PGLA have been observed to shrink by up to 20% at temperatures of 37°C. As a result, structures become smaller and their rigidity increases significantly, but desirable chemical and mechanical properties are lost.

[0008] What is needed in this field is an improved electrospun material. The following disclosure addresses this need. [Overview of the project]

[0009] In accordance with the purpose of the disclosed compositions and methods embodied and generally described herein, the subject of the disclosure is compositions and methods for producing and using electrospun materials.

[0010] For example, this specification discloses compositions and methods for producing and using electrospun materials. Such disclosed materials may overcome limitations found in conventional nonwoven materials, such as poor cell infiltration and migration, toxicity of residual solvents, low mechanical strength, and challenges in producing thick sheets. The disclosed compositions and methods include electrospun materials having properties such as at least thick sheets, softness, little to no residual solvent, sufficient mechanical strength for many medical device and implantation applications, and / or porosity to promote cell infiltration and migration.

[0011] For example, this specification discloses electrospun materials and methods for producing electrospun materials. In some examples, the electrospun materials may include polymer fibers comprising at least glycolide monomers and lactide monomers, having properties such as at least softness, bulkiness, specific pore size, little to no solvent retention, and mechanical and dimensional stability for use in implantable medical devices.

[0012] For example, in this specification, an electrospinning material comprising two fiber populations is disclosed, wherein one fiber population comprises polymer fibers of a block semi-crystalline copolymer comprising at least residues of glycolide monomers or lactide monomers, and the second fiber population comprises a semi-crystalline polymer, and the electrospinning material comprises a polyester, a polyether ester, or a polyester carbonate. In some embodiments, the electrospinning structure meets the requirement that all polymers used to prepare the first fiber population and the second fiber population have a glass transition temperature of 25 °C or lower, the residual solvent is less than 2,000 ppm, the tensile modulus at room temperature is less than 30 MPa, and it is wettable when placed in water for less than 5 seconds, or a combination thereof. <> <>

[0013] <> In some embodiments, the pre-electrospinning material is a triblock polymer that contains less than 90% and more than 55% of its composition of glycolide monomers or lactide monomers. <> <>

[0014] <> In some embodiments, the material is a triblock polymer structure having an amorphous segment containing either trimethylene carbonate or caprolactone. <> <>

[0015] <> In some embodiments, the material is a triblock polymer structure having an amorphous segment with a glass transition temperature below 0 °C. <> <>

[0016] <> In some embodiments, the material comprises a block copolymer comprising an amorphous segment (A), a semi-crystalline end graft (B), and an initiator (I), and its structure may be I-A-B, and the initiator may be a monofunctional, bifunctional, trifunctional, and other polyfunctional site. <> <>

[0017] <> In some embodiments, the residual solvent of the material is less than 1,000 ppm. <> <>

[0018] <> In some embodiments, the residual solvent is less than 2,000 ppm. <> <>

[0019] In some examples, the residual hexafluoro-2-propanol in the material is less than 1,000 ppm.

[0020] In some examples, the residual hexafluoro-2-propanol in the material is less than 2,000 ppm.

[0021] In some examples, the density of the material is 350 kg / m³. 3 It is less than.

[0022] In some examples, the deflection of the material relative to a 50mm sheet is 1° or more.

[0023] In some embodiments, the material has at least two fiber clusters of polyester or polyester carbonate.

[0024] In some embodiments, the material has at least two fiber clusters, the second fiber cluster comprising polydioxanone.

[0025] In some embodiments, the material is a blend of polymers including polyester, polyester carbonate, polyether, or a combination thereof.

[0026] In some embodiments, the material includes at least one physiologically active agent selected from the group consisting of anti-inflammatory agents, anesthetic agents, antineoplastic agents, antimicrobial agents, bactericides, antithrombotic agents, and cell proliferation promoters.

[0027] In some embodiments, the material is a medical device or a composite product.

[0028] In some embodiments, the material is a bioabsorbable pouch.

[0029] Furthermore, this specification also discloses electrospun materials comprising polymer fibers obtained from block copolymers of at least glycolide monomers or lactide monomers. In some examples, the electrospun materials have a polymer glass transition temperature of less than 25°C, a residual solvent of less than 2,000 ppm, a tensile modulus of less than 30 MPa at room temperature, or a combination thereof.

[0030] In some examples, the electrospun material is a triblock polymer containing less than 90% and more than 55% of its composition of glycolide monomers or lactide monomers.

[0031] In some embodiments, the material is a triblock polymer structure having amorphous segments containing either trimethylene carbonate or caprolactone.

[0032] In some embodiments, the material is a triblock polymer structure having amorphous segments with a glass transition temperature of less than 0°C.

[0033] In some examples, the glass transition temperature of the material is less than 25°C.

[0034] In some embodiments, the material comprises a block copolymer including amorphous segments (A), semicrystalline end grafts (B), and an initiator (I), the structure of which may be IAB, and the initiator may be monofunctional, difunctional, trifunctional, or other polyfunctional moieties.

[0035] In some examples, the residual solvent content of the material is less than 1,000 ppm.

[0036] In some examples, the residual hexafluoro-2-propanol in the material is less than 1,000 ppm.

[0037] In some examples, the residual hexafluoro-2-propanol in the material is less than 2,000 ppm.

[0038] In some examples, the density of the material is 350 kg / m³. 3 It is less than.

[0039] In some examples, the deflection of the material relative to a 50mm sheet is 1° or more.

[0040] In some embodiments, the material has at least two fiber clusters of polyester or polyester carbonate.

[0041] In some embodiments, the material has at least two fiber clusters, the second fiber cluster comprising polydioxanone.

[0042] In some embodiments, the material is a blend of polymers including polyester, polyester carbonate, polyether, or a combination thereof.

[0043] In some embodiments, the material can be immersed in water at room temperature in less than 5 seconds.

[0044] In some embodiments, the material includes at least one physiologically active agent selected from the group consisting of anti-inflammatory agents, anesthetic agents, antineoplastic agents, antimicrobial agents, bactericides, antithrombotic agents, and cell proliferation promoters.

[0045] In some embodiments, the material is a medical device or a composite product.

[0046] In some embodiments, the material is a bioabsorbable pouch.

[0047] Further advantages may be described in part in the following description or learned through the implementation of the embodiments described below. The advantages described below will be realized and achieved by the elements and combinations specifically indicated in the attached claims. It should be understood that both the above summary and the following detailed description are merely illustrative and explanatory, and not limiting.

[0048] The exemplary features, properties, and various advantages of this disclosure will become apparent from the accompanying drawings and the following detailed description of various embodiments. Non-limiting and non-exclusive embodiments are described with reference to the accompanying drawings, and similar labels or reference numbers refer to similar parts throughout the various drawings unless otherwise specified. The size and relative position of elements in the drawings are not necessarily drawn to scale. For example, the shapes of various elements have been selected, enlarged, and positioned to improve the readability of the drawings. Certain shapes of elements depicted have been selected for ease of recognition in the drawings. [Brief explanation of the drawing]

[0049] [Figure 1A] These are microscopic images of different parts of an electrospun material created from MG5 copolymer. [Figure 1B] These are microscopic images of different parts of an electrospun material created from MG5 copolymer. [Figure 2A] These are micrographs of different parts of electrospun materials prepared from the first multiaxial copolymer MG5 and the second polymer PPD-3 (polydioxanone) polymer. [Figure 2B] These are micrographs of different parts of electrospun materials prepared from the first multiaxial copolymer MG5 and the second polymer PPD-3 (polydioxanone) polymer. [Figure 3A] These are micrographs of different parts of an electrospun material prepared from the first polymer multiaxial copolymer MG5 and the second copolymer RD7. [Figure 3B] These are micrographs of different parts of an electrospun material prepared from the first polymer multiaxial copolymer MG5 and the second copolymer RD7. [Figure 4A] These are microscopic images of different parts of an electrospun material created from MG9 copolymer. [Figure 4B] These are microscopic images of different parts of an electrospun material created from MG9 copolymer. [Figure 5A]These are micrographs of different parts of electrospun materials prepared from the first copolymer MX1 ​​and the second polymer PPD-3. [Figure 5B] These are micrographs of different parts of electrospun materials prepared from the first copolymer MX1 ​​and the second polymer PPD-3. [Figure 6A] These are microscopic images of different parts of an electrospun material created from PPD-3 homopolymer. [Figure 6B] These are microscopic images of different parts of an electrospun material created from PPD-3 homopolymer. [Figure 7A] These are micrographs of different parts of electrospun materials prepared from the first copolymer MX2 and the second polymer PPD-3. [Figure 7B] These are micrographs of different parts of electrospun materials prepared from the first copolymer MX2 and the second polymer PPD-3. [Figure 8A] These are micrographs of different parts of electrospun materials prepared by adding an activator to the first copolymer MX2 and the second polymer PPD-3. [Figure 8B] These are micrographs of different parts of electrospun materials prepared by adding an activator to the first copolymer MX2 and the second polymer PPD-3. [Figure 9A] These are microscopic images of different parts of an electrospun material created from RD-7 copolymer. [Figure 9B] These are microscopic images of different parts of an electrospun material created from RD-7 copolymer. [Figure 10A] These are microscopic images of different parts of an electrospun material created from MDP3 copolymer. [Figure 10B] These are microscopic images of different parts of an electrospun material created from MDP3 copolymer. [Figure 11A] These are microscopic images of different parts of an electrospun material prepared from PCL homopolymer. [Figure 11B] These are microscopic images of different parts of an electrospun material prepared from PCL homopolymer. [Figure 12A] These are microscopic images of different parts of an electrospun material made from PLA homopolymer. [Figure 12B] These are microscopic images of different parts of an electrospun material made from PLA homopolymer. [Figure 13A] These are micrographs of electrospun materials prepared from MG5, PPD3, and PEG. [Figure 13B] These are micrographs of electrospun materials prepared from MG5, PPD3, and PEG. [Figure 14] This is a two-layer electrospun fabric pouch with a 0.5cm welded seam. [Figure 15] This is an electrospun layer structure with a 2 mm ultrasonically welded seam. [Modes for carrying out the invention]

[0050] Those skilled in the art will understand that one or more embodiments of the present invention may achieve a particular objective, while one or more other embodiments may achieve other particular objectives. Each objective may not be equally applicable in all respects to all embodiments of the present invention. Therefore, the aforementioned objectives may be considered alternatively with respect to any one embodiment of the present invention. These and other objectives and features of the present invention will become more fully apparent when the following detailed description is read in conjunction with the accompanying figures and examples. However, it should be understood that the above summary of the invention and the following detailed description relate to preferred embodiments and do not limit the present invention or other alternative embodiments. In particular, although the present invention is described herein with reference to several specific embodiments, it should be understood that this description is illustrative and should not be construed as limiting the invention. Those skilled in the art may conceive of various modifications and applications without departing from the spirit and scope of the invention as set forth in the appended claims. Similarly, other objectives, features, advantages, and superiorities of the present invention are evident from this summary and certain embodiments described below and will be readily apparent to those skilled in the art. Such objectives, features, advantages, and superiorities will become apparent, in addition to the above description, in conjunction with the attached examples, data, figures, and any reasonable inferences derived therefrom, either individually or by considering the references incorporated herein.

[0051] The methods and compositions described herein may be more readily understood by referring to the following detailed description of specific embodiments of the disclosed subject matter and the examples contained herein.

[0052] Before the methods and compositions of the present invention are disclosed and described, it should be understood that the embodiments described below are not limited to specific synthesis methods or specific reagents and are naturally subject to change. It should also be understood that the terms used herein are for the purpose of describing specific embodiments only and are not intended to limit them.

[0053] Furthermore, various publications are referenced throughout this specification. The disclosures of these publications are incorporated by reference to this application in whole, in order to more fully describe the current state of the art relating to the disclosed content. The disclosed references are also discussed in the texts relating to them, and the material contained herein is incorporated by reference individually and specifically.

[0054] In this specification and the following claims, several terms are used, but they are defined as having the following meanings:

[0055] Throughout this description and the claims, the word “comprise,” as well as other forms of the word such as “comprising” and “comprises,” means “including, but not limited to,” and is not intended to exclude, for example, other adducts, components, elements, or steps.

[0056] As used herein and in the appended claims, the singular forms “a,” “an,” and “the” refer to multiple subjects unless the context clearly indicates otherwise. Thus, for example, a reference to “composition” includes mixtures of two or more such compositions, a reference to “compound” includes mixtures of two or more such compound, a reference to “pharmaceutical” includes mixtures of two or more such pharmaceuticals, and so on.

[0057] "Optional" or "optionally" means whether the event or situation described thereafter is possible or impossible, and the description includes both cases in which the event or situation occurs and cases in which it does not occur.

[0058] Values ​​may be expressed as “mean” values ​​in this specification. “Mean” usually refers to the average value of a statistic.

[0059] "Effectively" means within 5%, for example, within 4%, within 3%, within 2%, or within 1%.

[0060] "Exemplary" means "an example of," and is not intended to suggest a preferred or ideal embodiment. "Such as" is used for explanatory purposes, not restrictively.

[0061] Throughout this specification, the distinguishing terms “First” and “Second” are used solely to help distinguish different components, features, or steps of the disclosed subject matter. The distinguishing terms “First” and “Second” are not intended to imply any particular order, quantity, priority, or importance of the components or steps to which these terms are applied.

[0062] As used herein, the term “or any combination thereof” refers to all permutations and combinations of the items listed before that term. For example, “A, B, C, or any combination thereof” is intended to include at least one of A, B, C, AB, AC, BC, or ABC, and also includes BA, CA, CB, CBA, BCA, ACB, BAC, or CAB, where the order is important in the particular context. Continuing this example, combinations that explicitly include repetitions of one or more items or terms are explicitly included, such as BB, AAA, AB, BBC, AAABCCCC, CBBAAA, CABABB, etc. A person skilled in the art will understand that, unless otherwise evident from the context, there is generally no limit to the number of items or terms in any combination.

[0063] References in parts by weight of a particular element or component in a composition in the specification and the last set of claims indicate a weight relationship between the element or component in the composition or article in which the parts by weight are represented and any other element or component. Thus, in a composition containing 2 parts by weight of component X and 5 parts by weight of component Y, X and Y exist in a weight ratio of 2:5, and such a ratio exists whether or not additional components are included in the composition.

[0064] The weight percentage (wt%) of an ingredient is based on the total weight of the formulation or composition in which that ingredient is contained, unless otherwise stated.

[0065] In this specification, polymers and copolymers may be used interchangeably, and those skilled in the art will understand their respective meanings.

[0066] The term "(meth)acrylic..." includes "acrylic...", "methacrylic...", or mixtures thereof.

[0067] In this specification, the term “rigidity” has the conventional definition of a measure of resistance to deformation of an elastic material when a force is applied along a given degree of freedom. Similarly, in this specification, the terms “flexibility” and “elasticity” refer to the ability of a material to elastically deform when a force is applied along a given degree of freedom, and not necessarily to plastically deform. In some circumstances, some plastic deformation may occur, and the measurements provided herein may include total deformation that includes both elastic and plastic deformation. In this specification, a material or structure is said to be flexible if it deforms when a force is applied, but returns to its original shape before the force was applied without the need for heat when the force is removed.

[0068] This disclosure provides compositions and methods for producing and using electrospun materials. Such disclosed electrospun nonwovens overcome the limitations observed in conventionally known electrospun materials. In electrospinning polyester materials, trade-offs can occur in the material selection process. For example, certain polyester fiber compositions for electrospinning may be strong and can be spun into thicker sheets, but it may be difficult to extract residual solvents from the resulting electrospun material, and the resulting electrospun material may not exhibit thermal stability. Also, certain polyester fiber compositions may tend to produce stiffer nonwovens (tensile modulus > 50 MPa). Furthermore, there are known polyester fiber compositions that are more flexible and easier to remove residual solvents from, but they cannot be electrospun into thick sheets, and the resulting electrospun material (e.g., fabric) has low mechanical strength.

[0069] Previous research by D'Amato (D'Amato, Anthony R., et al. Electrospinning 2.1(2018):15-28.) highlighted the challenge of solvent retention in electrospun sheets. In particular, residual HFIP solvent after spinning reached 78,000 ppm and 54,000 ppm, respectively, for polyglycolide and polylactide-co-polycaprolactone scaffolding materials. Some of the inventors previously showed that under low vacuum (<5 Tor), solvent removal to below 8,000 ppm is difficult, especially in polymer formulations with high glycoolide content (≧90 wt%). In D'Amato's study, the residual solvent in polyglycolide only decreased to 39,000 ppm even after 14 days at room temperature. Furthermore, D'Amato showed that solvent removal significantly increased the tensile modulus by up to 3-4 times. This presents a unique challenge in designing feasible materials, and this disclosure provides methods and compositions for materials with low residual solvent and low elastic modulus after electrospinning.

[0070] Softness is a desirable tactile characteristic of electrospun fabrics, characterized by low residual solvent and low modulus of elasticity after electrospinning, and is a subjective measure related to the perceived deformability and handling of the electrospun fabric. Several methods exist for analytically identifying materials based on characteristics related to softness. These include (1) a measure of fabric stiffness by cantilever bending angle, detailed in ASTM D1388; (2) mechanical stiffness by tensile modulus; (3) friction; (4) fiber diameter; (5) hysteresis scale; and other measures known to those skilled in the art. One method for comparing the softness of fabrics is a relative measure, such as a panel test. Another method for analytically comparing fabrics, namely multidimensional evaluation of fabrics, has been developed to provide tactile measurements; for example, the TSA unit from Emtec (Leipzig, Germany) incorporates acoustic analysis for determining roughness, plane stiffness, elasticity, and resilience.

[0071] A known challenge with nonwoven fabrics produced by electrospinning is the formation of structural thickness. Essentially, electrospinned nonwoven fabrics produce interconnected pancake-like pores, and the thickness usually increases logarithmically as layers of fabric are added during fabric production. In other words, the increase in material deposition does not correlate linearly with the fabric thickness. This is thought to be the result of several factors, one of which is the retention of solvent within the deposited fibers (drying rate during fiber movement between the needle and collector, and drying rate during residence time on the collector during subsequent material deposition), and the compressibility of the electrospinned pores. Electrospinned compositions and processes used in electrospinning that allow for a more linear approximation of the relationship between fabric thickness and material deposition create a more reproducible process with improved consistency in the nonwoven performance of a particular fabric composition. This approximate linear relationship in the fabric can be measured by the ratio of fabric thickness to basis weight.

[0072] Fabrics with increased porosity, interconnectivity, and bulkier pores, such as those disclosed herein, are beneficial for many applications. Previously known electrospun fabrics have demonstrated functionality as tissue engineering scaffolds because they can produce fibers on a size scale corresponding to extracellular matrix fibers. However, such electrospun fabrics have little to no bulkiness and flat pores that limit cell penetration. In contrast, the compositions and fabrics disclosed herein, with their bulkier pores, may allow for increased cell penetration depth. The bulkier pore structure may also enable increased interstitial channeling for angiogenesis and material transport in transplant tissue scaffolds. Depending on the application, the bulkier pore structure of electrospun materials may improve fluid conductivity and absorption in the treatment of burns and diabetic foot ulcers. This increase in pore volume and bulkiness may also enable increased delivery rates of one or more activators and carrier materials, such as core-shell polymer microspheres.

[0073] In textile terminology, bulkiness sometimes refers to the structural ratio of fibers to air. Bulky fibrous structures (e.g., yarn) or fabrics contain more air than fibers. More bulky fibrous structures or fabrics can be much thicker than low-bulk fabrics / fibrous structures, even at the same fabric weight (e.g., grams per square meter), where individual filaments are compressed. Bulky fabrics can also be compressed; that is, they are low in density and fluffy.

[0074] The drying rate during the electrospinning process can affect the properties of the fabric and is difficult to measure directly. However, the drying time can be simulated and evaluated using a thin film haze test. In this test, the spinning solution is dropped onto a glass plate and spread into a thin film of 5 microns or less using a doctor blade in a well-ventilated area. The time from application of the thin film to the haze of the thin film, room temperature, and humidity can be reported.

[0075] Previously, it was believed that highly porous and thick structures were associated with soft but weak fabrics, while stronger fabrics were associated with hard, less porous, and thinner structures. In one embodiment, this disclosure provides a highly porous and thick electrospun material having softer and stronger fabric properties. This specification overcomes the conventionally accepted trade-off between low residual solvent content and the thickness of the porous structure, and in one embodiment, provides an electrospun material that exhibits improved mechanical performance and thermal stability, as well as improved softness (deformability) and flexibility. One method for comparing the performance of different electrospun fabrics is to measure the apparent burst strength and stiffness and normalize the mechanical performance to the fabric thickness, or more importantly, the basis weight. This is expressed as (load in Newtons) / (thickness in mm) or (load in Newtons) / (g / cm²). 3 It can be expressed in terms of density per unit.

[0076] In one embodiment, the disclosed polymer composition is an absorbent copolymer synthesized from cyclic monomers of glycolide, lactide, caprolactone, trimethylene carbonate (TMC), or para-dioxanone. In one embodiment, the percentage of a particular monomer is less than 90%, less than 85%, less than 80%, or less than 75%. In one embodiment, the percentage of a certain monomer is greater than 50%, greater than 55%, greater than 60%, or greater than 65%. For example, the proportion of a particular monomer can be 50% to 90% (e.g., 50% to 70%, 70% to 90%, 50% to 60%, 60% to 70%, 70% to 80%, 80% to 90%, 50% to 85%, 50% to 80%, 50% to 75%, 50% to 65%, 55% to 90%, 60% to 90%, 65% to 90%, 75% to 90%, 55% to 85%, 60% to 80%, or 65% to 75%). In one embodiment, the disclosed copolymer comprises a block structure of three or more block segments. In one embodiment, the disclosed copolymer structure comprises a linear structure. In one embodiment, the disclosed copolymer is flexible or amorphous and comprises a multi-arm prepolymer comprising three or more arms. In one embodiment, an electrospun material produced using the disclosed copolymer has dimensional stability and thermal stability.

[0077] The polymer compositions used in electrospun fabrics disclosed herein may include polymers or copolymers such as polyester, polyester carbonate, polyether, polyether ester, or copolymers thereof. In one embodiment, the composition may include bioabsorbable polymers such as glycolic acid and lactic acid copolymers (e.g., poly(glycolic acid-lactic acid) (PGLA) and poly(lactic acid-glycolic acid) (PLGA)), polyglycolic acid (PGA) and its copolymers, polyhydroxyalkanoates (PHA) (e.g., polyhydroxybutyric acid (PHB), poly-4-hydroxybutyric acid (P4HB), polyhydroxyvalerate (PHV), polyhydroxyhexanoic acid (PHH), polyhydroxyoctanoic acid (PHO) and their copolymers), polycaprolactone (PCL), or combinations thereof. In one embodiment, the composition includes bioabsorbable polyester. The following polymers are disclosed, which are degradable by hydrolysis or other biodegradation mechanisms and comprise monomer units of trimethylene carbonate, lactide, glycolide, epsilon-caprolactone, and para-dioxanone.

[0078] In one embodiment, the polymer is an absorbable copolymer of PGLA. In one embodiment, the monomer ratio of glycosides in the PGLA used for polymerization to lactide may be 95:5, 90:10, 85:15, 80:20, 75:25, 70:30, 65:35, 60:40, 55:45, or a ratio between these amounts. In one embodiment, the monomer ratio is 90:10. In one embodiment, the disclosed electrospun composition may include a bioabsorbable polyether ester such as polydioxanone (PDO). Also disclosed is a copolymer in which the majority (w / w) of the polymer includes polymers containing PDO, poly(epsilon-caprolactone) and its copolymer, and poly(L-lactic acid), etc. In one embodiment, the amount of PDO may be in the range of 10% to 80%. In one embodiment, the amount of PDO is about 33%.

[0079] In one embodiment, the composition may include, but is not limited to, PET, polyurethane, polypropylene, PEEK, or various types of nylon, which are non-absorbent fibers. The non-absorbent fibers may be present in an amount ranging from 10% to 80%.

[0080] In one embodiment, the disclosed electrospun fabric comprises at least two fiber clusters. One fiber cluster comprises a polymer that loses more than 50% of its strength in less than 7 days. In one embodiment, one fiber cluster loses more than 50% of its strength in more than 7 days, more than 14 days, or more than 30 days.

[0081] In one embodiment, the disclosed electrospun fabric comprises one or two fiber clusters containing a polymer having two or more block sections. One fiber cluster, or at least one block section of a polymer, contains a polymer that loses more than 50% of its strength in less than seven days. In one embodiment, one fiber cluster, or at least one block section of a polymer, loses more than 50% of its strength in more than seven days, more than 14 days, or more than 30 days.

[0082] In one embodiment, the polymer or polymer block species for imparting at least one of porosity, thickness, softness, thermal stability, or improved mechanical properties to the fabric disclosed herein may include a bioabsorbable polyether ester containing poly(para-dioxanone). In one embodiment, such a polymer or polymer block species may constitute at least 30 w / w% of the thermally stable electrospun material. In one embodiment, the polymer or polymer block species may include a bioabsorbable polyester which may be a copolymer synthesized from monomers of glycolide, lactide, caprolactone, or para-dioxanone.

[0083] In one embodiment, the polymer or polymer block species for imparting at least one of the improvements in porosity, thickness, softness, thermal stability, or mechanical properties to the fabric disclosed herein may include bioabsorbable polyesters containing glycolide repeating units. In one embodiment, this contributing species may account for at least 50% of the electrospun material. In one embodiment, such polymer or polymer block species may include bioabsorbable polyesters that are copolymers synthesized from monomers of glycolide, lactide, caprolactone, trimethylene carbonate (TMC), or para-dioxanone.

[0084] In one embodiment, the polymer or polymer block species for imparting at least one of the improvements in porosity, thickness, softness, thermal stability, or mechanical properties to the fabrics disclosed herein may include a bioabsorbable polyester containing poly(caprolactone). In one embodiment, such a polymer or polymer block species may constitute at least 10% of the disclosed electrospun material. In one embodiment, such a polymer or polymer block species may include a bioabsorbable polyester that is a copolymer synthesized from monomers of glycolide, lactide, caprolactone, trimethylene carbonate (TMC), or para-dioxanone. In one embodiment, the polymer or polymer block species for imparting at least one of the improvements in porosity, thickness, softness, thermal stability, or mechanical properties to the fabrics disclosed herein may include a bioabsorbable copolyester containing poly(caprolactone-glycolide-TMC). In one embodiment, this contributing species may constitute at least 10% of the electrospun material. In one embodiment, such polymers or polymer block species may include bioabsorbable polyesters, which may be copolymers synthesized from monomers of glycolide, lactide, caprolactone, trimethylene carbonate (TMC), or para-dioxanone.

[0085] In one embodiment, the polymer contained in the electrospun composition used to form an electrospun material such as a fabric may include a polymer that is thermally stable at 25°C, 37°C, 50°C, or 100°C or higher.

[0086] In one embodiment, an electrospun composition used to form an electrospun material such as a fabric may have a solution viscosity of about 300 to 100 cP at its electrospun temperature. Such a solution viscosity can be achieved by adjusting the polymer(s) concentration in the electrospun composition. Currently, solution viscosity is thought to depend on temperature, polymer concentration, molecular weight, solvent affinity, branching, arm structures, block structures, and the addition of other chemical moieties that may affect the molecular volume.

[0087] In one embodiment, the electrospun fabric of multiple fiber groups may include at least two fiber groups, at least one of which is a thermally stable polyether ester, and at least one of which is a thermally unstable bioabsorbable polyester. These at least two fiber groups may be dispersed throughout the three-dimensional structure of the electrospun fabric of multiple fibers, and can mimic the fibrous topography of the extracellular matrix.

[0088] In one embodiment, the thermally stable polyether ester may constitute at least 30 w / w% of the thermally stable electrospun material. In one embodiment, the thermally stable polyether ester may also contain poly(para-dioxanone). In one embodiment, the thermally unstable bioabsorbable polyester may also contain poly(L-lactide-co-glycolide) copolymer. In one embodiment, the thermally stable polyether ester constitutes at least 33% of the multi-fiber collective electrospun fabric. In one embodiment, the pore size of the multi-fiber collective electrospun fabric can be maintained within 10% even after the electrospun fabric is exposed to temperatures up to 50°C.

[0089] In one embodiment, a method for producing an electrospun material, such as a fabric, may include dissolving a bioabsorbable polyester and a polyether ester in one or more solvents. The bioabsorbable polyester may be dissolved in a solvent solution that does not contain the polyether ester, or both the bioabsorbable polyester and the polyether ester may be dissolved together in a single solvent solution. The obtained solution(s) may then be mixed and extruded onto a substrate to form an electrospun material, such as a fabric. For example, the electrospun material, such as a fabric, may be formed into a three-dimensional structure in which the bioabsorbable polyester and polyether ester are dispersed throughout the entire three-dimensional structure of the electrospun material, such as a fabric.

[0090] In one embodiment, the disclosed electrospun material may include a bioabsorbable polyester comprising trimethylene and / or caprolactone repeating units.

[0091] In one embodiment, the electrospun composition disclosed or the electrospun material produced by the method disclosed herein may contain one or more therapeutic agents, drugs, or activators. For example, the pores of the disclosed electrospun material may contain one or more therapeutic agents, drugs, or activators, for example, by filling them.

[0092] This disclosure provides electrospun materials having properties such as reduced shrinkage when exposed to temperatures up to 50°C, handling properties, mechanical properties, and morphology. The thermal stability of electrospun materials may be achieved by utilizing a secondary polymer component in the polymer used in the electrospun material that, in conjunction with the main polymer component, provides a stabilizing effect. Currently, the stabilizing effect is thought to be due to secondary components such as “stabilizing” fibers that provide long-range stability, such as the overall dimensions of the fabric, and short-range stability due to individual unstable fiber elements that are not necessarily bonded by other stabilizing fibers. Thermally stable electrospun materials have been disclosed in at least PCT application numbers PCT / US2015 / 013732, PCT / US2015 / 013723, and related U.S. patents, international patents, and patent applications, each of which is incorporated herein by reference in whole.

[0093] The diameter of the electrospun fibers of this disclosure may be in the range of 0.1 to 10 μm, 0.25 to 5 μm, 0.4 to 1.6 μm, or 1.75 μm or less. Although not bound by any particular theory, it is currently believed in the art that in the manufacture of electrospun materials, the larger the fiber diameter, the larger the pore diameter, and the smaller the fiber diameter, the smaller the pore diameter. In one embodiment, the disclosed electrospun material may have a smaller fiber diameter and a larger pore diameter.

[0094] The methods for producing electrospun materials disclosed herein may include controlling the pore size of the resulting electrospun material. For example, cryogenic electrospinning can produce highly porous fabrics that are more porous than conventional electrospinning methods performed at room temperature using a collection drum also at room temperature. In one embodiment, in cryogenic electrospinning, the collector, such as a collection drum, may be cooled below the freezing (melting) point of water. The greater the temperature gradient, the greater the likelihood of ice accumulation. The humidity of the environment surrounding the electrospinning apparatus may exceed 30% to ensure sufficient ambient humidity for ice formation in the resulting electrospun material. For example, cooling the collection drum to about -80°C with dry ice causes ice crystals to form as the electrospun fibers accumulate on the collection drum during electrospinning. A mat of ice crystals embedded in the fibers accumulates on the cooled collection drum. In one embodiment, a second fiber layer may be deposited on the surface of the first fiber layer, and then, as is known to those skilled in the art, the two-layer fabric can be freeze-dried to evaporate the ice crystals. In one embodiment, the electrospinning method may include a freeze-drying step after the first fiber deposition step in electrospinning or a subsequent fiber deposition step. The electrospinned fabric may be removed from the collector and placed under vacuum (≤1.5 Torr) at a temperature lower than the melting point of the solvent used (by a cooling source). For example, if the solvent is water, the freeze-drying temperature must be 0°C or lower. The two-layer structure may include two layers, each having one or more different properties from the other. The first layer, which is initially deposited on the collector, may have desired mechanical strength properties, and the second layer may include a porous base structure that allows cell growth. In one embodiment, these different properties may be due to differences in the porosity of the two layers. As a result of the freeze-drying treatment, the first layer has approximately 10 μm 2 The outer layer has small pores with an area of ​​approximately 100-2500 μm. 2 , or several hundred to several thousand micrometers 2 Larger pores in the range may occur. In one embodiment, each layer may be thermally stable by using a thermally stable polymer co-spun through a separate spinneret with a thermally unstable polymer.

[0095] This disclosure includes a single-step method for providing pore structure control.

[0096] In one embodiment, the electrospun materials disclosed herein exhibit modularity in strength, modulus, and porosity. In one embodiment, the electrospun materials disclosed herein can be formed into a variety of shapes, including core-shell arrangements, sea-island structures, pie-like structures, and variations in fiber arrangement across the entire cross-section of the structures disclosed herein. In one embodiment, the electrospun materials disclosed herein can function as carriers for physiologically active substances, such as various pharmaceuticals, while simultaneously providing structures with excellent dimensional and thermal stability under necessary conditions, particularly biologically important, including 37°C, and even 50°C, which is required for storage stability, transport, and sterilization.

[0097] In fact, the present disclosure may be used to form layered fibers, core-sheath fibers, blended fibers, and / or composite fibers. Composite fibers may include fibers blended from two separate polymer systems that are heterogeneously or homogeneously mixed. One advantage of using these structures is the inward growth of the structure due to the presence of a biodegradable laminate adjacent to a mixed aggregate of bulk material. Furthermore, it may be possible to produce structured surfaces in which oriented fiber surfaces are formed, in contrast to randomly oriented surfaces. However, randomly oriented fibers, in contrast to oriented fibers, may be used to form adhesive surfaces.

[0098] In one embodiment, the disclosed electrospun material comprises at least two independent fiber groups, the ratio of which may be any desired ratio, 50:50, or one major fiber group and one secondary fiber group, and the material may be formed from separate spinning solutions. The electrospun material may also be called a web, mesh, or fabric, and is formed in a single process step without requiring further chemical or mechanical treatment to impart thermal, dimensional, and mechanical stability. It also does not require, for example, treatment by ultraviolet light or other means, introduction of crosslinking agents or stabilizers, or lamination of the web to improve structural integrity.

[0099] In one embodiment, this specification discloses compositions and methods for producing nonwoven fabrics or meshes. These nonwoven fabrics or meshes are based on a fiber web. The properties of the web determine the physical properties of the final product. These properties largely depend on the web shape, which is determined by the method of web formation. Web shape includes the principal direction of the fibers (orientation or randomness), the shape of the fibers (e.g., straight, hooked, curled), the degree of interlocking or entanglement between fibers, crimp and bulkiness in the Z-direction, and orientation. The resulting electrospun fabric structure and density result in properties such as mechanical properties, feel, and applicability, which are directly related to the intended use of the material. Web properties are also influenced by fiber diameter, fiber welding, fiber length, fiber surface properties such as fiber porosity, pore size, web weight, and the chemical and mechanical properties of the polymers constituting the fibers. Various methods for forming fiber webs include spunmelt, spunbond, meltblown, solution spinning (wet spinning), centrifugal melt spinning, liquid shear spinning, and electrospinning. In one embodiment, the fiber web is formed by electrospinning. Electrospinning is provided herein as an example of other nonwoven fabric processes, and the disclosed compositions are also applicable to these nonwoven fabric processes.

[0100] This disclosure may use a composition of one or more polymers or copolymers, e.g., polymers, copolymers, or one or more polymers or copolymers combined to form a composite fiber. For example, a method for mixing fibers is disclosed, which includes electrospinning at least two different independent fiber groups, each containing a polymer or copolymer, from separate spinnerets, thereby producing a mixed fiber. In electrospun materials such as mesh, for example, the polymer composition and ratio of the resulting fibers can vary based on the amount of polymer (fiber) deposited and can be controlled by the flow rate of fibers extruded to form the mesh.

[0101] The distribution of different fibers and fiber types in electrospun materials can vary. For example, one or more fiber types may differ in polymer composition. The distribution may be uniform, for example, horizontally or vertically, or uniform throughout the entire web, such as uniformly across the entire thickness, length, and width of the web. The distribution may be random, with one fiber type randomly distributed throughout the web as the dominant fiber population. Furthermore, the distribution may be such that "patches" or localized areas of one fiber type are present throughout the web, with groups of that fiber type present in some places but absent in others, forming a lamination of that fiber population among one or more different fiber types or variations of fiber types. In one embodiment, the disclosed electrospun material exhibits a uniform and random distribution throughout the entire thickness or depth of the resulting web. In one embodiment, the weight ratio of the first fiber type to the second fiber type may be 85 / 15, 80 / 20, 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, and 50 / 50, as well as values ​​between the listed ratios. In one embodiment, the ratio of the first fiber type to the second fiber type may be 67% to 33%.

[0102] The disclosed fibers may include polymers such as polyester, polyester carbonate, polyether, polyether ester, or copolymers thereof. In one embodiment, the main fiber is a bioabsorbable polymer such as polyglycolide (PGA) and its copolymers, poly(glycolic acid-lactic acid) (PGLA) and poly(lactic acid-glycolic acid) (PLGA), poly(glycolide-co-TMC), poly(glycolide-co-caprolactone-co-TMC), polyglycolic acid (PGA) and its copolymers, polyhydroxyalkanoates (PHA) (e.g., polyhydroxybutyric acid (PHB), poly-4-hydroxybutyric acid (P4HB), polyhydroxyvalerate (PHV), polyhydroxyhexanoic acid (PHH), polyhydroxyoctanoic acid (PHO) and their copolymers), polycaprolactone (PCL), or combinations thereof, homopolymers or copolymers thereof. In one embodiment, the main fiber is a bioabsorbable polyester. Furthermore, any polymer that is degradable by hydrolysis or other biodegradation mechanisms and contains the following monomer units of trimethylene carbonate, lactide, glycolide, epsilon-caprolactone, and para-dioxanone is applicable.

[0103] In one embodiment, the disclosed copolymer comprises a block structure in which at least one block is amorphous and at least one block is semicrystalline. For example, the amorphous block may include a polyester or polyester carbonate synthesized from a ring-opening cyclic monomer. Examples of these cyclic monomers include, but are not limited to, glycolides, lactides, epsilon-caprolactone, trimethylene carbonate, para-dioxanone, 1,5-dioxepane-2-one, or morpholine-2,5-dione. The semicrystalline block may include a polyester or polyester carbonate synthesized from a ring-opening cyclic monomer. Examples of cyclic monomers useful for semicrystalline blocks include, but are not limited to, glycolides, lactides, epsilon-caprolactone, trimethylene carbonate, para-dioxanone, 1,5-dioxepane-2-one, and morpholine-2,5-dione. In one embodiment, the disclosed copolymer comprises a block structure of three or more blocks (also called segments). In one embodiment, the copolymer structure comprises a linear structure. In one embodiment, the copolymer structure comprises a multiaxial prepolymer having end grafts in each arm. In one embodiment, the copolymer structure comprises a multiaxial prepolymer having three or more arms, each having an end graft. The end grafts may be synthesized from one or more monomers known and / or disclosed herein, and may be homogeneous or comprise one or more blocks. In one embodiment, the polymer has dimensional stability and thermal stability after electrospinning.

[0104] In one embodiment, the disclosed polymer is an absorbent copolymer synthesized from a single major monomer component of a selected monomer (glycolide, lactide, caprolactone, or para-dioxanone). In one embodiment, the major monomer component is less than 90 w / w%, less than 85 w / w%, less than 80 w / w%, or less than 75 w / w%, and includes one or more other monomers as minor components. In one embodiment, the monomer ratio of the major monomer component is greater than 50 w / w%, greater than 55%, greater than 60%, or greater than 65%. In one embodiment, the copolymer comprises a block structure of three or more block segments. In one embodiment, the copolymer structure comprises a linear structure. In one embodiment, the copolymer structure comprises a multiaxial prepolymer having terminal grafts in each arm. In one embodiment, the copolymer structure comprises a multiaxial prepolymer having three or more arms, each having a terminal graft. The terminal grafts may be synthesized from one or more monomers known and / or disclosed herein, and may be homogeneous or contain one or more blocks. The disclosed polymers have dimensional and thermal stability after electrospinning. In this specification, the terms polymer and copolymer may be used interchangeably, and those skilled in the art will be able to determine which term is intended when it is necessary to distinguish between them.

[0105] In one embodiment, at least one block of the absorbent block copolymer used in electrospinning has a glass transition temperature of less than 25°C, less than 15°C, or less than 0°C. In one embodiment, the electrospun fabric made from the absorbent block copolymer is thermally and dimensionally stable even when exposed to temperatures up to 75°C.

[0106] In one embodiment, the absorbent block copolymer used in a method for manufacturing electrospun fabric has semicrystalline segments with a glass transition temperature above 25°C. In one embodiment, the semicrystalline block undergoes crystallization by solvent-induced crystallization during the electrospinning process, by shifting the glass transition temperature to below 25°C. The shift in the glass transition temperature allows for a thermal transition above the glass transition temperature, resulting in limited additional crystallization and associated shrinkage of a particular fiber group or polymer block without additional treatment.

[0107] In one embodiment, the absorbent block copolymer used in the method for manufacturing electrospun fabric has semicrystalline segments having a glass transition temperature higher than the electrospinning temperature. The electrospinning temperature is generally the ambient temperature at which electrospinning is performed. Generally, no further heating or cooling of the polymer solution or collector is performed, so unless otherwise specified, it is assumed that the polymer solution, atmosphere, and collector are all at essentially the same temperature. In one embodiment, the semicrystalline block crystallizes by solvent-induced crystallization, as the glass transition temperature shifts below the electrospinning temperature. The shift in the glass transition temperature allows for a thermal transition above the glass transition temperature, resulting in limited additional crystallization and associated shrinkage without additional treatment.

[0108] In one embodiment, the electrospinning method provides a spinning temperature at which a semicrystalline polymer has a glass transition temperature above the electrospinning temperature and undergoes solvent-induced crystallization during the spinning process. In another embodiment, a semicrystalline polymer having a glass transition temperature higher than the electrospinning temperature crystallizes during the electrospinning process. In yet another embodiment, the electrospinning method provides an ambient temperature at which a semicrystalline polymer has a glass transition temperature above the ambient temperature and undergoes solvent-induced crystallization during or after the spinning process. This occurs because the solvent evaporates from the electrospinning fibers being formed, and the polymer concentration rises to a level at which spontaneous crystallization occurs during the solidification of the fibers.

[0109] In one embodiment, a semicrystalline polymer having a glass transition temperature higher than the electrospinning temperature crystallizes during the electrospinning process. In one embodiment, certain polymers that undergo rapid solvent-induced crystallization when electrospinned fibers are formed between the nozzle and collector have a sufficiently high modulus of elasticity, resulting in poor shape conformability when collected on the collector drum. This poor shape conformability minimizes compression in the z-direction, producing a bulkier fabric. This is directly related to the solvent evaporation rate, the solvent-induced crystallization rate, and the transient stiffness (or modulus of elasticity) of the fibers at the time of fiber collection on the collector.

[0110] In one embodiment, the heat of fusion of the disclosed polymer used in the method for manufacturing electrospun fabric can be analyzed by differential scanning calorimetry at a rate of 20°C / min using a sample amount of 3 to 15 mg, and when heated to equilibrium above the glass transition temperature after electrospinning, the increase in heat of fusion is less than 40%, less than 30%, less than 20%, less than 10%, less than 5%, and less than 2%.

[0111] In one embodiment, the disclosed semicrystalline polymer or copolymer used in a method for manufacturing electrospun fabric has a glass transition temperature that is less than 30°C higher than the electrospinning temperature, less than 20°C higher than the electrospinning temperature, or less than 15°C higher than the electrospinning temperature.

[0112] In one embodiment, the disclosed semicrystalline polymer or copolymer used in the method for manufacturing electrospun fabric may crystallize to an equilibrium state (no change in heat of fusion as measured by differential scanning calorimetry) at a temperature 10°C higher than the glass transition temperature in less than 1 hour, less than 30 minutes, less than 10 minutes, less than 5 minutes, or less than 2 minutes. In one embodiment, the disclosed semicrystalline polymer or copolymer used in the method for manufacturing electrospun fabric may crystallize to an equilibrium state (no change in heat of fusion as measured by differential scanning calorimetry) at a temperature 20°C higher than the glass transition temperature in less than 1 hour, less than 30 minutes, less than 10 minutes, less than 5 minutes, or less than 2 minutes. In one embodiment, the disclosed semicrystalline polymer or copolymer used in the method for manufacturing electrospun fabric may crystallize to an equilibrium state (no change in heat of fusion as measured by differential scanning calorimetry) at a temperature 30°C higher than the glass transition temperature in less than 1 hour, less than 30 minutes, less than 10 minutes, less than 5 minutes, or less than 2 minutes.

[0113] One aspect that may affect the dimensional and thermal stability of electrospun materials is the extent to which electrospun materials made from a particular polymer(s) retain and release spinning solvent. In one aspect, a disclosed polymer composition used in a method for manufacturing an electrospun material results in an electrospun fabric with residual solvent of less than 5,000 ppm, less than 2,000 ppm, or less than 1,000 ppm. The electrospun material may be further dried after electrospinning to reach even lower levels of less than 2,000 ppm, less than 1,000 ppm, or less than 100 ppm. This specification discloses polymer nonwoven materials with little or no residual solvent, which may include the polymer, solvent, electrospinning conditions, and the dimensions / density of the electrospun sheet fibers that determine the amount of residual solvent remaining in the fabric.

[0114] In one embodiment, the molecular weight due to the intrinsic viscosity of the polymer is less than 3 dL / g, less than 2.5 dL / g, less than 2.0 dL / g, less than 1.75 dL / g, or less than 1.5 dL / g. In another embodiment, the molecular weight due to the intrinsic viscosity of the polymer is greater than 0.5 dL / g, greater than 0.7 dL / g, or greater than 0.9 dL / g. In yet another embodiment, the molecular weight due to the intrinsic viscosity of the polymer is between 0.5 dL / g and 3 dL / g, between 0.7 and 2.5 dL / g, between 0.7 dL / g and 2.0 dL / g, between 0.7 dL / g and 1.75 dL / g, or between 0.7 dL / g and 1.5 dL / g.

[0115] In one embodiment, the solvent for electrospinning is a polar solvent. Examples include, but are not limited to, hexafluoro-2-propanol, chloroform, dichloromethane, 1,1,1-trifluoroacetone, dimethylformamide, and dimethyl sulfoxide. In one embodiment, a solvent mixture may be used in the electrospinning method.

[0116] In one embodiment, the disclosed polymer used in a method for manufacturing electrospun fabric has a heat of fusion greater than 20 J / g, greater than 25 J / g, greater than 30 J / g, greater than 35 J / g, or greater than 40 J / g when analyzed by differential scanning calorimetry at a rate of 20°C / min with a sample size of 3 to 15 mg. In one embodiment, the disclosed polymer used in a method for manufacturing electrospun fabric has a heat of fusion less than 100 J / g, less than 90 J / g, less than 80 J / g, less than 75 J / g, less than 50 J / g, or less than 20 J / g when analyzed by differential scanning calorimetry at a rate of 20°C / min with a sample size of 3 to 15 mg. In one embodiment, the disclosed polymer used in a method for manufacturing electrospun cloth has a heat of fusion of 1 J / g to 100 J / g, 1 J / g to 90 J / g, 3 J / g to 80 J / g, 3 J / g to 75 J / g, 3 J / g to 50 J / g, or 5 J / g to 20 J / g when analyzed by differential scanning calorimetry at a rate of 20°C / min with a sample size of 3 to 15 mg.

[0117] In one embodiment, the diameter of the disclosed polymer fibers used in the method for manufacturing electrospun fabric is less than 10 μm, less than 9 μm, or less than 8 μm when analyzed by scanning electron microscopy of the fibers in the electrospun sheet. In another embodiment, the diameter of the disclosed fibers used in the method for manufacturing electrospun fabric is greater than 0.2 μm, greater than 0.3 μm, or greater than 0.4 μm when analyzed by scanning electron microscopy of the fibers in the electrospun sheet. In yet another embodiment, the diameter of the disclosed polymer fibers used in the method for manufacturing electrospun fabric is in the diameter range of 0.1 μm to 3 μm, 0.1 μm to 5 μm, 0.1 μm to 8 μm, 0.1 μm to 9 μm, and 0.1 μm to 10 μm when analyzed by scanning electron microscopy of the fibers in the electrospun sheet.

[0118] To improve cell infiltration, the electrospun material may contain fibers comprising at least two fiber clusters or two or more polymer blocks, where one cluster or one or more polymer blocks biodegrade to enable cell infiltration into the electrospun material. In one embodiment, the electrospun material comprises two fiber clusters made from two different absorbent polymers. The first fiber cluster is thermally stable and / or may have a mass loss of less than four months. In one example, the polymer from the first fiber cluster comprises a polymer or copolymer in which at least 50% of the composition is derived from glycolide. The second fiber cluster is thermally stable and may have a mass loss of more than four months. In one example, the second fiber cluster comprises a polymer or copolymer in which at least 50 w / w% of the composition is derived from glycolide, lactide, or para-dioxanone. The first fiber cluster may account for more than 40%, more than 50%, more than 55%, or more than 60% of the electrospun sheet. The first fiber group may account for 40%-50%, 45-60%, 55-65%, or 60-99% of the electrospun sheet.

[0119] In one embodiment, the tensile modulus of the disclosed electrospun material, when analyzed according to a standard method, is less than 150 MPa, less than 100 MPa, less than 50 MPa, less than 30 MPa, and less than 15 MPa. In one embodiment, the tensile modulus of the disclosed electrospun material, when analyzed according to a standard method, is greater than 1 MPa, greater than 5 MPa, or greater than 10 MPa. In one embodiment, the tensile modulus of the disclosed electrospun material, when analyzed according to a standard method, is in the range of 1 MPa to 50 MPa, 1 MPa to 30 MPa, 10 MPa to 30 MPa, or 15 MPa to 30 MPa.

[0120] In one embodiment, the electrospun material disclosed in this disclosure may further contain one or more bioactive agents or therapeutic agents useful in a method of delivering a therapeutic agent. The method comprises the step of applying the disclosed electrospun material to a treatment site, wherein the polymer of the disclosed electrospun material comprises at least one polymer type and one or more bioactive agents and / or therapeutic agents. A biocompatible polymer composition containing a therapeutic agent can be prepared by cold working or hot working methods known to those skilled in the art, depending on the heat resistance of the therapeutic agent. Cold working is generally used for therapeutic agents that may be inactivated by heat. Briefly speaking, for a polymer component of the disclosed electrospun material containing one or more fiber clusters, one or more fiber clusters can be completely melted in the absence of a therapeutic agent. Each molten composition is cooled below room temperature to slow the crystallization of the polymer(s) in the composition. In one embodiment, the cooling is carried out at a rate of about 10°C per minute. Then, one or more therapeutic agents are added to the molten composition below room temperature and thoroughly mixed with the polymer composition to produce a homogeneous mixture.

[0121] In one embodiment, the disclosed electrospun material may have one or more bioactive agents and / or therapeutic agents applied to one or more selected portions of the disclosed electrospun material, rather than applying one or more bioactive agents and / or therapeutic agents to the entire structure. In one embodiment, the disclosed electrospun material can be immersion-coated or spray-coated with one or more bioactive agents, or with a composition that releases one or more bioactive agents over a desired time frame. In one embodiment, the electrospun fibers themselves may be synthesized to release bioactive agents (see, for example, U.S. Patent No. 8,128,954, the entire contents of which are incorporated herein by reference).

[0122] Bioactive and / or therapeutic agents include fibrotic agents, antifungal agents, antibacterial agents, anti-inflammatory agents, anti-adhesion agents, bone formation and calcification promoters, antibacterial and antibiotic agents, immunosuppressants, immunostimulants, antiseptics, anesthetics, antioxidants, cell / tissue growth promoters, lipopolysaccharide complexing agents, peroxides, scar formation inhibitors, antineoplastic agents, anticancer agents, and agents that promote integration into the extracellular matrix (ECM).

[0123] Examples of fibrosis-inducing agents include talcum powder, metallic beryllium and their oxides, copper, silk, silica, crystalline silicates, talc, quartz powder, and ethanol; extracellular matrix components selected from fibronectin, collagen, fibrin, or fibrinogen; polymers selected from polylysine, poly(ethylene-co-vinyl acetate), chitosan, N-carboxybutyl chitosan, and RGD proteins or peptide sequences longer than one amino acid; vinyl chloride or polymers of vinyl chloride; cyanoacrylate and cross-linked poly Adhesives selected from the group consisting of (ethylene glycol)methylated collagen; inflammatory cytokines (e.g., TGFβ, PDGF, VEGF, bFGF, TNFα, NGF, GM-CSF, IGF-α, IL-1, IL-1-β, IL-8, IL-6, and growth hormone); connective tissue growth factor (CTGF); bone morphogenetic proteins (BMPs) (e.g., BMP-2, BMP-3, BMP-4, BMP-5, BMP-6, or BMP-7); leptin, and bleomycin or analogues or derivatives thereof, etc. Optionally, the device may further include growth-promoting agents that stimulate cell proliferation. Examples of growth-promoting agents include dexamethasone, isotretinoin (13-cisretinoic acid), 17-e-estradiol, estradiol, 1-α-25-dihydroxyvitamin D3, diethylstilbesterol, cyclosporine A, L-NAME, all-trans retinoic acid (ATRA), and their analogues and derivatives. (See U.S. Patent Publication 2006 / 0240063, the entire contents of which are incorporated herein by reference.)

[0124] Examples of antifungal agents include, but are not limited to, polyene antifungal agents, azole antifungal agents, and echinocandin.

[0125] Examples of antimicrobial agents and antibiotics include, but are not limited to, triclosan, erythromycin, penicillin, cephalosporins, rifampin, minocycline, doxycycline, gentamicin, vancomycin, tobramycin, clindamycin, and mitomycin.

[0126] Examples of anti-inflammatory drugs include, but are not limited to, non-steroidal anti-inflammatory drugs such as ketorolac, naproxen, diclofenac sodium, and flurbiprofen.

[0127] Examples of anti-adhesion agents include, but are not limited to, talcum powder, beryllium metal and its oxides, copper, silk, silica, crystalline silicates, talc, quartz powder, and ethanol.

[0128] Examples of bone formation-promoting or calcification-promoting agents include, but are not limited to, bone graft materials such as hydroxyapatite, tricalcium phosphate, calcium chloride, calcium carbonate, and calcium sulfate, bioactive glass, and bone morphogenetic proteins (BMPs) such as BMP-2, BMP-3, BMP-4, BMP-5, BMP-6, and BMP-7.

[0129] Examples of immunosuppressants include, but are not limited to, glucocorticoids, alkylating agents, antimetabolites, and immunophilin-acting drugs such as cyclosporine and tacrolimus.

[0130] Examples of immunostimulants include, but are not limited to, interleukins, interferons, cytokines, Toll-like receptor (TLR) agonists, cytokine receptor agonists, CD40 agonists, Fc receptor agonists, immunostimulatory nucleic acids including CpG, complement receptor agonists, or adjuvants.

[0131] Examples of preservatives include chlorhexidine and tibezonium iodide, but are not limited to these.

[0132] Examples of antioxidants include, but are not limited to, antioxidant vitamins, carotenoids, and flavonoids.

[0133] Examples of anesthetics include, but are not limited to, lidocaine, mepivacaine, pirocaine, bupivacaine, prilocaine, and etidocaine.

[0134] Examples of cell proliferation-promoting factors include, but are not limited to, epidermal growth factor, human platelet-derived TGF-β, endothelial growth factor, thymocyte-activating factor, platelet-derived growth factor, fibroblast growth factor, fibronectin, or laminin.

[0135] Examples of lipopolysaccharide complexing agents include polymyxin, but the invention is not limited to this.

[0136] Examples of peroxides include, but are not limited to, benzoyl peroxide and hydrogen peroxide.

[0137] Examples of antineoplastic / anticancer agents include, but are not limited to, paclitaxel, carboplatin, miconazole, leflunamide, and ciprofloxacin.

[0138] Examples of scar formation inhibitors include, but are not limited to, cell cycle inhibitors such as taxanes and immunomodulators such as serolimus or biolimus (see, for example, sections

[0064] to

[0363] of U.S. Patent Publication No. 2005 / 0149158, and the entirety thereof, which is incorporated herein by reference).

[0139] Examples of drugs that facilitate integration into ECM include, but are not limited to, gentamicin.

[0140] In certain therapeutic approaches, it has been recognized that combining agents / drugs within the same disclosed electrospun material is useful for achieving optimal effects. Therefore, for example, combining antibacterial and anti-inflammatory agents with the disclosed electrospun material may yield synergistic effects.

[0141] In one embodiment, synthetic absorbable polymers can be formed into scaffolds and drug delivery devices for medical grafts and / or tissue engineering. For example, electrospinning can be used to produce microfibrous materials with topography similar to that of the natural extracellular matrix. In one embodiment, fiber formation by electrospinning can occur on the order of milliseconds. This may inhibit or delay the crystallization of the polymer, potentially resulting in high-density materials with small pores and little bulk or softness, which may not be suitable for the intended application. Examples of applications include, but are not limited to, scaffolds for tissue engineering, burn dressings, wound healing membranes, hernia meshes, isolation barriers, device coatings or envelopes, topical drug delivery, reinforced scaffolds, slings, void fillers, wraps, tissue bulking, and occlusions. These applications may take the form of, but are not limited to, flat sheets, pouches, 3D contour sheets, tubular structures, thin strips, tapes, and coatings.

[0142] In one embodiment, a method for manufacturing a graft or scaffold material is disclosed. PGLA and poly(para-dioxanone) (PPD) were obtained from Purac and Evonic, respectively, and each was separately dissolved in hexafluoroisopropanol (HFIP) obtained from Dupont. The resulting solutions were then electrospinned using an electrospinning apparatus with an electric field of 1.74 kV / cm. Polymer solutions were prepared by weighing 0.8 g of PGLA and 0.9 g of PPD and dissolving both in 10 mL of HFIP overnight at 50°C with moderate shaking (75 rpm). After overnight incubation (≥12 hours), the solutions were cooled to room temperature (e.g., 22±3°C) over 1 hour and then filled into syringes. The solutions were filled into 12 ml syringes and dispensed from adjacent but separate 20-gauge needles at intervals of approximately 0.5 inches. To produce various fabric compositions, the flow rate and needle count were adjusted for each type of solution (PPD vs. PGLA) to create fabrics with different compositions and properties.

[0143] In another embodiment, PGLA and PPD solutions were extruded from separate 20-gauge needle arrays at varying flow rates of 1–12 mL / hour. Composite materials were produced under conditions of PGLA-to-PPD ratios of 2:0, 2:1, 1:1, 1:2, and 0:2. These ratios can be produced by multiple methods or combinations thereof, specifically by varying (1) the relative number of needles, (2) the flow rate of individual needles, and (3) the solution concentration. In this particular embodiment, various compositions were produced by varying the number of needles while keeping the solution concentration constant. The resulting fabric contained distinct, relatively uniform small-diameter fibers deposited on a randomly oriented fiber mat. Observations by SEM and optical microscope did not clearly distinguish between PGLA and PPD fibers. However, the presence of fibers without significant size or deformation indicated that the fibers were formed from individual solutions and contained only one material. This was in contrast to very large fibers or non-uniform or film-like morphologies that may be associated with the mixing of solutions. These electrospun samples were evaluated for morphology, tensile mechanical properties, free shrinkage, and crystallization.

[0144] In one embodiment, PGLA was dissolved in HFIP at a 4.8% concentration, and PPD was dissolved in HFIP at a 5.3% concentration. Electrospinning involved extruding the different solutions through alternating rows of needles (spacing 0.57 inches apart) in a needle array, producing a mixture of PGLA and PPD fibers. The flow rate for the PGLA solution was 5 mL / hour / needle, and the flow rate for the PPD solution was 2.5 mL / hour / needle. Electrospun fabric was prepared using equal numbers of needles for both PGLA and PET solutions, resulting in a fabric with a weight ratio of 33% PPD and 67% PGLA. The final composition was also varied by changing the relative number of each needle type.

[0145] Mechanical analysis revealed that the addition of PPD reduced the ultimate tensile load and elongation at high content levels, such as above 50%, and reduced the suture pull-out strength at all filling levels with PPD above 33%. In one embodiment, a PPD content of 33% exhibited optimal mechanical properties while minimizing thermal shrinkage. DSC analysis showed a reduction in crystallization peaks in heat-treated samples.

[0146] In one aspect, the softness of the material can be characterized by the deflection angle or the tensile modulus. The amount of residual solvent in the material affects the softness of the material. This is because the residual solvent acts like a plasticizer for the material. However, all bioabsorbable electrospun materials need to keep the amount of residual solvent low to ensure biocompatibility. Semi-crystalline polymers with a high glycolide content (>85%) or a high lactide content (>85%) are very difficult to remove residual solvents such as HFIP, and the mechanical properties may be misinterpreted by the amount of residual solvent. For example, although the deflection angle obtained for MX2 in Example 6 was 69° for a 50 mm sample, it should be 0° when the residual solvent value is as low as about 10,000 ppm. In this embodiment, the tensile modulus of the soft material needs to be 40 MPa or less, 30 MPa or less, 25 MPa or less, 22 MPa or less. The residual solvent of these samples may be less than 5,000 ppm, less than 2,000 ppm, less than 1,000 ppm, or less than 500 ppm.

[0147] In one aspect, the electrospun material disclosed is infiltratable in water, saline, or phosphate-buffered saline at room temperature in less than 2 minutes, less than 1 minute, less than 30 seconds, less than

[0148] In one aspect, the electrospun material is a block copolymer comprising an amorphous segment (A), a semi-crystalline end graft (B), and an initiator (I), and its structure may be I-A-B, and the initiator may be a monofunctional, difunctional, trifunctional, and other polyfunctional sites. In one aspect, the electrospun material is bioabsorbable. Bioabsorbable means that the material is decomposed in the human body under normal physiological conditions.

[0149] In one aspect, the electrospun material is bulky. One measure of bulkiness is the density of the material. In one aspect, the electrospun material has a density of less than 375 kg / m 3 less than 350 kg / m 3 less than 340 kg / cm 3 less than 150 kg / m3 Extremely high density, 200 kg / m³ 3 Extremely high density, 225 kg / cm³ 3 It has an extremely high density.

[0150] In one embodiment, the electrospun material comprises a semicrystalline polyether. Examples of polyethers include polyethylene glycol, polypropylene glycol, or copolymers thereof. The copolymer may have a block structure or a random structure. The molecular weight of the copolymer may be greater than 700 Da, greater than 1,000 Da, or greater than 2,000 Da.

[0151] In one embodiment, the electrospun material has a deflection angle greater than 1°, greater than 5°, greater than 10°, greater than 20°, or greater than 30° for a 50 mm sample tested with a modified version of ASTM D1388.

[0152] In one embodiment, the material (e.g., polyester or polyester carbonate) is a triblock polymer structure having amorphous segments with a glass transition temperature of less than 0°C, less than -20°C, or less than -40°C.

[0153] In one embodiment, the disclosed electrospun material may have a three-dimensional structure. In one embodiment, the fiber clusters may be distributed throughout the three-dimensional structure such that the relative ratio of fibers remains substantially constant throughout the fabric structure. In one embodiment, the fabric structure may be modified such that the ratio of fibers changes throughout the structure, for example, so that some fibers are mainly outside the three-dimensional structure and not so much, or not at all, inside.

[0154] While the subject matter of the present invention is described in detail with respect to specific exemplary embodiments and their methods, it will be understood by those skilled in the art that, with a grasp of the foregoing, modifications, variations, and equivalents to these embodiments can be readily manufactured. Therefore, the scope of this disclosure is illustrative rather than restrictive, and this disclosure does not preclude the inclusion of modifications, variations, and / or additions to the subject matter of the present invention that would be readily understood by those skilled in the art.

[0155] The following examples are intended to further illustrate certain aspects of the methods and compositions described herein and are not intended to limit the scope of the claims. [Examples]

[0156] The following examples are provided below to illustrate the methods and results of the subject matter disclosed herein. These examples are not intended to encompass all aspects of the subject matter disclosed herein, but rather to illustrate representative methods, compositions, and results. These examples are not intended to exclude equivalents and variations of the invention that would be apparent to those skilled in the art.

[0157] While we strive for accuracy regarding numerical values ​​(e.g., quantities, temperatures, etc.), please be aware that some errors or variations may occur.

[0158] Deformability-following electrospun structures obtained from absorbent polymers: Example 1: Polymers for electrospinning were selected from the group consisting of linear homopolymers, linear random copolymers, linear block copolymers, and triaxial block copolymers. Linear homopolymers were prepared by ring-opening polymerization (ROP) using a tin octanoate catalyst, using a single monomer type polymerized from a monofunctional or bifunctional initiator (e.g., 1,3-propanediol), to obtain high molecular weight polymers as a single unbranched chain. Similarly, linear random copolymers were prepared by ROP using an initiator and catalyst, but these copolymers had multiple monomer repeating units, which were randomly distributed throughout the polymer chain.

[0159] Linear block copolymers were produced by a two-step polymerization process. In the first step, prepolymers with specific monomer ratios listed in the table were produced by ROP using a bifunctional initiator and a tin octanoate catalyst. These prepolymers had low molecular weight. In the second step, the prepolymer was reacted with additional monomers and catalysts to further increase the molecular weight by adding a second block (also called a terminal graft) with a different composition from the first block, as shown in the table below.

[0160] Triaxial block copolymers were produced via a two-step polymerization process using a trifunctional initiator as a raw material. In the first step of polymerization, a prepolymer with specific monomer ratios shown in the table was produced by ROP using a trifunctional initiator (trimethylolpropane) and a tin octanoate catalyst. This three-arm prepolymer was further reacted in the second step with additional monomers and catalysts to add a second block with a different composition from the first block, thereby further increasing the molecular weight.

[0161] All polymer materials were ground to narrow the particle distribution by sieving them with a 1 mm classification screen to remove fine particles and with a 4 mm classification screen to remove coarse particles. The sieved materials were purified by a vacuum extraction process and dried until they had a low moisture content. [Table 1]

[0162] Example 2: Production of single-component electrospun fabric from multiaxial copolymer MG-5 using a customized multi-spinneret electrospinning chamber and rotary collector. The polymer solution was prepared using hexafluoroisopropanol (HFIP) as the solvent and spun at 25°C and a shear rate of 400 s. -1 The solution viscosity was 550–600 cP. To achieve this viscosity, a polymer concentration of 16% was targeted, and the mixture was heated to 50°C in a container, mixed at 50 rpm for 42 hours, and tested using a viscometer.

[0163] The polymer composition was transferred to eight 60 ml syringes and filled to a capacity of 54 ml, with each syringe dispensing 52 ml of solution. Using two 4-channel high-pressure syringe pumps, the solution was dispensed at a flow rate of 0.2 ml / min while applying a voltage of 35 kV. The electrospun material was then collected on a rotating mandrel located 236 mm away from eight 20-gauge needles.

[0164] The recovered electrospun materials were vacuum-dried overnight at room temperature and then tested for suture pull-out strength (SPO), tensile strength, bursting strength, basis weight, thickness, residual HFIP by gas chromatography (GC), fiber diameter by scanning electron microscopy (SEM), and softness. See Figures 1A and 1B. [Table 2]

[0165] Example 3: Multicomponent electrospun fabric was prepared from a first polymer, a multiaxial polymer (MG5), and a second polymer, PPD-3 (polydioxanone) polymer, using a customized multi-spinneret electrospinning chamber and rotary collector. The polymer solution was prepared using hexafluoroisopropanol (HFIP) as the solvent and spun at 25°C and a shear rate of 400 s. -1 The target solution viscosity was 350–600 cP. To achieve this viscosity, the polymer concentration in the solution was targeted at 7–16%, and the mixture was mixed at 50 rpm for 42 hours using a container heated to 50°C or without heating, and tested using a viscometer.

[0166] The material was transferred to eight 60 ml syringes, each filled to a capacity of 54 ml so that 52 ml of solution could be dispensed from each syringe. Using two 4-channel high-pressure syringe pumps, the solution was dispensed at a flow rate of 0.2 ml / min while applying a voltage of 35 kV. The material was then collected on a rotating mandrel located 236 mm away from the eight 20-gauge needles.

[0167] The recovered materials were vacuum-dried overnight at room temperature and tested for suture pull-out strength (SPO), tensile strength, bursting strength, basis weight, thickness, residual HFIP by gas chromatography (GC), fiber diameter by scanning electron microscopy (SEM), and softness. See Figures 2A and 2B. [Table 3]

[0168] Example 4: A multi-component fabric prepared from a first polymer, a proprietary multiaxial copolymer MG5, and a second copolymer RD7, using a customized multi-spinneret electrospinning chamber and rotary collector. The polymer solution was prepared using hexafluoroisopropanol (HFIP) as the solvent and spun at 25°C and a shear rate of 400 s. -1 The target solution viscosity was 200–600 cP. To achieve this viscosity, the polymer concentration in the solution was targeted at 10–16%, and the mixture was mixed at 50 rpm for 42 hours in a container heated to 50°C, and tested using a viscometer.

[0169] The material was transferred to eight 60 ml syringes, each filled to a capacity of 54 ml so that 52 ml of solution could be dispensed from each syringe. Using two 4-channel high-pressure syringe pumps, the solution was dispensed at a flow rate of 0.2 ml / min while applying a voltage of 35 kV. The material was then collected on a rotating mandrel located 236 mm away from the eight 20-gauge needles.

[0170] The recovered materials were vacuum-dried overnight at room temperature and tested for suture pull-out strength (SPO), tensile strength, bursting strength, basis weight, thickness, residual HFIP by gas chromatography (GC), fiber diameter by scanning electron microscopy (SEM), and softness. See Figures 3A and 3B. [Table 4]

[0171] Example 5: A single-component fabric produced from a proprietary multiaxial copolymer MG9 using a customized multi-spinneret electrospinning chamber and rotary collector. The polymer solution was prepared using hexafluoroisopropanol (HFIP) as the solvent and spun at 25°C and a shear rate of 400 s. -1 The target solution viscosity was 350–500 cP. To achieve this viscosity, the polymer concentration was targeted at 7–15% relative to the solution, and the mixture was mixed at 50 rpm for 42 hours in a container heated to 50°C, and tested using a viscometer.

[0172] The material was transferred to eight 60 ml syringes, each filled to a capacity of 54 ml, allowing for the dispensing of 48–52 ml of solution per syringe. Two 4-channel high-pressure syringe pumps were used to dispense the solution at a flow rate of 0.05–0.25 ml / min while applying a voltage of 35 kV. The material was then collected on a rotating mandrel located 236 mm away from the eight 20-gauge needles.

[0173] The recovered materials were vacuum-dried overnight at room temperature and tested for suture pull-out strength (SPO), tensile strength, bursting strength, basis weight, thickness, residual HFIP by gas chromatography (GC), fiber diameter by scanning electron microscopy (SEM), and softness. See Figures 4A and 4B. [Table 5]

[0174] Example 6: Single-component fabric produced from the proprietary polymer MX2 using a customized multi-spinneret electrospinning chamber and rotary collector. The polymer solution was prepared using hexafluoroisopropanol (HFIP) as the solvent and spun at 25°C and a shear rate of 400 s. -1 The target solution viscosity was 300–400 cP. To achieve this viscosity, the polymer concentration was targeted at 8–11% relative to the solution, and the mixture was mixed at 50 rpm for 42 hours in a container heated to 50°C, and tested using a viscometer.

[0175] The material was transferred to eight 60 ml syringes, each filled to a capacity of 54 ml so that 52 ml of solution could be dispensed from each syringe. Using two 4-channel high-pressure syringe pumps, the solution was dispensed at a flow rate of 0.2 ml / min while applying a voltage of 30 kV. The material was then collected on a rotating mandrel located 260 mm away from the eight 20-gauge needles.

[0176] The recovered materials were vacuum-dried overnight at room temperature and tested for suture pull-out strength (SPO), tensile strength, bursting strength, basis weight, thickness, residual HFIP by gas chromatography (GC), fiber diameter by scanning electron microscopy (SEM), and softness. Figures are not shown. [Table 6]

[0177] Example 7: Multicomponent fabric prepared from a first polymer, multiaxial copolymer MX2, and a second copolymer RD7, using a customized multi-spinneret electrospinning chamber and rotary collector. The polymer solution was prepared using hexafluoroisopropanol (HFIP) as the solvent and spun at 25°C and a shear rate of 400 s. -1 The target solution viscosity was 220–400 cP. To achieve this viscosity, the polymer concentration in the solution was targeted at 10–11%, and the mixture was heated to 50°C in a container at 50 rpm for 42 hours, after which it was tested using a viscometer.

[0178] The material was transferred to eight 60 ml syringes, each filled to a capacity of 54 ml so that 52 ml of solution could be dispensed from each syringe. Using two 4-channel high-pressure syringe pumps, the solution was dispensed at a flow rate of 0.15 ml / min while applying a voltage of 30 kV. The material was then collected on a rotating mandrel located 260 mm away from the eight 20-gauge needles.

[0179] The recovered materials were vacuum-dried overnight at room temperature and tested for suture pull-out strength (SPO), tensile strength, bursting strength, basis weight, thickness, residual HFIP by gas chromatography (GC), fiber diameter by scanning electron microscopy (SEM), and softness. The materials were then dried again in a 120°C oven for 20 minutes and tested again for suture pull-out strength (SPO), tensile strength, bursting strength, basis weight, thickness, residual HFIP by gas chromatography (GC), fiber diameter by scanning electron microscopy (SEM), and softness. Figures are not shown. [Table 7]

[0180] Example 8: A multi-component fabric prepared from a first polymer, multiaxial copolymer MX1, and a second polymer, PPD-3, using a customized multi-spinneret electrospinning chamber and rotary collector. The polymer solution was prepared using hexafluoroisopropanol (HFIP) as the solvent and spun at 25°C and a shear rate of 400 s. -1 The target solution viscosity was 330–480 cP. To achieve this viscosity, the polymer concentration in the solution was targeted at 7–11%, and the mixture was mixed at 50 rpm for 42 hours using a container heated to 50°C, or without heating, and tested using a viscometer.

[0181] The material was transferred to eight 30-60 ml syringes, each filled to a capacity of 22-36 ml to allow for the dispensing of 7-35 ml of solution. Using two 4-channel high-pressure syringe pumps, the solution was dispensed at a flow rate of 0.08-0.22 ml / min while applying a voltage of 30 kV. The material was then collected on a rotating mandrel located 236 mm away from eight 20-25 gauge needles.

[0182] The recovered materials were dried for 3 to 5 nights under heated vacuum at 38–45°C and tested for suture pull-out strength (SPO), tensile strength, bursting strength, basis weight, thickness, residual HFIP by gas chromatography (GC), fiber diameter by scanning electron microscopy (SEM), and softness. See Figures 5A and 5B. [Table 8]

[0183] Example 9: A single-component fabric prepared from a proprietary homopolymer PPD-3 using a customized multi-spinneret electrospinning chamber and rotary collector. The polymer solution was prepared using hexafluoroisopropanol (HFIP) as the solvent and spun at 25°C and a shear rate of 400 s. -1 The target solution viscosity was 350–500 cP. To achieve this viscosity, the polymer concentration in the solution was targeted at 7–11%, and the mixture was mixed at 50 rpm for 42 hours, after which it was tested using a viscometer.

[0184] The material was transferred to eight 60 ml syringes, each filled to a capacity of 54 ml, allowing for the dispensing of 35–50 ml of solution per syringe. Using two 4-channel high-pressure syringe pumps, the solution was dispensed at a flow rate of 0.04–0.2 ml / min while applying a voltage of 35 kV. The material was then collected on a rotating mandrel located 200–260 mm away from the eight 20-gauge needles.

[0185] The recovered materials were vacuum-dried overnight at room temperature and tested for suture pull-out strength (SPO), tensile strength, bursting strength, basis weight, thickness, residual HFIP by gas chromatography (GC), fiber diameter by scanning electron microscopy (SEM), and softness. See Figures 6A and 6B. [Table 9]

[0186] Example 10: A multi-component fabric prepared from a first polymer, multiaxial copolymer MX2, and a second polymer, PPD-3, using a customized multi-spinneret electrospinning chamber and rotary collector. The polymer solution was prepared using hexafluoroisopropanol (HFIP) as the solvent and spun at 25°C and a shear rate of 400 s. -1 The target solution viscosity was 330–480 cP. To achieve this viscosity, the polymer concentration in the solution was targeted at 7–11%, and the mixture was mixed at 50 rpm for 42 hours using a container heated to 50°C, or without heating, and tested using a viscometer.

[0187] The material was transferred to eight 30-60 ml syringes, each filled to a capacity of 22-36 ml so that 7-16 ml of solution could be dispensed. Using two 4-channel high-pressure syringe pumps, the solution was dispensed at a flow rate of 0.08-0.22 ml / min while applying a voltage of 30 kV. The material was then collected on a rotating mandrel located 236 mm away from eight 20-25 gauge needles.

[0188] The recovered materials were dried under heated vacuum at 38°C for 3 to 5 nights and tested for suture pull-out strength (SPO), tensile strength, bursting strength, basis weight, thickness, residual HFIP by gas chromatography (GC), fiber diameter by scanning electron microscopy (SEM), and softness. See Figures 7A and 7B. [Table 10]

[0189] Example 11: A multi-component fabric was prepared by adding an activator to the first polymer, multiaxial copolymer MX2, and the second polymer, PPD-3, using a customized multi-spinneret electrospinning chamber and rotary collector. The polymer / agent solution was prepared using hexafluoroisopropanol (HFIP) as the solvent and spun at 25°C and a shear rate of 400 s. -1The target solution viscosity is 330–480 cP. To achieve this viscosity, the polymer concentration in the solution was targeted at 7–11%, and the mixture was mixed at 50 rpm for 42 hours using a container heated to 50°C or without heating, and tested using a viscometer.

[0190] The material was transferred to eight 30-60 ml syringes, each filled to a capacity of 22-36 ml so that 7-16 ml of solution could be dispensed. Using two 4-channel high-pressure syringe pumps, the solution was dispensed at a flow rate of 0.08-0.22 ml / min while applying a voltage of 30 kV. The material was then collected on a rotating mandrel located 236 mm away from eight 20-25 gauge needles.

[0191] The recovered materials were dried under heated vacuum at 38°C for 3 to 5 nights and tested for suture pull-out strength (SPO), tensile strength, bursting strength, basis weight, thickness, residual HFIP by gas chromatography (GC), fiber diameter by scanning electron microscopy (SEM), and softness. See Figures 8A and 8B. [Table 11]

[0192] Example 12: A single-component fabric produced from the proprietary multiaxial copolymer RD-7 using a customized multi-spinneret electrospinning chamber and rotary collector. The polymer solution was prepared using hexafluoroisopropanol (HFIP) as the solvent and spun at 25°C and a shear rate of 400 s. -1 The target solution viscosity was 100–400 cP. To achieve this viscosity, the polymer concentration was targeted at 7–13% relative to the solution, and the mixture was mixed at 50 rpm for 42 hours in a container heated to 50°C, and tested using a viscometer.

[0193] The material was transferred to eight 60 ml syringes, each filled to a capacity of 54 ml, allowing for the dispensing of 35–52 ml of solution per syringe. Using two 4-channel high-pressure syringe pumps, the solution was dispensed at a flow rate of 0.05–0.2 ml / min while applying a voltage of 20–35 kV. The material was then collected on a rotating mandrel located 200–260 mm away from the eight 20-gauge needles.

[0194] The recovered materials were vacuum-dried overnight at room temperature and tested for suture pull-out strength (SPO), tensile strength, bursting strength, basis weight, thickness, residual HFIP by gas chromatography (GC), fiber diameter by scanning electron microscopy (SEM), and softness. See Figures 9A and 9B. [Table 12]

[0195] Example 13: A single-component fabric prepared from a proprietary copolymer MDP3 using a customized multi-spinneret electrospinning chamber and rotary collector. The polymer solution was prepared using hexafluoroisopropanol (HFIP) as the solvent and spun at 25°C and a shear rate of 400 s. -1 The target solution viscosity was 400–600 cP. To achieve this viscosity, a polymer concentration of 6–7.5% relative to the solution was targeted, and the mixture was mixed in a container at 50 rpm for 42 hours, after which it was tested using a viscometer.

[0196] The material was transferred to eight 60 ml syringes, each filled to a capacity of 54 ml, allowing for the dispensing of 35–52 ml of solution per syringe. Two 4-channel high-pressure syringe pumps were used to dispense the solution at a flow rate of 0.05–0.2 ml / min while applying a voltage of 30–35 kV. The material was then collected on a rotating mandrel located 200–260 mm away from the eight 20-gauge needles.

[0197] The recovered materials were vacuum-dried overnight at room temperature to 70°C and tested for suture pull-out strength (SPO), tensile strength, bursting strength, basis weight, thickness, residual HFIP by gas chromatography (GC), fiber diameter by scanning electron microscopy (SEM), and softness. See Figures 10A and 10B. [Table 13]

[0198] Example 14: Single-component fabric produced from a proprietary homopolymer PCL using a customized multi-spinneret electrospinning chamber and rotary collector. The polymer solution was prepared using hexafluoroisopropanol (HFIP) as the solvent and spun at 25°C and a shear rate of 400 s. -1 The target solution viscosity was 400–600 cP. To achieve this viscosity, a polymer concentration of 10–12% relative to the solution was targeted, and the mixture was mixed in a container at 50 rpm for 42 hours, after which it was tested using a viscometer.

[0199] The material was transferred to eight 60 ml syringes, each filled to a capacity of 54 ml, allowing for the dispensing of 7–24 ml of solution per syringe. Using two 4-channel high-pressure syringe pumps, the solution was dispensed at a flow rate of 0.1–0.2 ml / min while applying a voltage of 25–30 kV. The material was then collected on a rotating mandrel located 200–260 mm away from the eight 20-gauge needles.

[0200] The recovered materials were vacuum-dried overnight at room temperature and tested for suture pull-out strength (SPO), tensile strength, bursting strength, basis weight, thickness, residual HFIP by gas chromatography (GC), fiber diameter by scanning electron microscopy (SEM), and softness. See Figures 11A and 11B. [Table 14]

[0201] Example 15: Single-component fabric produced from a proprietary homopolymer PLA using a customized multi-spinneret electrospinning chamber and rotary collector. The polymer solution was prepared using hexafluoroisopropanol (HFIP) as the solvent and spun at 25°C and a shear rate of 400 s. -1 The target solution viscosity was 400–600 cP. To achieve this viscosity, a polymer concentration of 10–12% relative to the solution was targeted, and the mixture was mixed in a container at 50 rpm for 42 hours, after which it was tested using a viscometer.

[0202] The material was transferred to eight 60 ml syringes, each filled to a capacity of 26 to 63 ml, allowing for the dispensing of 6 to 58 ml of solution. Two 4-channel high-pressure syringe pumps were used to dispense the solution at a flow rate of 0.05 to 0.2 ml / min while applying a voltage of 13 to 35 kV. The material was then collected on a rotating mandrel located 200 to 260 mm away from the eight 20-gauge needles.

[0203] The recovered materials were vacuum-dried overnight at room temperature to 70°C and tested for suture pull-out strength (SPO), tensile strength, bursting strength, basis weight, thickness, residual HFIP by gas chromatography (GC), fiber diameter by scanning electron microscopy (SEM), and softness. See Figures 12A and 12B. [Table 15]

[0204] Example 16: A single-component fabric produced from the proprietary copolymer ML-6 using a customized multi-spinneret electrospinning chamber and rotary collector. The polymer solution was prepared using hexafluoroisopropanol (HFIP) as the solvent and spun at 25°C and a shear rate of 400 s. -1 The target solution viscosity was 200–600 cP. To achieve this viscosity, a polymer concentration of 8–16% relative to the solution was targeted, and the mixture was mixed in a container at 50 rpm for 42 hours, after which it was tested using a viscometer.

[0205] The material was transferred to eight 60 ml syringes, each filled to a capacity of 26 to 63 ml, allowing for the dispensing of 6 to 58 ml of solution. Using two 4-channel high-pressure syringe pumps, the solution was dispensed at a flow rate of 0.1 to 0.3 ml / min while applying a voltage of 13 to 35 kV. The material was then collected on a rotating mandrel located 200 to 260 mm away from the eight 20-gauge needles.

[0206] The recovered materials were vacuum-dried overnight at room temperature and tested for suture pull-out strength (SPO), tensile strength, bursting strength, basis weight, thickness, residual HFIP by gas chromatography (GC), and softness. [Table 16]

[0207] Example 17: Single-component fabric produced from the proprietary copolymer ML7 using a customized multi-spinneret electrospinning chamber and rotary collector. The polymer solution was prepared using hexafluoroisopropanol (HFIP) as the solvent and spun at 25°C and a shear rate of 400 s. -1 The target solution viscosity was 200–600 cP. To achieve this viscosity, a polymer concentration of 8–16% relative to the solution was targeted, and the mixture was mixed in a container at 50 rpm for 42 hours, after which it was tested using a viscometer.

[0208] The material was transferred to eight 60 ml syringes, each filled to a capacity of 26 to 63 ml so that 6 to 58 ml of solution could be dispensed. Using two 4-channel high-pressure syringe pumps, the solution was dispensed at a flow rate of 0.05 to 0.3 ml / min while applying a voltage of 13 to 35 kV. The material was then collected on a rotating mandrel located 200 to 260 mm away from the eight 20-gauge needles.

[0209] The recovered materials were vacuum-dried overnight at room temperature and tested for tensile strength, thickness, residual HFIP by gas chromatography (GC), and softness. [Table 17]

[0210] Example 18: Single-component fabric produced from the proprietary copolymer ML8 using a customized multi-spinneret electrospinning chamber and rotary collector. The polymer solution was prepared using hexafluoroisopropanol (HFIP) as the solvent and spun at 25°C and a shear rate of 400 s. -1 The target solution viscosity was 200–600 cP. To achieve this viscosity, a polymer concentration of 8–16% relative to the solution was targeted, and the mixture was mixed in a container at 50 rpm for 42 hours, after which it was tested using a viscometer.

[0211] The material was transferred to eight 60 ml syringes, each filled to a capacity of 26 to 63 ml so that 6 to 58 ml of solution could be dispensed. Using two 4-channel high-pressure syringe pumps, the solution was dispensed at a flow rate of 0.05 to 0.3 ml / min while applying a voltage of 13 to 35 kV. The material was then collected on a rotating mandrel located 200 to 260 mm away from the eight 20-gauge needles.

[0212] The recovered materials were vacuum-dried overnight at room temperature and tested for suture pull-out strength (SPO), tensile strength, bursting strength, basis weight, thickness, residual HFIP by gas chromatography (GC), and softness. [Table 18]

[0213] Example 19: Multicomponent fabric prepared from a first polymer multiaxial copolymer MG5 and a second copolymer ML8 using a customized multi-spinneret electrospinning chamber and rotary collector. The polymer solution was prepared using hexafluoroisopropanol (HFIP) as the solvent and spun at 25°C and a shear rate of 400 s. -1The target solution viscosity was 200–600 cP. To achieve this viscosity, a polymer concentration of 8–16% relative to the solution was targeted, and the mixture was mixed in a container at 50 rpm for 42 hours, after which it was tested using a viscometer.

[0214] The material was transferred to eight 60 ml syringes, each filled to a capacity of 26 to 63 ml so that 6 to 58 ml of solution could be dispensed. Using two 4-channel high-pressure syringe pumps, the solution was dispensed at a flow rate of 0.05 to 0.3 ml / min while applying a voltage of 13 to 35 kV. The material was then collected on a rotating mandrel located 200 to 260 mm away from the eight 20-gauge needles.

[0215] The recovered materials were vacuum-dried overnight at room temperature and tested for suture pull-out strength (SPO), tensile strength, bursting strength, basis weight, thickness, residual HFIP by gas chromatography (GC), and softness. [Table 19]

[0216] Example 20: Multicomponent fabric prepared from a first polymer multiaxial copolymer MG5 and a second copolymer ML8 using a customized multi-spinneret electrospinning chamber and rotary collector. The polymer solution was prepared using hexafluoroisopropanol (HFIP) as the solvent and spun at 25°C and a shear rate of 400 s. -1 The target solution viscosity was 200–600 cP. To achieve this viscosity, a polymer concentration of 8–16% relative to the solution was targeted, and the mixture was mixed in a container at 50 rpm for 42 hours, after which it was tested using a viscometer.

[0217] The material was transferred to eight 60 ml syringes, each filled to a capacity of 26 to 63 ml so that 6 to 58 ml of solution could be dispensed. One or two 4-channel high-pressure syringe pumps were used to dispense the solution at a flow rate of 0.05 to 0.3 ml / min while applying a voltage of 13 to 35 kV. The material was then collected on a rotating mandrel located 200 to 260 mm away from four to eight 20-gauge needles.

[0218] The recovered materials were vacuum-dried overnight at room temperature and tested for suture pull-out strength (SPO), tensile strength, bursting strength, basis weight, thickness, residual HFIP by gas chromatography (GC), fiber diameter by scanning electron microscopy (SEM), and softness. [Table 20]

[0219] Example 21: A drug-filled multicomponent fabric was prepared using a customized multi-spinneret electrospinning chamber and rotary collector, containing two activators, minocycline and rifampicin, in a first polymer multiaxial copolymer MG5 and a second copolymer RD-7. The polymer / drug solution was prepared using hexafluoroisopropanol (HFIP) as the solvent and spun at 25°C and a shear rate of 400 s. -1 The target solution viscosity was 200–600 cP. To achieve this viscosity, a polymer concentration of 10–20% of the solution was targeted, and the mixture was mixed in a container at 50 rpm for 42 hours, after which it was tested using a viscometer.

[0220] The material was transferred to eight 60 ml syringes, each filled to a capacity of 26 to 63 ml, allowing for the dispensing of 6 to 58 ml of solution. Two 4-channel high-pressure syringe pumps were used to dispense the solution at a flow rate of 0.05 to 0.3 ml / min while applying a voltage of 13 to 35 kV. The material was then collected on a rotating mandrel located 160 to 260 mm away from the eight 20-gauge needles.

[0221] The recovered materials were vacuum-dried overnight at room temperature and then tested for tensile strength, thickness, and softness. [Table 21]

[0222] Example 22: Hydrophilicity adjustment of a multi-component electrospun fabric prepared from a first polymer multiaxial copolymer MG5, a second homopolymer PPD3, and a hydrophilic additive PEG (polyethylene glycol) using a customized multi-spinneret electrospinning chamber and rotary collector. The polymer / hydrophilic additive solution was prepared using hexafluoroisopropanol (HFIP) as the solvent and spun at 25°C and a shear rate of 400 s. -1 The target solution viscosity was 200–600 cP. To achieve this viscosity, the polymer concentration was targeted at 5–20% relative to the solution, and the mixture was mixed at 50 rpm for 42 hours using a container heated to 50°C, or without heating, and tested using a viscometer.

[0223] The material was transferred to eight 20 ml syringes, and each syringe was filled to a total volume of 26 ml, allowing for the dispensing of 15–24 ml of solution. Using two 4-channel high-pressure syringe pumps, the solution was dispensed at a flow rate of 0.05–0.3 ml / min while applying a voltage of 13–35 kV. The material was then collected on a rotating mandrel located 160–260 mm away from the eight 20-gauge needles.

[0224] The recovered materials were tested for suture pull-out strength (SPO), tensile strength, bursting strength, basis weight, thickness, residual HFIP by gas chromatography (GC), fiber diameter by scanning electron microscopy (SEM), wettability, and softness. Wettability was tested by placing the sample in room-temperature water and measuring the time it took for the water to be absorbed. The sample absorbed water in 2 seconds. See Figures 13A and 13B. [Table 22] [Table 23-1]

Table 23-2

[0225] Example 23: Pouch forming A flat electrospinning cloth with a thickness of 0.2 mm was laser cut into a rectangle of 7.0 cm × 8.0 cm with a corner radius of 1.0 cm. The cutting used a 60-watt CO2 laser at 30% energy, and a clean line with minimal heat-affected zone was obtained. The two cut rectangles were overlapped and put into an ultrasonic welder (Branson 2000Xc) and joined with an energy of 0.1 J / mm 2 to form a firm seam with a width of 0.5 cm around half of the rectangle without affecting the deformation followability of the electrospinning cloth. The welded pouch was sealed in an aluminum foil pouch and finally sterilized by electron beam irradiation. Refer to Figure 14.

[0226] Example 24: Use of the pouch in housing electronic devices The pouch in the aforementioned example is used in combination with CIED implantation. First, remove the sterile pouch from its protective packaging and inspect it for damage. Next, soak the pouch in sterile water, saline solution, or Ringer's lactate solution. Insert the implantable electronic device into the soaked pouch through the unwelded opening, and pass the connected lead wires out through the opening. The pouch containing the graft and the connected lead wires are implanted into a surgically prepared pocket, the skin incision is closed with sutures or adhesive, and a sterile bandage is applied.

[0227] Example 25: Formation of a laminated structure A flat electrospun fabric with a thickness of 0.2 mm was cut into 20 mm x 30 mm rectangles. Five pieces of fabric were stacked and placed in an ultrasonic welding machine (Branson 2000Xc) at 0.2 J / mm². 2 By joining with this energy, a firmly fixed joint with a width of 2 mm was formed around the entire circumference of the laminated member without reducing the suture holding power or the mechanical strength of the laminated member. See Figure 15.

[0228] Example 26: Use of laminated structures in rotator cuff repair The laminated structure described in the previous example is used as part of a rotator cuff repair. First, a surgical entry point is created and a cannula is placed to facilitate implantation. The rotator cuff is repaired in the usual manner. The laminated structure is inserted through the cannula and then positioned on top of the repaired tendon and secured with surgical staples. During the disintegration period, this laminated structure acts as a barrier between the rotator cuff and the surrounding tissue. The surgical site is closed with sutures or adhesive and further protected with a sterile bandage or dressing.

[0229] Exemplary embodiments Taking into consideration the compositions and methods described herein, certain specific embodiments of the present invention are described below. However, these particularly enumerated embodiments should not be construed as having any limiting effect on any different claims, including different or more general teachings, described herein, nor should the “specific” embodiments be construed as being limited in any way other than the inherent meaning of the language and formulas used literally therein.

[0230] Example 1: An electrospun material comprising two fiber groups, wherein one fiber group comprises polymer fibers of a block semicrystalline copolymer containing at least glycoside monomer or lactide monomer residues, and the second fiber group comprises a semicrystalline polymer comprising polyester, polyether ester, or polyester carbonate, and the electrospun structure is a. All polymers used to prepare the first fiber ensemble and the second fiber ensemble have a glass transition temperature of 25°C or lower. b. The residual solvent is less than 2,000 ppm. c. The tensile modulus at room temperature is less than 30 MPa. d. It can be infiltrated when placed in water for less than 5 seconds. The requirements are met, Electrospun materials.

[0231] Example 2: An electrospun material according to any example in this section, particularly the electrospun material described in Example 1, wherein the electrospun material is a triblock polymer containing less than 90% and more than 55% of its composition of glycolide monomers or lactide monomers.

[0232] Example 3: An electrospun material according to any example in this section, particularly Example 1, wherein the material is a triblock polymer structure having amorphous segments containing either trimethylene carbonate or caprolactone.

[0233] Example 4: An electrospinning material according to any example in this section, particularly the electrospinning material described in Example 1, wherein the material is a triblock polymer structure having an amorphous segment with a glass transition temperature below 0 °C.

[0234] Example 5: An electrospinning material according to any example in this section, particularly the electrospinning material described in Example 1, wherein the material comprises a block copolymer containing an amorphous segment (A), a semi-crystalline end graft (B), and an initiator (I), and its structure may be I-A-B, and the initiator may be a monofunctional, difunctional, trifunctional, or other polyfunctional site.

[0235] Example 6: An electrospinning material according to any example in this section, particularly the electrospinning material described in Example 1, wherein the material has a residual solvent of less than 1,000 ppm.

[0236] Example 7: An electrospinning material according to any example in this section, particularly the electrospinning material described in Example 1, wherein the material has a residual solvent of less than 2,000 ppm.

[0237] Example 8: An electrospinning material according to any example in this section, particularly the electrospinning material described in Example 1, wherein the material has a residual hexafluoro-2-propanol of less than 1,000 ppm.

[0238] Example 9: An electrospinning material according to any example in this section, particularly the electrospinning material described in Example 1, wherein the material has a residual hexafluoro-2-propanol of less than 2,000 ppm.

[0239] Example 10: An electrospinning material according to any example in this section, particularly the electrospinning material described in Example 1, wherein the material has a density of less than 350 kg / m 3 and less.

[0240] Example 11: An electrospinning material according to any example in this section, particularly the electrospinning material described in Example 1, wherein the material has a deflection of 1 ° or more in a 50 mm sheet.

[0241] Example 12: Any example of this section, in particular the electrospun material described in Example 1, wherein the material has at least two fiber clusters of polyester or polyester carbonate.

[0242] Example 13: An electrospun material according to any example of this section, in particular the electrospun material described in Example 1, wherein the material has at least two fiber groups, the second fiber group comprising polydioxanone.

[0243] Example 14: Any example of this section, in particular the electrospun material described in Example 1, wherein the material is a blend of polymers including polyester, polyester carbonate, polyether, or a combination thereof.

[0244] Example 15: An electrospun material according to any example of this section, in particular the electrospun material described in Example 1, wherein the material contains at least one physiologically active agent selected from the group consisting of anti-inflammatory agents, anesthetic agents, antineoplastic agents, antimicrobial agents, bactericides, antithrombotic agents, and cell proliferation promoters.

[0245] Example 16: Any example of this section, in particular an electrospun material as described in Example 1, wherein the material is a medical device or a composite product.

[0246] Example 17: Any example of this section, in particular an electrospun material described in Example 1, wherein the material is a bioabsorbable pouch.

[0247] Example 18: An electrospun material comprising polymer fibers obtained from a block copolymer of at least a glycolide monomer or lactide monomer, wherein the electrospun material is a. Polymer glass transition temperature below 25℃, b. Residual solvent less than 2,000 ppm, c. Tensile modulus less than 30 MPa at room temperature. A field-spun material having the following properties.

[0248] Example 19: An electrospun material according to any example in this section, particularly Example 18, wherein the electrospun material is a triblock polymer containing less than 90% and more than 55% of its composition of glycolide monomers or lactide monomers.

[0249] Example 20: An electrospun material according to any example in this section, particularly Example 18, wherein the material is a triblock polymer structure having amorphous segments containing either trimethylene carbonate or caprolactone.

[0250] Example 21: An electrospun material according to any example in this section, particularly Example 18, wherein the material is a triblock polymer structure having amorphous segments having a glass transition temperature of less than 0°C.

[0251] Example 22: An electrospun material according to any example in this section, particularly Example 18, wherein the material has a glass transition temperature of less than 25°C.

[0252] Example 23: An electrospun material according to any example in this section, particularly Example 18, wherein the material comprises a block copolymer comprising an amorphous segment (A), a semicrystalline end graft (B), and an initiator (I), the structure of which may be IAB, and the initiator may be monofunctional, difunctional, trifunctional, or other polyfunctional moieties.

[0253] Example 24: An electrospun material according to any example in this section, particularly the electrospun material described in Example 18, wherein the material has a residual solvent of less than 1,000 ppm.

[0254] Example 25: An electrospun material according to any example in this section, particularly Example 18, wherein the material has a residual hexafluoro-2-propanol content of less than 1,000 ppm.

[0255] Example 26: An electrospun material according to any example in this section, particularly Example 18, wherein the material has a residual hexafluoro-2-propanol content of less than 2,000 ppm.

[0256] Example 27: An electrospun material according to any example in this section, particularly Example 18, wherein the material is 350 kg / m 3 Electrospun material having a density of less than 1.

[0257] Example 28: An electrospun material according to any example in this section, particularly Example 18, wherein the material has a deflection of 1° or more in a 50 mm sheet.

[0258] Example 29: An electrospun material according to any example of this section, in particular the electrospun material described in Example 18, wherein the material has at least two fiber clusters of polyester or polyester carbonate.

[0259] Example 30: An electrospun material according to any example of this section, in particular Example 18, wherein the material has at least two fiber groups, the second fiber group comprising polydioxanone.

[0260] Example 31: An electrospun material according to any example of this section, in particular Example 18, wherein the material is a blend of polymers including polyester, polyester carbonate, polyether, or a combination thereof.

[0261] Example 32: An electrospun material according to any example in this section, particularly Example 18, wherein the material is immersable in water at room temperature in less than 5 seconds.

[0262] Example 33: An electrospun material according to any example of this section, in particular Example 18, wherein the material comprises at least one physiologically active agent selected from the group consisting of anti-inflammatory agents, anesthetic agents, antineoplastic agents, antimicrobial agents, bactericides, antithrombotic agents, and cell proliferation promoters.

[0263] Example 34: An electrospun material according to any example in this section, particularly Example 18, wherein the material is a medical device or a composite product.

[0264] Example 35: An electrospun material, any example of this section, in particular the electrospun material described in Example 18, wherein the material is a bioabsorbable pouch.

[0265] Other obvious advantages specific to the present invention, and the various embodiments described herein, will be apparent to those skilled in the art. Certain functions and subcombinations are useful and may be adopted without reference to other functions and subcombinations. This is contemplated and is within the scope of the claims. Since many embodiments are possible without departing from the scope of this disclosure, it should be understood that all content described herein or shown in the accompanying drawings should be interpreted as illustrative rather than restrictive.

[0266] The methods and compositions of the appended claims are not limited to the specific methods and compositions described herein, which are intended as examples of some aspects of the claims, and any functionally equivalent methods and compositions are within the scope of this disclosure. In addition to those shown and described herein, various modifications of the methods and compositions are intended to be included in the appended claims. Furthermore, while only certain representative methods, compositions, and aspects thereof are specifically described herein, other methods and compositions, as well as various combinations of features of the methods and compositions, are intended to be included in the appended claims, even if not specifically described. Thus, while combinations of steps, elements, components, or constituents can be explicitly mentioned herein, all other combinations of steps, elements, components, and constituents are also included, even if not explicitly mentioned.

Claims

1. An electrospun material comprising two fiber groups, wherein one fiber group comprises polymer fibers of a block semicrystalline copolymer containing at least a residue of glycolide monomer or lactide monomer, and the second fiber group comprises a semicrystalline polymer comprising polyester, polyether ester, or polyester carbonate, and the electrospun structure is a. All polymers used to prepare the first fiber ensemble and the second fiber ensemble have a glass transition temperature of 25°C or lower. b. The residual solvent is less than 2,000 ppm. c. The tensile modulus at room temperature is less than 30 MPa. d. It can be immersed when placed in water for less than 5 seconds. The requirements are met, Electrospun materials.

2. The electrospun material according to claim 1, wherein the electrospun material is a triblock polymer containing less than 90% and more than 55% of its composition of glycolide monomers or lactide monomers.

3. The electrospun material according to claim 1, wherein the material is a triblock polymer structure having an amorphous segment containing either trimethylene carbonate or caprolactone.

4. The electrospun material according to claim 1, wherein the material is a triblock polymer structure having amorphous segments having a glass transition temperature of less than 0°C.

5. The electrospun material according to claim 1, wherein the material comprises a block copolymer containing an amorphous segment (A), a semicrystalline end graft (B), and an initiator (I), the structure of which may be I-A-B, and the initiator may be monofunctional, difunctional, trifunctional, or other polyfunctional moieties.

6. The electrospun material according to claim 1, wherein the material has a residual solvent of less than 1,000 ppm.

7. The electrospun material according to claim 1, wherein the residual solvent is less than 2,000 ppm.

8. The electrospun material according to claim 1, wherein the material has a residual hexafluoro-2-propanol content of less than 1,000 ppm.

9. The electrospun material according to claim 1, wherein the material has a residual hexafluoro-2-propanol content of less than 2,000 ppm.

10. The aforementioned material is 350 kg / m 3 The electrospun material according to claim 1, having a density of less than 1.

11. The electrospun material according to claim 1, wherein the material has a deflection of 1° or more in a 50 mm sheet.

12. The electrospun material according to claim 1, wherein the material has at least two fiber groups of polyester or polyester carbonate.

13. The electrospun material according to claim 1, wherein the material has at least two fiber groups, and the second fiber group contains polydioxanone.

14. The electrospun material according to claim 1, wherein the material is a blend of polymers including polyester, polyester carbonate, polyether, or a combination thereof.

15. The electrospun material according to claim 1, wherein the material comprises at least one physiologically active agent selected from the group consisting of anti-inflammatory agents, anesthetic agents, antineoplastic agents, antimicrobial agents, bactericides, antithrombotic agents, and cell proliferation promoters.

16. The electrospun material according to claim 1, wherein the material is a medical device or a composite product.

17. The electrospun material according to claim 1, wherein the material is a bioabsorbable pouch.

18. A electrospun material comprising polymer fibers obtained from at least a block copolymer of a glycoside monomer or lactide monomer, wherein the electrospun material is a. Polymer glass transition temperature below 25°C b. Residual solvent less than 2,000 ppm, c. Tensile modulus less than 30 MPa at room temperature. A field-spun material having the following properties.

19. The electrospun material according to claim 18, wherein the electrospun material is a triblock polymer containing less than 90% and more than 55% of its composition of glycolide monomer or lactide monomer.

20. The electrospun material according to claim 18, wherein the material is a triblock polymer structure having amorphous segments containing either trimethylene carbonate or caprolactone.

21. The electrospun material according to claim 18, wherein the material is a triblock polymer structure having amorphous segments having a glass transition temperature of less than 0°C.

22. The electrospun material according to claim 18, wherein the material has a glass transition temperature of less than 25°C.

23. The electrospun material according to claim 18, wherein the material comprises a block copolymer containing an amorphous segment (A), a semicrystalline end graft (B), and an initiator (I), the structure may be I-A-B, and the initiator may be monofunctional, difunctional, trifunctional, or other polyfunctional moieties.

24. The electrospun material according to claim 18, wherein the material has a residual solvent of less than 1,000 ppm.

25. The electrospun material according to claim 18, wherein the material has a residual hexafluoro-2-propanol content of less than 1,000 ppm.

26. The electrospun material according to claim 18, wherein the material has a residual hexafluoro-2-propanol content of less than 2,000 ppm.

27. The aforementioned material is 350 kg / m 3 The electrospun material according to claim 18, having a density of less than [amount missing].

28. The electrospun material according to claim 18, wherein the material has a deflection of 1° or more in a 50 mm sheet.

29. The electrospun material according to claim 18, wherein the material has at least two fiber groups of polyester or polyester carbonate.

30. The electrospun material according to claim 18, wherein the material has at least two fiber groups, and the second fiber group contains polydioxanone.

31. The electrospun material according to claim 18, wherein the material is a blend of polymers including polyester, polyester carbonate, polyether, or a combination thereof.

32. The electrospun material according to claim 18, wherein the material is permeable in water at room temperature in less than 5 seconds.

33. The electrospun material according to claim 18, wherein the material comprises at least one physiologically active agent selected from the group consisting of anti-inflammatory agents, anesthetic agents, antineoplastic agents, antimicrobial agents, bactericides, antithrombotic agents, and cell proliferation promoters.

34. The electrospun material according to claim 18, wherein the material is a medical device or a composite product.

35. The electrospun material according to claim 18, wherein the material is a bioabsorbable pouch.

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