Polymers suitable for additive manufacturing

Abstract

The polymers and formulation compositions are designed to have properties that allow them to be effectively used in additive manufacturing processes, particularly to create articles in which molten monofilament polymer is laid down on top of rows of previously deposited molten monofilament polymer.

Description

[Technical field]

[0001] [CROSS REFERENCE TO RELATED APPLICATIONS] This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Application No. 62 / 814,777, filed March 6, 2019, which is incorporated by reference in its entirety for all purposes. FIELD OF THE DISCLOSURE This disclosure relates generally to additive printing, polymer compositions for use therein, and medical bioabsorbable polymer-containing articles produced therefrom. [Background technology]

[0002] Additive manufacturing, also known as 3D printing, has evolved from a curiosity to an industrial process over the past two decades, driven primarily by advances in equipment and computer software. As our ability to create sophisticated structures improves, so does the need for improved multifunctional materials to underpin this growing technology. One popular additive manufacturing method is Fused Filament Fabrication (FFF). Most FFF additive manufacturing utilizes a single-phase thermoplastic polymer monofilament to generate printed lines by melt extrusion. The printed lines are in a horizontal plane, also called the XY-plane, in which there can be multiple independent printed lines depending on the desired design of the article. Multiple articles may be printed simultaneously, in which case multiple first printed lines are placed in a single (first) XY plane. To create a three-dimensional article, i.e., to create an article with a Z-direction, one or more second printed lines are placed in a second XY plane that is located above the first XY plane defined by the location of the first printed lines. The height of the print, i.e. the length in the Z direction, is defined by the number of XY planes printed overlapping each other. After printing an article, one may test how strong it is, i.e., how much force is required to break or fracture the printed article. When performing such tests, one often finds that the strength in the XY direction is greater than the strength in the Z direction. That is, the bond between a first plane and a second plane can be broken much easier compared to the force required to break a particular XY plane. That is, the printed article has asymmetric strength, which is generally undesirable. Thus, there remains a need in the art for improved materials that can be used in additive manufacturing, particularly for manufacturing articles with reduced strength asymmetry. The present invention is directed to addressing this need. Not all subject matter discussed in the "Background Art" section is necessarily prior art, and should not be considered prior art solely as a result of its discussion in the "Background Art" section. Accordingly, recognition of prior art problems discussed in the "Background Art" section or related to the subject matter should not be treated as prior art unless expressly stated to be prior art. Rather, discussion of subject matter in the "Background Art" section should be treated as part of the inventor's approach to a particular problem that may itself be inventive. Summary of the Invention

[0003] That is, the present disclosure provides compositions useful for additive manufacturing, methods of practicing additive manufacturing using the disclosed compositions, and products produced by additive manufacturing processes, and related subject matter. The polymers and blended compositions are designed to have properties that allow them to be effectively used in additive manufacturing processes, particularly to create articles in which molten monofilament polymer is placed on top of rows of previously deposited molten monofilament polymer.

[0004] In one embodiment, the disclosure provides a monofilament fiber comprising a multiaxial polymer of formula M(B)2 or M(B)3, where M comprises repeat units and B also comprises repeat units. In the multiaxial polymer, the majority of the repeat units in M ​​are polymerized residues of TMC and / or CAP and the minority of the repeat units in M ​​are polymerized residues of LAC and / or GLY, whereas the majority of the repeat units in B are polymerized residues of GLY and / or LAC and the minority of the repeat units in B are polymerized residues of TMC and / or CAP. Thus, the midblock M has properties that are primarily due to the presence of residues of TMC and / or CAP and influenced by minor amounts of residues of LAC and / or GLY, whereas the end graft B has properties that are primarily due to the presence of residues of LAC and / or GLY and influenced by minor amounts of residues of TMC and / or CAP. Optionally, M contains both TMC and CAP repeat units, such that M is a copolymer having a majority of a mixture of CAP and TMC residues as repeat units, with a minor percentage of repeat units derived from GLY and / or LAC.

[0005] For example, the disclosure provides a monofilament fiber comprising a multiaxial polymer of formula M(B)2 or M(B)3, where M can be a homopolymer or a copolymer and comprises a plurality of repeating units, at least 50 mol %, e.g., 70 mol %, of the repeating units in M ​​are the polymerization product of at least one of trimethylene carbonate and ε-caprolactone, and B can be a homopolymer or a copolymer and comprises a plurality of repeating units, at least 50 mol %, e.g., 70 mol %, of the repeating units in B are the polymerization product of at least one of glycolide and lactide, and optionally both glycolide and lactide. In one embodiment, M is a copolymer. The present disclosure also provides an assembly comprising a monofilament fiber wound on a spool, the monofilament fiber comprising a multiaxial polymer of formula M(B)2 or M(B)3, where M is a homopolymer or copolymer and comprises a plurality of repeat units from polymerization of a first monomer, where at least 50 mol %, e.g., 70 mol % of the repeat units in M ​​are the polymerization product of at least one of trimethylene carbonate and ε-caprolactone, i.e., the first monomer is TMC and / or CAP to provide monomer M, and optionally at least two monomers, e.g., TMC and CAP, or TMC and CAP and LAC, or TMC and CAP and GLY, and B is a homopolymer or copolymer and comprises a plurality of repeat units from polymerization of a second monomer, wherein at least 50 mol %, e.g., 70 mol % of the repeat units in B are the polymerization product of at least one of glycolide and lactide (i.e., the second monomer is selected from LAC and GLY, and optionally can be a mixture of polymerized residues of LAC and GLY, optionally a mixture thereof).The disclosure also provides a kit, the kit comprising an assembly within a pouch, the assembly comprising a monofilament fiber wound on a spool, the monofilament fiber comprising a multiaxial polymer of formula M(B)2 or M(B)3, where M is a homopolymer or a copolymer and comprises a plurality of repeating units, and at least 50 mol %, e.g., 70 mol %, of the repeating units in M ​​are the polymerization product of at least one of trimethylene carbonate and ε-caprolactone, and B is a homopolymer or a copolymer and comprises a plurality of repeating units, and at least 50 mol %, e.g., 70 mol %, of the repeating units in B are the polymerization product of at least one of glycolide and lactide.

[0006] Thus, in one embodiment, the disclosure provides a kit including an assembly in a pouch, the assembly including a monofilament fiber wound on a spool, the monofilament fiber including a multiaxial polymer of formula M(B)2 or M(B)3, where M includes a plurality of repeat units, at least 50 mol % of the repeat units in M ​​are the polymerization product of at least one of trimethylene carbonate and ε-caprolactone, and B includes a plurality of repeat units, at least 50 mol % of the repeat units in B are the polymerization product of at least one of glycolide and lactide. The present disclosure also provides an assembly including a monofilament fiber wound on a spool, the monofilament fiber comprising a multiaxial polymer of formula M(B)2 or M(B)3, where M comprises a plurality of repeat units from the polymerization of a first monomer, where at least 50 mol % of the repeat units in M ​​are the polymerization product of at least one of trimethylene carbonate and ε-caprolactone, and B comprises a plurality of repeat units from the polymerization of a second monomer, where at least 50 mol % of the repeat units in B are the polymerization product of at least one of glycolide and lactide. The present disclosure also provides a monofilament fiber comprising a multiaxial polymer of formula M(B)2 or M(B)3, where M comprises a plurality of repeating units from a first monomer polymerization, where at least 50 mol% of the repeating units in M ​​are a polymerization product of at least one of trimethylene carbonate and ε-caprolactone, and B comprises a plurality of repeating units from a second monomer polymerization, where at least 50 mol% of the repeating units in B are a polymerization product of at least one of glycolide and lactide, and the present disclosure further provides a method of additive manufacturing, where the method comprises melting the monofilament to obtain a molten form of a fiber, depositing the molten form to obtain an initial article, and cooling the initial article to room temperature to form a three-dimensional solid article, and the present disclosure further provides a three-dimensional article made by this method.

[0007] Some additional exemplary embodiments of the present disclosure are briefly described below. 1) A monofilament comprising a linear polymer of formula M(B)2, where M comprises at least 5% by weight of the total weight of the M(B)2 polymer and has a Tg of less than 25°C. 2) The monofilament of embodiment 1, wherein B comprises a polymer having repeating units, at least 20 mol % of the repeating units being low crystalline or non-crystalline. 3) Monofilaments comprising a linear polymer of formula M(B)2, where B represents at least 5% by weight of the total weight of the M(B)2 polymer and comprises a polymer having a Tg of less than 25°C. 4) The monofilament of embodiment 3, wherein M comprises a polymer having repeating units, at least 20 mol % of the repeating units being low crystalline or non-crystalline. 5) Monofilaments comprising a triaxial polymer of formula M(B)3, where M comprises at least 5% by weight of the total weight of the M(B)3 polymer and has a Tg of less than 25°C. 6) The monofilament of embodiment 5, wherein B comprises a polymer having repeating units, at least 20 mol % of the repeating units being low crystalline or non-crystalline. 7) Monofilaments comprising a triaxial polymer of formula M(B)3, where B represents at least 5% by weight of the total weight of the M(B)3 polymer and comprises a polymer having a Tg of less than 25°C. 8) The monofilament of embodiment 7, wherein M comprises a polymer having repeating units, at least 20 mol % of the repeating units being low crystalline or non-crystalline. 9) A monofilament comprising a linear polymer of formula M(B)2, where B comprises a polymer having repeating units, at least 20 mol % of the repeating units being low crystalline or amorphous. 10) The monofilament of embodiment 9, wherein M comprises a polymer that accounts for at least 5% by weight of the total weight of the M(B)2 polymer and has a Tg of less than 25° C. 11) A monofilament comprising a linear polymer of formula M(B)2, where M comprises a polymer having repeating units, at least 20 mol % of the repeating units being low crystalline or amorphous. 12) The monofilament of embodiment 11, wherein B comprises a polymer that accounts for at least 5% by weight of the total weight of the M(B)2 polymer and has a Tg of less than 25° C. 13) A monofilament comprising a triaxial polymer of formula M(B)3, where B comprises a polymer having repeating units, at least 20 mol % of the repeating units being low crystalline or amorphous. 14) The monofilament of embodiment 13, wherein M comprises a polymer that accounts for at least 5% by weight of the total weight of the M(B)3 polymer and has a Tg of less than 25° C. 15) A monofilament comprising a triaxial polymer of formula M(B)3, where M comprises a polymer having repeating units, at least 20 mol % of the repeating units being low crystalline or amorphous. 16) The monofilament of embodiment 15, wherein B comprises a polymer that accounts for at least 5% by weight of the total weight of the M(B)3 polymer and has a Tg of less than 25° C. 17) The monofilament of any one of embodiments 1 to 16, wherein M comprises a polymer selected from the group consisting of poly(trimethylene carbonate), poly(lactide), and poly(trimethylene carbonate-co-lactide). 18) The monofilament according to any one of embodiments 1 to 16, wherein M comprises a polyether, such as poly(ethylene oxide), or a polyester, such as polyethylene succinate or polypropylene succinate. 19) The monofilament according to any one of embodiments 1 to 16, wherein at least 20 mol % of the low crystalline or non-crystalline repeating units are polymerized residues of monomers selected from CAP and TMC. 20) The monofilament of embodiment 19, wherein the at least 20 mol% is less than 100 mol%. 21) The monofilament according to embodiment 19, wherein the at least 20 mol% is less than 90 mol%, i.e., 20 to 90 mol%. 22) The monofilament according to embodiment 19, wherein the at least 20 mol% is less than 80 mol%, i.e., 20 to 80 mol%. 23) The monofilament of embodiment 19, wherein the low crystalline or non-crystalline repeating unit is a polymerized residue of a monomer selected from lactide, glycolide, and polydioxanone. 24) The monofilament according to any one of the preceding embodiments, wherein B comprises a residue selected from the polymerization of a monomer selected from glycolide, lactide, TMC, CAP, and dioxanone. 25) The monofilament of embodiment 24, wherein at least 50% of the residues in B are selected from the polymerization of a monomer selected from TMC, CAP, and dioxanone. 26) The monofilament of embodiment 24, wherein residues selected from the polymerization of glycolide and lactide account for less than 100% of the residues in B. 27) The monofilament according to any one of embodiments 1 to 26, which is solid at ambient temperature but fluid at elevated temperatures, which are the operating temperatures of the additive manufacturing process, having an MFI value of about 2.5 to 30 g / 10 min. 28) The monofilament according to any one of embodiments 1 to 26, which has an orientation coefficient of less than 50% and is undrawn. 29) The monofilament according to any one of embodiments 1 to 26, having a diameter in the range of 1 to 5 mm. 30) The monofilament according to any one of embodiments 1 to 26, having a columnar buckling resistance of at least 1 Newton (N). 31) A method of additive manufacturing comprising: a. melting the monofilament according to any one of embodiments 1 to 30 to obtain a molten monofilament; and b. Cooling the molten monofilament to room temperature to form a three-dimensional solid article. The method includes: 32) A kit comprising a monofilament according to any one of embodiments 1 to 30 and instructions for use of said monofilament in a method for additive manufacturing. 33) A kit comprising an assembly as described herein, e.g., a monofilament wound on a spool, and instructions for using the assembly in a method of additive manufacturing.

[0008] The features and additional features of the invention mentioned herein, and the manner of obtaining same, will become apparent and the invention will be best understood by reference to the following more detailed description, in which all references disclosed herein are incorporated by reference in their entirety as if each were individually incorporated. This Summary is provided to introduce certain concepts in a simplified form that are more fully described below in the Detailed Description. Unless otherwise expressly stated, this Summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter. The details of one or more embodiments are set forth in the following description. Features illustrated or described in connection with one exemplary embodiment may be combined with features of other embodiments. Thus, any of the various embodiments described herein may be combined to provide further embodiments. Aspects of the embodiments may be modified, if necessary, to employ concepts of the various patents, applications, and publications identified herein to provide further embodiments. Other features, objects, and advantages will become apparent from the description, drawings, and claims. Exemplary features of the present disclosure, its nature and various advantages will become apparent from the accompanying drawings and the following detailed description of various embodiments, the non-limiting and non-exhaustive embodiments of which are described with reference to the accompanying drawings. [Brief description of the drawings]

[0009] [Figure 1] 1 shows the geometry of the test printed articles used to evaluate print performance. [Diagram 2]1 is a graph showing the ultimate stress of layer adhesion of a 3D printed part. [Diagram 3] Differential scanning calorimetry (DSC) curves are shown. [Figure 4] The DSC curve is shown. [Diagram 5] The DSC curve is shown. [Figure 6] 1 is a graph showing the ultimate stress of layer adhesion of a 3D printed part. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The present disclosure may be understood more readily by reference to the following detailed description of the embodiments of the present disclosure and the "Examples" described herein. Briefly, the present disclosure provides methods of additive printing, polymer compositions for use therein, and products produced therefrom. Accordingly, the present disclosure provides compositions useful for additive manufacturing, methods of performing additive manufacturing using the disclosed compositions, and products produced by additive manufacturing processes, and related subject matter. In one aspect, the present disclosure provides monofilaments useful in additive manufacturing, which, as discussed in detail herein, may be described in part by their properties, including melting point, melt flow index, and intrinsic viscosity.

[0011] Monofilament Composition The present disclosure provides monofilaments, specifically monofilaments formed from either biaxial (abbreviated as formula M(B)2) or triaxial (abbreviated as formula M(B)3) copolymers, where M and B are distinct polymer blocks having different compositions as described herein.

[0012] Below are briefly described some exemplary monofilaments of the present disclosure. 1) A monofilament comprising a linear polymer of formula M(B)2, where M comprises at least 5% by weight of the total weight of the M(B)2 polymer, and has a Tg of less than 25° C. Optionally, the Tg is less than any of 24° C., or 23° C., or 22° C., or 21° C., or 20° C., or 19° C., or 18° C., or 17° C., or 16° C., or 15° C., or 14° C., or 13° C., or 12° C., or 11° C., or 10° C., or 9° C., or 8° C., or 7° C., or 6° C., or 5° C., or 4° C., or 3° C., or 2° C., or 1° C., or 0° C. Independently, the polymer may be described by an M that accounts for at least any of 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, or 40% by weight of the total weight of the M(B)2 polymer. 2) The monofilament according to embodiment 1, wherein B comprises a polymer having repeat units, and at least 20 mol% of the repeat units are low crystallinity or non-crystalline. Optionally, at least 25 mol%, or 30 mol%, or 35 mol%, or 40 mol%, or 45 mol%, or 50 mol%, or 55 mol%, or 60 mol%, or 65 mol%, or 70 mol%, or 75 mol%, or 80 mol% of the repeat units are low crystallinity or non-crystalline, but optionally, not all of the repeat units are low crystallinity or non-crystalline, i.e., less than 100 mol%, for example, less than 98 mol%, or 96 mol%, or 94 mol%, or 92 mol%, or 90 mol%, or 88 mol%, or 86 mol%, or 84 mol%, or 82 mol%, or 80 mol% of the repeat units are low crystallinity or non-crystalline. 3) A monofilament comprising a linear polymer of formula M(B)2, where B comprises at least 5% by weight of the total weight of the M(B)2 polymer, and has a Tg of less than 25° C. Optionally, the Tg is less than any of 24° C., or 23° C., or 22° C., or 21° C., or 20° C., or 19° C., or 18° C., or 17° C., or 16° C., or 15° C., or 14° C., or 13° C., or 12° C., or 11° C., or 10° C., or 9° C., or 8° C., or 7° C., or 6° C., or 5° C., or 4° C., or 3° C., or 2° C., or 1° C., or 0° C. Independently, the polymer may be described by an M that accounts for at least any of 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, or 40% by weight of the total weight of the M(B)2 polymer. 4) The monofilament according to embodiment 3, wherein M comprises a polymer having repeat units, and at least 20 mol% of the repeat units are low crystallinity or non-crystalline. Optionally, at least 25 mol%, or 30 mol%, or 35 mol%, or 40 mol%, or 45 mol%, or 50 mol%, or 55 mol%, or 60 mol%, or 65 mol%, or 70 mol%, or 75 mol%, or 80 mol% of the repeat units are low crystallinity or non-crystalline, but optionally, not all of the repeat units are low crystallinity or non-crystalline, i.e., less than 100 mol%, for example, less than 98 mol%, or 96 mol%, or 94 mol%, or 92 mol%, or 90 mol%, or 88 mol%, or 86 mol%, or 84 mol%, or 82 mol%, or 80 mol% of the repeat units are low crystallinity or non-crystalline. 5) A monofilament comprising a triaxial polymer of formula M(B)3, where M comprises at least 5% by weight of the total weight of the M(B)3 polymer, and has a Tg of less than 25° C. Optionally, the Tg is less than any of 24° C., or 23° C., or 22° C., or 21° C., or 20° C., or 19° C., or 18° C., or 17° C., or 16° C., or 15° C., or 14° C., or 13° C., or 12° C., or 11° C., or 10° C., or 9° C., or 8° C., or 7° C., or 6° C., or 5° C., or 4° C., or 3° C., or 2° C., or 1° C., or 0° C. Independently, the polymer may be described by an M that accounts for at least any of 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, or 40% by weight of the total weight of the M(B)3 polymer. 6) The monofilament according to embodiment 5, wherein B comprises a polymer having repeat units, and at least 20 mol% of the repeat units are low crystallinity or non-crystalline. Optionally, at least 25 mol%, or 30 mol%, or 35 mol%, or 40 mol%, or 45 mol%, or 50 mol%, or 55 mol%, or 60 mol%, or 65 mol%, or 70 mol%, or 75 mol%, or 80 mol% of the repeat units are low crystallinity or non-crystalline, but optionally, not all of the repeat units are low crystallinity or non-crystalline, i.e., less than 100 mol%, for example, less than 98 mol%, or 96 mol%, or 94 mol%, or 92 mol%, or 90 mol%, or 88 mol%, or 86 mol%, or 84 mol%, or 82 mol%, or 80 mol% of the repeat units are low crystallinity or non-crystalline. 7) A monofilament comprising a triaxial polymer of formula M(B)3, where B comprises at least 5% by weight of the total weight of the M(B)3 polymer, and has a Tg of less than 25° C. Optionally, the Tg is less than any of 24° C., or 23° C., or 22° C., or 21° C., or 20° C., or 19° C., or 18° C., or 17° C., or 16° C., or 15° C., or 14° C., or 13° C., or 12° C., or 11° C., or 10° C., or 9° C., or 8° C., or 7° C., or 6° C., or 5° C., or 4° C., or 3° C., or 2° C., or 1° C., or 0° C. Independently, the polymer may be described by an M that accounts for at least any of 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, or 40% by weight of the total weight of the M(B)3 polymer. 8) The monofilament according to embodiment 7, wherein M comprises a polymer having repeat units, and at least 20 mol% of the repeat units are low crystallinity or non-crystalline. Optionally, at least 25 mol%, or 30 mol%, or 35 mol%, or 40 mol%, or 45 mol%, or 50 mol%, or 55 mol%, or 60 mol%, or 65 mol%, or 70 mol%, or 75 mol%, or 80 mol% of the repeat units are low crystallinity or non-crystalline, but optionally, not all of the repeat units are low crystallinity or non-crystalline, i.e., less than 100 mol%, for example, less than 98 mol%, or 96 mol%, or 94 mol%, or 92 mol%, or 90 mol%, or 88 mol%, or 86 mol%, or 84 mol%, or 82 mol%, or 80 mol% of the repeat units are low crystallinity or non-crystalline. 9) Monofilaments comprising a linear polymer of formula M(B)2, B comprising a polymer having repeat units, at least 20 mol% of the repeat units being low crystalline or non-crystalline. Optionally, at least 25 mol%, or 30 mol%, or 35 mol%, or 40 mol%, or 45 mol%, or 50 mol%, or 55 mol%, or 60 mol%, or 65 mol%, or 70 mol%, or 75 mol%, or 80 mol% of the repeat units are low crystalline or non-crystalline, but optionally not all of the repeat units are low crystalline or non-crystalline, i.e., less than 100 mol%, for example less than 98 mol%, or 96 mol%, or 94 mol%, or 92 mol%, or 90 mol%, or 88 mol%, or 86 mol%, or 84 mol%, or 82 mol%, or 80 mol% of the repeat units are low crystalline or non-crystalline. 10) The monofilament of embodiment 9, wherein M comprises a polymer that comprises at least 5% by weight of the total weight of the M(B)2 polymer and has a Tg of less than 25° C. Optionally, the Tg is less than any of 24° C., or 23° C., or 22° C., or 21° C., or 20° C., or 19° C., or 18° C., or 17° C., or 16° C., or 15° C., or 14° C., or 13° C., or 12° C., or 11° C., or 10° C., or 9° C., or 8° C., or 7° C., or 6° C., or 5° C., or 4° C., or 3° C., or 2° C., or 1° C., or 0° C. Independently, the polymer may be described by an M that accounts for at least any of 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, or 40% by weight of the total weight of the M(B)2 polymer. 11) A monofilament comprising a linear polymer of formula M(B)2, where M comprises a polymer having repeat units, at least 20 mol% of the repeat units being low crystalline or non-crystalline. Optionally, at least 25 mol%, or 30 mol%, or 35 mol%, or 40 mol%, or 45 mol%, or 50 mol%, or 55 mol%, or 60 mol%, or 65 mol%, or 70 mol%, or 75 mol%, or 80 mol% of the repeat units are low crystalline or non-crystalline, but optionally not all of the repeat units are low crystalline or non-crystalline, i.e., less than 100 mol%, for example less than 98 mol%, or 96 mol%, or 94 mol%, or 92 mol%, or 90 mol%, or 88 mol%, or 86 mol%, or 84 mol%, or 82 mol%, or 80 mol% of the repeat units are low crystalline or non-crystalline. 12) The monofilament of embodiment 11, wherein B comprises a polymer that comprises at least 5% by weight of the total weight of the M(B)2 polymer and has a Tg of less than 25° C. Optionally, the Tg is less than any of 24° C., or 23° C., or 22° C., or 21° C., or 20° C., or 19° C., or 18° C., or 17° C., or 16° C., or 15° C., or 14° C., or 13° C., or 12° C., or 11° C., or 10° C., or 9° C., or 8° C., or 7° C., or 6° C., or 5° C., or 4° C., or 3° C., or 2° C., or 1° C., or 0° C. Independently, the polymer may be described by an M that accounts for at least any of 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, or 40% by weight of the total weight of the M(B)2 polymer. 13) A monofilament comprising a triaxial polymer of formula M(B)3, B comprising a polymer having repeat units, at least 20 mol% of the repeat units being low crystalline or non-crystalline. Optionally, at least 25 mol%, or 30 mol%, or 35 mol%, or 40 mol%, or 45 mol%, or 50 mol%, or 55 mol%, or 60 mol%, or 65 mol%, or 70 mol%, or 75 mol%, or 80 mol% of the repeat units are low crystalline or non-crystalline, but optionally not all of the repeat units are low crystalline or non-crystalline, i.e., less than 100 mol%, for example less than 98 mol%, or 96 mol%, or 94 mol%, or 92 mol%, or 90 mol%, or 88 mol%, or 86 mol%, or 84 mol%, or 82 mol%, or 80 mol% of the repeat units are low crystalline or non-crystalline. 14) The monofilament of embodiment 13, wherein M comprises a polymer that comprises at least 5% by weight of the total weight of the M(B)3 polymer and has a Tg of less than 25° C. Optionally, the Tg is less than any of 24° C., or 23° C., or 22° C., or 21° C., or 20° C., or 19° C., or 18° C., or 17° C., or 16° C., or 15° C., or 14° C., or 13° C., or 12° C., or 11° C., or 10° C., or 9° C., or 8° C., or 7° C., or 6° C., or 5° C., or 4° C., or 3° C., or 2° C., or 1° C., or 0° C. Independently, the polymer may be described by an M that accounts for at least any of 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, or 40% by weight of the total weight of the M(B)3 polymer. 15) A monofilament comprising a triaxial polymer of formula M(B)3, where M comprises a polymer having repeat units, at least 20 mol% of the repeat units being low crystalline or non-crystalline. Optionally, at least 25 mol%, or 30 mol%, or 35 mol%, or 40 mol%, or 45 mol%, or 50 mol%, or 55 mol%, or 60 mol%, or 65 mol%, or 70 mol%, or 75 mol%, or 80 mol% of the repeat units are low crystalline or non-crystalline, but optionally not all of the repeat units are low crystalline or non-crystalline, i.e., less than 100 mol%, for example less than 98 mol%, or 96 mol%, or 94 mol%, or 92 mol%, or 90 mol%, or 88 mol%, or 86 mol%, or 84 mol%, or 82 mol%, or 80 mol% of the repeat units may be specified as low crystalline or non-crystalline. 16) The monofilament of embodiment 15, wherein B comprises a polymer that comprises at least 5% by weight of the total weight of the M(B)3 polymer and has a Tg of less than 25° C. Optionally, the Tg is less than any of 24° C., or 23° C., or 22° C., or 21° C., or 20° C., or 19° C., or 18° C., or 17° C., or 16° C., or 15° C., or 14° C., or 13° C., or 12° C., or 11° C., or 10° C., or 9° C., or 8° C., or 7° C., or 6° C., or 5° C., or 4° C., or 3° C., or 2° C., or 1° C., or 0° C. Independently, the polymer may be described by an M that accounts for at least any of 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, or 40% by weight of the total weight of the M(B)3 polymer. 17) The monofilament of any one of embodiments 1 to 16, wherein M comprises a polymer selected from the group consisting of poly(trimethylene carbonate), poly(lactide), and poly(trimethylene carbonate-co-lactide). 18) The monofilament according to any one of embodiments 1 to 16, wherein M comprises a polyether, such as poly(ethylene oxide), or a polyester, such as polyethylene succinate or polypropylene succinate. 19) The monofilament according to any one of embodiments 1 to 16, wherein at least 20 mol % of the low crystalline or non-crystalline repeating units are polymerized residues of monomers selected from CAP and TMC. 20) The monofilament of embodiment 19, wherein the at least 20 mol% is less than 100 mol%. 21) The monofilament according to embodiment 19, wherein the at least 20 mol% is less than 90 mol%, i.e., 20 to 90 mol%. 22) The monofilament according to embodiment 19, wherein the at least 20 mol% is less than 80 mol%, i.e., 20 to 80 mol%. 23) The monofilament of embodiment 19, wherein the low crystalline or non-crystalline repeating unit is a polymerized residue of a monomer selected from lactide, glycolide, and polydioxanone. 24) The monofilament according to any one of the preceding embodiments, wherein B comprises a residue selected from the polymerization of a monomer selected from glycolide, lactide, TMC, CAP, and dioxanone. 25) The monofilament of embodiment 24, wherein at least 50% of the residues in B are selected from the polymerization of a monomer selected from TMC, CAP, and dioxanone. 26) The monofilament of embodiment 24, wherein residues selected from the polymerization of glycolide and lactide account for less than 100% of the residues in B. 27) The monofilament according to any one of embodiments 1 to 26, which is solid at ambient temperature but fluid at elevated temperatures, which are the operating temperatures of the additive manufacturing process, having an MFI value of about 2.5 to 30 g / 10 min. 28) The monofilament according to any one of embodiments 1 to 26, which has an orientation coefficient of less than 50% and is undrawn. 29) The monofilament according to any one of embodiments 1 to 26, having a diameter in the range of 1 to 5 mm. 30) The monofilament according to any one of embodiments 1 to 26, having a columnar buckling resistance of at least 1 N.

[0013] As explained below, the monofilament may comprise a copolymer, which refers to a polymer composed of two or more different repeating units. To form the M block, the monomers may be reacted with an initiator. In one embodiment, the initiator is difunctional such that the monomers form repeat units extending from two sites of the initiator to form the M portion of the M(B)2 copolymer. Exemplary difunctional initiators include diols and diamines, such as ethylene glycol and ethylene diamine. In another embodiment, the initiator is trifunctional such that the monomers form repeat units extending from three sites of the initiator to form the M portion of the M(B)3 copolymer. Exemplary trifunctional initiators include triols and triamines, such as glycerol. In one embodiment, the initiator is tetrafunctional such that the monomers form repeat units extending from four sites of the initiator. Exemplary tetrafunctional initiators include tetraols and tetraamines, such as pentaerythritol. Tetrafunctional initiators may be used to form tetrafunctional M groups in M(B)4 copolymers. The polymer chains extending from the initiator may be segmented, i.e., each polymer chain extending directly from the initiator may itself be an initiation site for the extension of a second polymer chain. This situation may be represented as (I2)(A-A')2, where I2-A may also be represented herein as M, where the initiator (I2) has two initiation sites, a polymer segment A extends directly from I (forming M), and a polymer segment A' extends directly from the end of polymer segment A to form an A-A' polymer chain, two of such chains extending from the difunctional initiator. A similar situation may be represented as (I3)(AB)3, where I3-A may also be represented herein as M, where the initiator (I3) has three initiation sites, a polymer segment A extends directly from I (forming M), and a polymer segment A' extends directly from the end of polymer segment A to form an A-A' polymer chain, three of such chains extending from the initiator. When the initiator is difunctional, the resulting copolymer may be described as linear or biaxial, when the initiator is trifunctional, the resulting copolymer may be described as triaxial, and when the initiator is tetrafunctional, the resulting copolymer may be described as tetraaxial. Such copolymers may be collectively referred to as segmented copolymers, with polymer chain A being referred to as the mid-block or mid-segment, and polymer chain A' being referred to as the end-block or end-segment or end-graft. Any one or more of biaxial, triaxial, and tetraaxial polymers may be referred to herein as multiaxial polymers.

[0014] Lactide (LAC)-containing copolymers In one embodiment, the copolymer comprises repeat units of lactic acid or lactide (collectively LAC) monomer and one or more additional monomers, which may be selected from glycolic acid or glycolide (GLY), ε-caprolactone (CAP), and trimethylene carbonate (TMC). For example, the copolymer may include repeat units of LAC and GLY, and optionally no other monomers. In another embodiment, the copolymer may include repeat units of LAC and TMC, and optionally no other monomers. In a further embodiment, the copolymer may include repeat units of LAC and CAP, and optionally no other monomers. As another example, in one embodiment, the copolymer is a linear copolymer comprising repeating units of LAC, TMC, and CAP. In one embodiment, the linear copolymer comprises 70-80% by weight LAC, 10-20% by weight TMC, and 10-20% by weight CAP, each weight percent being based on the total weight of LAC, TMC, and CAP in the copolymer, e.g., 70-75% LAC, 10-15% TMC, and 10-15% CAP. In another example, the copolymer is a triaxial copolymer comprising repeating units of LAC, TMC, and CAP. In one embodiment, the triaxial copolymer comprises 70-80% by weight LAC, 10-20% by weight TMC, and 10-20% by weight CAP, each weight percent being based on the total weight of LAC, TMC, and CAP in the copolymer, e.g., 70-75% by weight LAC, 10-15% by weight TMC, and 10-15% CAP. As another example, in one embodiment, the copolymer is a linear copolymer compositionally described as 30-50 / 20-40 / 20-30 / 1-10 LAC / CAP / TMC / GLY, e.g., 40 / 30 / 26 / 4 LAC / CAP / TMC / GLY.

[0015] Glycolide (GLY)-containing copolymers In one embodiment, the copolymer comprises repeat units of glycolic acid or glycolide monomer and one or more additional monomers, which may be selected from lactic acid or lactide (LAC), ε-caprolactone (CAP), and trimethylene carbonate (TMC). For example, a copolymer may contain repeating units of GLY and LAC, and optionally no other monomers. As another example, the copolymer may include repeat units of GLY and TMC, and may optionally include no other monomers. As another example, the copolymer may include repeat units of GLY and CAP, and may optionally include no other monomers. For example, the copolymer may be a linear copolymer, and may include only 70-99% by weight GLY and 30-1% by weight CAP as monomers, with exemplary copolymers having 90-97% by weight GLY and 10-3% by weight CAP, or 70-80% by weight GLY and 30-20% by weight CAP. In another embodiment, the copolymer may be a triaxial copolymer, and may include only 70-99% by weight GLY and 30-1% by weight CAP as monomers, with exemplary copolymers having 90-97% by weight GLY and 10-3% by weight CAP, or 70-80% by weight GLY and 30-20% by weight CAP. In one embodiment, the initiator is polyethylene succinate, and in another embodiment, the initiator is trimethylene carbonate. As another example, the copolymer is a linear copolymer comprising repeating units of GLY, TMC, and CAP. In one embodiment, the linear copolymer comprises 50-60% by weight GLY, 20-30% by weight TMC, and 15-25% by weight CAP, each weight percentage being based on the total weight of GLY, TMC, and CAP in the copolymer, e.g., 50-55% GLY, 20-25% TMC, and 20-25% CAP. In another example, the copolymer is a triaxial copolymer comprising repeating units of GLY, TMC, and CAP. In one embodiment, the triaxial copolymer comprises 50-60% by weight GLY, 20-30% by weight TMC, and 15-25% by weight CAP, each weight percentage being based on the total weight of GLY, TMC, and CAP in the copolymer, e.g., 50-55% GLY, 20-25% TMC, and 20-25% CAP.

[0016] ε-caprolactone (CAP)-containing copolymer In one embodiment, the copolymer comprises repeat units of an ε-caprolactone monomer and one or more additional monomers, which may be selected from lactic acid / lactide (LAC), glycolic acid / glycolide (GLY), and trimethylene carbonate (TMC).

[0017] Trimethylene carbonate (TMC)-containing copolymer In one embodiment, the copolymer comprises repeat units of trimethylene carbonate (TMC) monomer and one or more additional monomers, which may be selected from lactic acid / lactide (LAC), glycolic acid / glycolide (GLY), and ε-caprolactone (CAP).

[0018] Dioxanone-containing copolymers In one embodiment, the copolymer includes repeat units of dioxanone monomers.

[0019] Lactone In one embodiment, the copolymer comprises repeat units of δ-valerolactone monomers. In one embodiment, the copolymer comprises repeat units of ε-decalactone monomers. In one embodiment, the copolymer comprises repeat units selected from δ-valerolactone and ε-decalactone monomers.

[0020] Linear Copolymer In one embodiment, the polymer is a linear polymer, which refers to a polymer with no branches in the backbone. As described herein, linear polymers may be described as M(B)2 or (I2)(A-A')2, where A and A' refer to various polymers (including copolymers), such as polyesters. When a polymer has the (I2)(A-A')2 structure, A may be referred to as the central block and A' may be referred to as the end grafts, and together A-A' are the arms of a linear polymer. However, linear polymers may instead be described as (I2)(A)2, where A refers to a polyester. In describing the composition of the arms of a linear copolymer, a convenient nomenclature for the arms is the residue description wt%1 / wt%2 monomer1 / monomer2. For example, a linear polymer represented by the residue description 65 / 35 GLY / TMC would indicate that each of the two arms is a copolymer formed of 65% GLY and 35% TMC residues by weight, with the weight percentage values ​​being based on the total weight of GLY and TMC in the polymer. By analogy, the residue description 93 / 5 / 2 GLY / CAP / TMC would indicate that each of the two arms is a copolymer formed of 93% GLY, 5% CAP, and 2% TMC residues by weight, with the weight percentage values ​​being based on the total weight of GLY, CAP, and TMC in the polymer. When a linear polymer has both a central block and terminal grafts, such a polymer may be designated as: central block wt% residue description; terminal graft wt% residue description. In this case, the wt% value indicates the ratio of the total residue mass present in the central block to the total mass of residues present in the polymer. For example, a linear polymer designated as central block 10% 85 / 15 CAP / LAC; terminal graft 94 / 9 LAC / GLY indicates that 10% of the total residue mass is present in the central block, and therefore 90% of the total residue mass is present in the terminal blocks. The central block contains 85% CAP residues and 15% LAC residues by weight, based on the total mass of residues present in the central block of the polymer. The terminal graft contains 94% LAC residues and 6% GLY residues by weight, based on the total mass of residues present in the arms of the polymer.

[0021] Below are additional exemplary linear polymers from which the monofilaments of the present disclosure may be made. In one embodiment, a linear polymer may be described as follows: 70~80 / 10~20 / 5~15 LAC / TMC / CAP; or 71~79 / 11~19 / 6~14 LAC / TMC / CAP; or 72~78 / 12~18 / 7~13 LAC / TMC / CAP; or 72~76 / 13~17 / 9~13 LAC / TMC / CAP.

[0022] In one embodiment, a linear polymer may be described as follows: Central block 5-15% TMC; end grafts 90-99 / 1-10 LAC / CAP; or Central block 5-7% TMC; end grafts 90-99 / 1-10 LAC / CAP; or Central block 6-8% TMC; end grafts 90-99 / 1-10 LAC / CAP; or Central block 7-9% TMC; end grafts 90-99 / 1-10 LAC / CAP; or Central block 8-10% TMC; end grafts 90-99 / 1-10 LAC / CAP; or Central block 9-11% TMC; end grafts 90-99 / 1-10 LAC / CAP; or Central block 10-12% TMC; end grafts 90-99 / 1-10 LAC / CAP; or Central block 11-13% TMC; end grafts 80-90 / 10-20 CAP / LAC; or Central block 12-14% TMC; end grafts 80-90 / 10-20 CAP / LAC; or Central block 13-15% TMC; end grafts 80-90 / 10-20 CAP / LAC; In any of the above, the end graft 90-99 / 1-10 LAC / CAP may optionally be replaced with an end graft 90-95 / 5-10 LAC / CAP.

[0023] In one embodiment, a linear polymer may be described as follows: Central block 5-15% PEG; end grafts 85-95 / 5-15 LAC / GLY; or Center block 5-7% PEG; end grafts 85-95 / 5-15 LAC / GLY; or Center block 6-8% PEG; end grafts 85-95 / 5-15 LAC / GLY; or Center block 7-9% PEG; end grafts 85-95 / 5-15 LAC / GLY; or Central block 8-10% PEG; end grafts 85-95 / 5-15 LAC / GLY; or Central block 9-11% PEG; end grafts 85-95 / 5-15 LAC / GLY; or Center block 10-12% PEG; end grafts 85-95 / 5-15 LAC / GLY; or Central block 11-13% PEG; end grafts 85-95 / 5-15 LAC / GLY; or Center block 12-14% PEG; end grafts 85-95 / 5-15 LAC / GLY; or Central block 13-15% PEG; end grafts 85-95 / 5-15 LAC / GLY; In any of the above, PEG refers to polyethylene glycol, and independently, 85-95 / 5-15 LAC / GLY may optionally be replaced with 88-92 / 8-12 LAC / GLY.

[0024] In one embodiment, a linear polymer may be described as follows: Center block 1-10% PEG; graft 1 1-5% TMC; end grafts 90-99% PDO; or Center block 1-3% PEG; graft 1 1-5% TMC; end grafts 90-99% PDO; or Center block 2-4% PEG; graft 1 1-5% TMC; end grafts 90-99% PDO; or Center block 3-5% PEG; graft 1 1-5% TMC; end grafts 90-99% PDO; or Center block 4-6% PEG; graft 1 1-5% TMC; end grafts 90-99% PDO; or Center block 5-7% PEG; graft 1 1-5% TMC; end grafts 90-99% PDO; or Center block 6-8% PEG; graft 1 1-5% TMC; end grafts 90-99% PDO; or Center block 7-9% PEG; graft 1 1-5% TMC; end grafts 90-99% PDO; or Central block 8-10% PEG; graft 1 1-5% TMC; end grafts 90-99% PDO; In any of the above, PEG refers to polyethylene glycol; independently, graft 1 1-5% TMC refers to graft 1 1% TMC; and independently, end graft 90-99% PDO refers to end graft 92-94% PDO.

[0025] In one embodiment, a linear polymer may be described as follows: Center block 1-10% PEG; end grafts 85-95 / 5-15 GLY / TMC; or central block 1-3% PEG; end grafts 85-95 / 5-15 GLY / TMC; or Center block 2-4% PEG; end grafts 85-95 / 5-15 GLY / TMC; or Center block 3-5% PEG; end grafts 85-95 / 5-15 GLY / TMC; or Center block 4-6% PEG; end grafts 85-95 / 5-15 GLY / TMC; or Center block 5-7% PEG; end grafts 85-95 / 5-15 GLY / TMC; or Center block 6-8% PEG; end grafts 85-95 / 5-15 GLY / TMC; or Center block 7-9% PEG; end grafts 85-95 / 5-15 GLY / TMC; or Central block 8-10% PEG; end grafts 85-95 / 5-15 GLY / TMC; In any of the above, PEG refers to polyethylene glycol and, independently, the end grafts 85-95 / 5-15 GLY / TMC refer to 88-92 / 8-12 GLY / TMC.

[0026] In one embodiment, a linear polymer may be described as follows: 85~95 / 5~15 LAC / TMC; or 86~94 / 6~14 LAC / TMC; or 87~93 / 7~13 LAC / TMC; or 88~92 / 8~12 LAC / TMC; or 89~91 / 9~11 LAC / TMC.

[0027] In one embodiment, a linear polymer may be described as follows: 60~70 / 20~30 / 1~10 GLY / PPG / PEG; or 61-69 / 22-30 / 2-8 GLY / PPG / PEG; or 62~68 / 24~30 / 3~7 GLY / PPG / PEG; Above, independently at each occurrence, PPG refers to polypropylene glycol and PEG refers to polyethylene glycol. In one embodiment, a linear polymer may be described as follows: 70~90 / 10~30 PDO / PEG; or 72~88 / 12~28 PDO / PEG; or 74~86 / 14~26 PDO / PEG; or 76~84 / 16~24 PDO / PEG; or 78~82 / 18~22 PDO / PEG; In the above, PEG refers to polyethylene glycol.

[0028] In one embodiment, a linear polymer may be described as follows: 65~75 / 15~25 / 5~15 / 1~10 LAC / PEG / TMC / CAP; or 66-74 / 16-24 / 6-14 / 1-8 LAC / PEG / TMC / CAP; or 67-73 / 17-23 / 7-13 / 1-6 LAC / PEG / TMC / CAP; or 68~72 / 18~22 / 8~12 / 1~4 LAC / PEG / TMC / CAP; In the above, PEG refers to polyethylene glycol.

[0029] In one embodiment, a linear polymer may be described as follows: 85~95 / 5~15 / 1~10 LAC / GLY / PEG; or 86~94 / 6~14 / 2~9 LAC / GLY / PEG; or 87~93 / 7~13 / 3~8 LAC / GLY / PEG; or 85~91 / 5~10 / 2~6 LAC / GLY / PEG; In the above, PEG refers to polyethylene glycol.

[0030] Triaxial Copolymer In one embodiment, the polymer is a triaxial polymer, which refers to a polymer having three arms radiating from a central core, and may be represented herein as M(B)3. As described herein, the triaxial polymer may be designated as (I3)(A-A')3, where A and A' refer to various polymers or copolymers, such as polyesters. When the polymer has an (I3)(A-A')3 structure, A may be referred to as the central block and A' may be referred to as the end graft. However, the triaxial polymer may instead be described as (I3)(A)3, where A refers to the polymer, such as polyester. In describing the composition of the arms of a triaxial copolymer, a convenient nomenclature for the arms is the residue description wt%1 / wt%2 monomer1 / monomer2. For example, a triaxial polymer represented by the residue description 65 / 35 GLY / TMC would indicate that each of the three arms is a copolymer formed of 65 wt% GLY and 35 wt% TMC residues, with the wt% values ​​being based on the total mass of GLY and TMC in the polymer. By analogy, the residue description 93 / 5 / 2 GLY / CAP / TMC would indicate that each of the three arms is a copolymer formed of 93 wt% GLY, 5 wt% CAP, and 2 wt% TMC residues, with the wt% values ​​being based on the total mass of GLY, CAP, and TMC in the polymer. When a triaxial polymer has both a central block and terminal grafts, such a polymer may be designated as: central block wt% residue description; terminal graft wt% residue description. In this case, the wt% values ​​indicate the ratio of the total residue mass present in the central block to the total mass of residues present in the polymer. For example, a triaxial polymer designated as central block 10% 85 / 15 CAP / LAC; terminal graft 94 / 9 LAC / GLY indicates that 10% of the total residue mass is present in the central block, and therefore 90% of the total residue mass is present in the terminal blocks. The central block contains 85% CAP residues and 15% LAC residues by weight, based on the total mass of residues present in the central block of the polymer. The terminal graft contains 94% LAC residues and 6% GLY residues by weight, based on the total mass of residues present in the arms of the polymer.

[0031] Below are additional exemplary triaxial polymers that may be used to make the monofilaments described herein. In one embodiment, the triaxial polymer may be described as follows: 50~60 / 20~30 / 15~25 GLY / TMC / CAP; or 51~59 / 21~29 / 16~24 GLY / TMC / CAP; or 52~58 / 22~28 / 17~23 GLY / TMC / CAP; or 53~57 / 23~27 / 18~22 GLY / TMC / CAP.

[0032] In one embodiment, the triaxial polymer may be described as follows: central block 1-10% polyethylene succinate; end grafts 70-80 / 20-30 GLY / CAP; or central block 1-3% polyethylene succinate; end grafts 70-80 / 20-30 GLY / CAP; or central block 2-4% polyethylene succinate; end grafts 70-80 / 20-30 GLY / CAP; or central block 3-5% polyethylene succinate; end grafts 70-80 / 20-30 GLY / CAP; or central block 4-6% polyethylene succinate; end grafts 70-80 / 20-30 GLY / CAP; or central block 5-7% polyethylene succinate; end grafts 70-80 / 20-30 GLY / CAP; or central block 6-8% polyethylene succinate; end grafts 70-80 / 20-30 GLY / CAP; or central block 7-9% polyethylene succinate; end grafts 70-80 / 20-30 GLY / CAP; or Central block 8-10% polyethylene succinate; end grafts 70-80 / 20-30 GLY / CAP; In any of the above, 70-80 / 20-30 GLY / CAP may optionally be replaced with 74-78 / 22-26 GLY / CAP.

[0033] In one embodiment, the triaxial polymer may be described as follows: Central block 1-10% TMC; end grafts 90-99 / 1-10 GLY / CAP; or Central block 1-3% TMC; end grafts 90-99 / 1-10 GLY / CAP; or Central block 2-4% TMC; end grafts 90-99 / 1-10 GLY / CAP; or Central block 3-5% TMC; end grafts 90-99 / 1-10 GLY / CAP; or Central block 4-6% TMC; end grafts 90-99 / 1-10 GLY / CAP; or Central block 5-7% TMC; end grafts 90-99 / 1-10 GLY / CAP; or Central block 6-8% TMC; end grafts 90-99 / 1-10 GLY / CAP; or Central block 7-9% TMC; end grafts 90-99 / 1-10 GLY / CAP; or Central block 8-10% TMC; end grafts 90-99 / 1-10 GLY / CAP; In any of the above, 90-99 / 1-10 GLY / CAP may optionally be replaced by 93-97 / 3-7 GLY / CAP; or 90-95 / 5-10 GLY / CAP.

[0034] In one embodiment, the triaxial polymer may be described as follows: Central block 1-10% TMC; end grafts 70-80 / 20-30 GLY / CAP; or Central block 1-3% TMC; end grafts 70-80 / 20-30 GLY / CAP; or Central block 2-4% TMC; end grafts 70-80 / 20-30 GLY / CAP; or Central block 3-5% TMC; end grafts 70-80 / 20-30 GLY / CAP; or Central block 4-6% TMC; end grafts 70-80 / 20-30 GLY / CAP; or Central block 5-7% TMC; end grafts 70-80 / 20-30 GLY / CAP; or Central block 6-8% TMC; end grafts 70-80 / 20-30 GLY / CAP; or Central block 7-9% TMC; end grafts 70-80 / 20-30 GLY / CAP; or Central block 8-10% TMC; end grafts 70-80 / 20-30 GLY / CAP; In any of the above, the 70-80 / 20-30 GLY / CAP may optionally be replaced with 72 / 28 GLY / CAP.

[0035] In one embodiment, the triaxial polymer may be described as follows: Central block 1-10% TMC; end grafts 80-99 / 1-20 GLY / TMC; or Central block 1-3% TMC; end grafts 80-99 / 1-20 GLY / TMC; or central block 2-4% TMC; end grafts 80-99 / 1-20 GLY / TMC; or Central block 3-5% TMC; end grafts 80-99 / 1-20 GLY / TMC; or Central block 4-6% TMC; end grafts 80-99 / 1-20 GLY / TMC; or Central block 5-7% TMC; end grafts 80-99 / 1-20 GLY / TMC; or Central block 6-8% TMC; end grafts 80-99 / 1-20 GLY / TMC; or Central block 7-9% TMC; end grafts 80-99 / 1-20 GLY / TMC; or Central block 8-10% TMC; end grafts 80-99 / 1-20 GLY / TMC; In any of the above, the terminal graft 80-99 / 1-20 GLY / TMC may optionally be replaced with a terminal graft 88-92 / 8-12 GLY / TMC.

[0036] In one embodiment, the triaxial polymer may be described as follows: Central block 1-10% TMC; end grafts 85-95 / 5-15 GLY / TMC; or Central block 1-3% TMC; end grafts 85-95 / 5-15 GLY / TMC; or Central block 2-4% TMC; end grafts 85-95 / 5-15 GLY / TMC; or Central block 3-5% TMC; end grafts 85-95 / 5-15 GLY / TMC; or Central block 4-6% TMC; end grafts 85-95 / 5-15 GLY / TMC; or Central block 5-7% TMC; end grafts 85-95 / 5-15 GLY / TMC; or Central block 6-8% TMC; end grafts 85-95 / 5-15 GLY / TMC; or Central block 7-9% TMC; end grafts 85-95 / 5-15 GLY / TMC; or Central block 8-10% TMC; end grafts 85-95 / 5-15 GLY / TMC; In any of the above, the terminal graft 85-95 / 5-15 GLY / TMC may optionally be replaced with a terminal graft 88-92 / 8-12 GLY / TMC.

[0037] In one embodiment, the triaxial polymer may be described as follows: 1~10 / 15~25 / 20~30 / 45~55 GLY / CAP / TMC / GLY; or 2~9 / 16~24 / 21~29 / 46~54 GLY / CAP / TMC / GLY; or 3~8 / 16~23 / 21~28 / 48~54 GLY / CAP / TMC / GLY; or 3~7 / 17~21 / 22~26 / 50~54 GLY / CAP / TMC / GLY.

[0038] In one embodiment, the triaxial polymer may be described as follows: Central block 5-15% 80-90 / 10-20 CAP / LAC; end grafts 90-99 / 1-10 LAC / GLY; or Central block 5-7% 80-90 / 10-20 CAP / LAC; end grafts 90-99 / 1-10 LAC / GLY; or Central block 6-8% 80-90 / 10-20 CAP / LAC; end grafts 90-99 / 1-10 LAC / GLY; or Central block 7-9% 80-90 / 10-20 CAP / LAC; end grafts 90-99 / 1-10 LAC / GLY; or Central block 8-10% 80-90 / 10-20 CAP / LAC; end grafts 90-99 / 1-10 LAC / GLY; or Central block 9-11% 80-90 / 10-20 CAP / LAC; end grafts 90-99 / 1-10 LAC / GLY; or Central block 10-12% 80-90 / 10-20 CAP / LAC; end grafts 90-99 / 1-10 LAC / GLY; or Central block 11-13% 80-90 / 10-20 CAP / LAC; end grafts 90-99 / 1-10 LAC / GLY; or Central block 12-14% 80-90 / 10-20 CAP / LAC; end grafts 90-99 / 1-10 LAC / GLY; or Central block 13-15% 80-90 / 10-20 CAP / LAC; terminal graft 90-99 / 1-10 LAC / GLY; In any of the above, the 80-90 / 10-20 CAP / LAC may optionally be replaced with 83-87 / 13-17 CAP / LAC, and independently, the terminal graft 90-99 / 1-10 LAC / GLY may optionally be replaced with 92-96 / 7-11 LAC / GLY.

[0039] In one embodiment, the triaxial polymer may be described as follows: Center block 15-25% PEG; graft 1 1-5% TMC; end grafts 90-99 / 1-10 LAC / GLY; or Center block 15-17% PEG; graft 1 1-5% TMC; end grafts 90-99 / 1-10 LAC / GLY; or Center block 16-18% PEG; graft 1 1-5% TMC; end grafts 90-99 / 1-10 LAC / GLY; or Center block 17-19% PEG; graft 1 1-5% TMC; end grafts 90-99 / 1-10 LAC / GLY; or Center block 18-20% PEG; graft 1 1-5% TMC; end grafts 90-99 / 1-10 LAC / GLY; or Center block 19-21% PEG; graft 1 1-5% TMC; end grafts 90-99 / 1-10 LAC / GLY; or Center block 20-22% PEG; graft 1 1-5% TMC; end grafts 90-99 / 1-10 LAC / GLY; or Center block 21-23% PEG; graft 1 1-5% TMC; end grafts 90-99 / 1-10 LAC / GLY; or Center block 22-24% PEG; graft 1 1-5% TMC; end grafts 90-99 / 1-10 LAC / GLY; or Center block 23-25% PEG; graft 1 1-5% TMC; end grafts 90-99 / 1-10 LAC / GLY; or In any of the above, PEG refers to polyethylene glycol, independently, graft 1 1-5% TMC refers to graft 1 1-2% TMC, and independently, end graft 90-99 / 1-10 LAC / GLY refers to end graft 90-94 / 6-10 LAC / GLY.

[0040] In one embodiment, the triaxial polymer may be described as follows: 65~75 / 25~35 / 1~10 GLY / CAP / TMC; or 66~74 / 26~34 / 2~9 GLY / CAP / TMC; or 67~73 / 27~33 / 3~8 GLY / CAP / TMC; or 68~72 / 28~32 / 4~7 GLY / CAP / TMC; or 69~71 / 29~31 / 5~6 GLY / CAP / TMC.

[0041] In one embodiment, the triaxial polymer may be described as follows: 60~70 / 30~40 GLY / TMC; or 61~69 / 31~39 GLY / TMC; or 62~68 / 32~38 GLY / TMC; or 63~67 / 33~37 GLY / TMC; or 64~66 / 34~36 GLY / TMC.

[0042] In one embodiment, the triaxial polymer may be described as follows: 90~99 / 1~10 / 1~10 GLY / CAP / TMC; or 91~98 / 2~9 / 2~9 GLY / CAP / TMC; or 92~97 / 3~8 / 3~8 GLY / CAP / TMC; or 93~96 / 4~7 / 4~7 GLY / CAP / TMC.

[0043] In one embodiment, the triaxial polymer may be described as follows: 80~90 / 1~10 / 1~10 GLY / TMC / CAP; or 81~89 / 2~10 / 2~9 GLY / TMC / CAP; or 82~88 / 3~10 / 3~8 GLY / TMC / CAP; or 83~87 / 4~10 / 4~7 GLY / TMC / CAP.

[0044] In one embodiment, the triaxial polymer may be described as follows: 65~75 / 25~35 / 1~10 GLY / TMC / polypropylene succinate; or 66~74 / 25~33 / 1~8 GLY / TMC / polypropylene succinate; or 67~73 / 25~30 / 1~5 GLY / TMC / Polypropylene succinate.

[0045] In one embodiment, the triaxial polymer may be described as follows: 30~40 / 30~40 / 15~25 / 10~20 CAP / LAC / GLY / TMC; or 31~39 / 31~39 / 15~23 / 11~19 CAP / LAC / GLY / TMC; or 32~38 / 32~38 / 15~21 / 12~18 CAP / LAC / GLY / TMC; or 32~37 / 32~37 / 15~19 / 12~16 CAP / LAC / GLY / TMC.

[0046] In one embodiment, the triaxial polymer may be described as follows: 35~45 / 35~45 / 25~35 LAC / CAP / TMC; or 36~44 / 36~44 / 25~34 LAC / CAP / TMC; or 37~43 / 36~43 / 25~33 LAC / CAP / TMC; or 37-42 / 36-42 / 25-32 LAC / CAP / TMC; or 37~41 / 36~41 / 25~31 LAC / CAP / TMC.

[0047] In one embodiment, the triaxial polymer may be described as follows: 35~45 / 25~35 / 20~30 / 1~10 LAC / CAP / TMC / GLY; or 36~44 / 26~34 / 21~29 / 1~9 LAC / CAP / TMC / GLY; or 37~43 / 27~33 / 22~28 / 1~8 LAC / CAP / TMC / GLY; or 38~42 / 28~32 / 24~27 / 1~6 LAC / CAP / TMC / GLY.

[0048] In one embodiment, the present disclosure provides a monofilament fiber comprising a multiaxial polymer of formula M(B)2 or M(B)3. Optionally, the multiaxial polymer has formula M(B)2. Optionally, the multiaxial polymer has formula M(B)3. The M portion of the multiaxial polymer may be referred to as a prepolymer or midblock or central block, while the B portion may be referred to as an arm or end graft. Optionally, the multiaxial polymer of formula M(B)2 or M(B)3 is formed by first forming the midblock M, i.e., a prepolymer, and then polymerizing or end grafting monomers onto M to provide M(B)2 or M(B)3. Multiaxial polymers are advantageously used to prepare monofilaments of the present disclosure, since the properties of M and B may be independently selected based on the selection of the monomer or monomers used to prepare M and the selection of the monomer or monomers used to prepare B. In one embodiment, the selection of the monomers used to prepare M is different from the selection of the monomers used to prepare B, and therefore the properties of M are different from the properties of B.

[0049] The M portion of the multiaxial polymer, which may also be referred to as the prepolymer portion of the multiaxial polymer of formula M(B)2 or M(B)3, comprises a plurality of repeat units that are the polymerization product of one or both of trimethylene carbonate (TMC) and ε-caprolactone (CAP). That is, trimethylene carbonate and ε-caprolactone are the monomers that polymerize to form M. Optionally, these two monomers are copolymerized such that the repeat units in M ​​are the polymerization products (also referred to as residues) of trimethylene carbonate and the polymerization products or residues of ε-caprolactone. In one embodiment, on a molar basis, the majority of the repeat units in M ​​are residues of trimethylene carbonate and / or ε-caprolactone. In other embodiments, more than 50 mol%, or at least 50 mol%, or at least 55 mol%, or at least 60 mol%, or at least 65 mol%, or at least 70 mol%, or at least 75 mol%, or at least 80 mol%, or at least 85 mol%, or at least 90 mol%, or at least 95 mol% of the repeating units in M ​​are residues of trimethylene carbonate and / or ε-caprolactone. Any two of these mol% values ​​may be combined in the present disclosure to form a range. For example, 80 mol% and 90 mol% may be combined to form a range of 80-90 mol%. As stated above, in one embodiment, the specified mol% is formed from a mixture of CAP and TMC residues. That is, M is a copolymer rather than a homopolymer of TMC and CAP residues, e.g., 80-90 mol% of the repeating units in M ​​may be residues of both TMC and CAP.

[0050] In M, as described above, the majority of the repeat units may be derived from TMC and / or CAP monomers, and in any embodiment, not all of the repeat units in M ​​are derived from TMC or CAP. In one embodiment, the majority of the repeat units are derived from TMC and / or CAP, but at least 3 mol% of the repeat units are not polymerization products of TMC or CAP, and in other embodiments, at least 5 mol%, or at least 8 mol%, or at least 10 mol%, or at least 15 mol% of the repeat units are not derived from TMC or CAP, but are optionally derived from one or more of glycolide (GLY) and lactide (LAC). For example, in one embodiment, 80-95 mol% of the repeat units in M ​​are derived from TMC and / or CAP, and the remaining 5-20 mol% are derived from LAC and / or GLY. In one embodiment, 85-95 mol% of the repeat units in M ​​are derived from TMC and / or CAP, and the remaining 5-15 mol% are derived from LAC and / or GLY. In one embodiment, 85-90 mol % of the repeating units in M ​​are derived from TMC and / or CAP, and the remaining 5-10 mol % are derived from LAC and / or GLY. In one embodiment, 1-20 mol % of the repeating units in M ​​are a polymerization product of at least one of glycolide and lactide. In one embodiment, at least 70 mol% of the repeating units in M ​​are the polymerization product of at least one of trimethylene carbonate and ε-caprolactone. In another embodiment, M is a copolymer since at least 70 mol% of the repeating units in M ​​are the copolymerization product of both trimethylene carbonate and ε-caprolactone. Optionally, the remaining repeating units in M ​​are the residues from the polymerization of one or both of glycolide and lactide. In one embodiment, M is a copolymer formed from the residues of monomers selected from TMC and / or CAP and further comprising at least one of LAC and GLY. For example, M can be a copolymer of repeating units derived from TMC, CAP, and LAC. As another example, M can be a copolymer of repeating units derived from TMC, CAP, and GLY. As another example, M can be a copolymer of repeating units derived from TMC and LAC. As another example, M can be a copolymer of repeating units derived from TMC and GLY. As another example, M can be a copolymer of repeating units derived from CAP and LAC. As another example, M can be a copolymer of CAP and GLY repeating units.

[0051] The B portion of the polyaxial polymer, which may also be referred to as the arms or end graft portion of the polyaxial polymer of formula M(B)2 or M(B)3, comprises a plurality of repeat units that are the polymerization product of one or both of glycolide (GLY) and lactide (LAC). That is, GLY and LAC are monomers that are polymerized to form B. Optionally, these two monomers are copolymerized such that the repeat units in B are the polymerization product (also referred to as the residue) of GLY and the polymerization product or residue of LAC. In one embodiment, on a molar basis, the majority of the repeat units in B are residues of LAC and / or GLY. In other embodiments, at least 55 mol%, or at least 60 mol%, or at least 65 mol%, or at least 70 mol%, or at least 75 mol%, or at least 80 mol%, or at least 85 mol%, or at least 90 mol%, or at least 95 mol% of the repeat units in B are residues of GLY and / or LAC. In the present disclosure, any two of these mole percent values ​​may be combined to form a range. For example, 80 mol % and 90 mol % may be combined to form a range of 80-90 mol %. As noted above, in one embodiment, the specified mol % is formed from a mixture of LAC and GLY residues. That is, B is a copolymer rather than a homopolymer of GLY and LAC residues, e.g., 80-90 mol % of the repeat units in B may be residues of both GLY and LAC. However, in one embodiment, only polymerized residues of LAC are present in B, and in another embodiment, only polymerized residues of GLY are present in B.

[0052] In B, as described above, the majority of the repeat units may be derived from GLY and / or LAC monomers, and in any embodiment, not all of the repeat units in B are derived from GLY or LAC. In one embodiment, the majority of the repeat units are derived from LAC and / or GLY, but at least 3 mol% of the repeat units are not polymerization products of GLY or LAC, and in other embodiments, at least 5 mol%, or at least 8 mol%, or at least 10 mol%, or at least 15 mol% of the repeat units are not derived from LAC or GLY, but are optionally derived from one or more of trimethylene carbonate (TMC) and ε-caprolactone (CAP). For example, in one embodiment, 80-95 mol% of the repeat units in B are derived from GLY and / or LAC, and the remaining 5-20 mol% are derived from TMC and / or CAP. In one embodiment, 85-95 mol% of the repeat units in B are derived from GLY and / or LAC, and the remaining 5-15 mol% are derived from TMC and / or CAP. In one embodiment, 85-90 mol % of the repeating units in B are derived from GLY and / or LAC, and the remaining 5-10 mol % are derived from TMC and / or CAP. In one embodiment, 1-20 mol % of the repeating units in B are a polymerization product of at least one of trimethylene carbonate and ε-caprolactone. In one embodiment, at least 70 mol % of the repeating units in B are the polymerization product of at least one of lactide and glycolide. Optionally, the polymerization product of only one of LAC and GLY is present in B. In another embodiment, at least 70 mol % of the repeating units in B are the copolymerization product of both GLY and LAC, such that B is a copolymer. Optionally, the remaining repeating units in B are the residues from the polymerization of one or both of TMC and CAP. In one embodiment, B is a copolymer formed from residues of TMC and GLY. In one embodiment, B is a copolymer formed from residues of TMC and LAC. In one embodiment, B is a copolymer formed from residues of CAP and GLY. In one embodiment, B is a copolymer formed from residues of CAP and LAC.

[0053] In one embodiment, the monofilament is made from a multiaxial polymer as described herein, the polymer being in semi-crystalline form. Advantageously, the polymer is somewhat crystalline so that when exposed to high temperatures in the print head of an additive manufacturing printer, converting the amorphous polymer to a crystalline polymer does not consume excessive heat in the print head. That is, if the polymer is already in semi-crystalline form when it enters the print head, less heat in the print head is consumed in converting the amorphous polymer to a crystalline polymer. Since print heads usually have limited thermal energy, if too much print head heat is required to convert the amorphous polymer to a crystalline polymer, there will not be enough heat left in the print head to convert it to the molten form required to deposit the monofilament and form the printed part. In one embodiment, the multiaxial polymers M(B)2 and M(B)3 of the present disclosure in monofilament form are semi-crystalline.

[0054] Optionally, B comprises a majority of the mass of the multiaxial polymer and M comprises a minor portion of the mass of the multiaxial polymer. For example, in one embodiment, M comprises less than 50% by mass of the multiaxial polymer and B comprises more than 50% by mass of the multiaxial polymer. In one embodiment, M comprises at least 10% by mass or at least 15% by mass, but less than 50% by mass of the multiaxial polymer. In one embodiment, B comprises no more than 90% by mass or no more than 85% by mass, but more than 50% by mass of the multiaxial polymer. Thus, in one embodiment, the disclosure provides a monofilament fiber comprising a multiaxial polymer of formula M(B)2 or M(B)3, where M comprises repeat units and B also comprises repeat units, where a majority of the repeat units in M ​​are polymerized residues of TMC and / or CAP and a minority of the repeat units in M ​​are polymerized residues of CAP and / or GLY, whereas a majority of the repeat units in B are polymerized residues of GLY and / or LAC and a minority of the repeat units in B are polymerized residues of TMC and / or CAP. Thus, the midblock M has properties that are primarily due to the presence of residues of TMC and / or CAP and influenced by minor amounts of residues of LAC and / or GLY, whereas the end graft B has properties that are primarily due to the presence of residues of LAC and / or GLY and influenced by minor amounts of residues of TMC and / or CAP.

[0055] The present disclosure provides monofilament fibers comprising these multiaxial polymers of formula M(B)2 or M(B)3, as well as assemblies and kits comprising the monofilament fibers, and their use in additive printing. For example, the present disclosure provides the following exemplary numbered embodiments: 1) a kit including an assembly located within a pouch, the assembly including a monofilament fiber wound on a spool, the monofilament fiber including a multiaxial polymer of formula M(B)2 or M(B)3; aM is a homopolymer or copolymer and comprises a plurality of repeating units, wherein a majority, e.g., at least 70 mole %, of the repeating units in M ​​are the polymerization product of at least one of trimethylene carbonate and ε-caprolactone, and optionally, M is a copolymerization product of at least one of trimethylene carbonate and ε-caprolactone with at least one of lactide and glycolide; and bB comprises a plurality of repeating units, and a majority, e.g., at least 70 mol %, of the repeating units in B are the polymerization product of at least one of glycolide and lactide. kit. 2) The kit of embodiment 1, wherein the spool is stable to a temperature of at least 90°C. 3) The pouch has a moisture vapor transmission rate (MVTR) of 0.002g / 100in 2 3. The kit of embodiment 1 or 2, wherein the administration period is 1-24 h. 4) The kit of embodiment 1 or 2, wherein the pouch is a sealed pouch. 5) The kit of embodiment 1 or 2, wherein the pouch comprises multiple layers, at least one of the multiple layers comprising a metal foil. 6) The kit according to any one of embodiments 1 to 5, wherein the monomer content of the monofilament fiber is less than 2% by mass. 7) The kit according to any one of embodiments 1 to 6, wherein the monofilament fiber is undrawn. 8) The kit according to any one of embodiments 1 to 7, wherein the orientation coefficient of the monofilament fibers is less than 50%. 9) The kit according to any one of embodiments 1 to 8, wherein the monofilament fiber has an essentially circular cross section and a cross-sectional diameter of 1.6 to 3.1 mm. 10) The kit according to any one of embodiments 1 to 9, wherein the mass of the monofilament fiber is 50 to 1,500 g. 11) The kit of any one of embodiments 1 to 10, wherein the monofilament fiber is solid at ambient temperature but fluid at elevated temperature, the fluid having an MFI value of about 2.5 to 30 g / 10 min, and the elevated temperature is an operating temperature of an additive manufacturing process. 12) A kit according to any one of embodiments 1 to 11, wherein the multiaxial polymer is USP Class VI biocompatible. 13) The kit of any one of embodiments 1 to 12, wherein the multiaxial polymer has the formula M(B)3. 14) The kit of any one of embodiments 1 to 12, wherein the multiaxial polymer has the formula M(B)2. 15) The kit according to any one of the preceding embodiments, wherein M represents at least 10% by weight of the polymer. 16) The kit according to any one of the preceding embodiments, wherein B represents at least 50% by weight of the polymer. 17) The kit of any one of embodiments 1 to 16, wherein 1 to 20 mol % of the repeating units in M ​​are a polymerization product of at least one of glycolide and lactide. 18) The kit of any one of embodiments 1 to 17, wherein 1 to 20 mol % of the repeating units in B are a polymerization product of at least one of trimethylene carbonate and ε-caprolactone. 19) The kit of any one of embodiments 1-18, wherein M comprises repeating units of trimethylene carbonate and ε-caprolactone. 20) A kit according to any one of embodiments 1 to 19, further comprising instructions for use of the assembly in an additive manufacturing method. 21) An assembly comprising a monofilament fiber wound on a spool, the monofilament fiber comprising a multiaxial polymer of formula M(B)2 or M(B)3, where M comprises a plurality of repeating units from the polymerization of a first monomer, where at least 70 mol % of the repeating units in M ​​are the polymerization product of at least one of trimethylene carbonate and ε-caprolactone, and B comprises a plurality of repeating units from the polymerization of a second monomer, where at least 70 mol % of the repeating units in B are the polymerization product of at least one of glycolide and lactide. 22) The assembly of embodiment 21, wherein the spool is stable to a temperature of at least 90°C. 23) The assembly of embodiment 21 or 22, wherein the monomer content of the monofilament fiber is less than 2% by weight. 24) The assembly of any one of embodiments 21-23, wherein the monofilament fiber is undrawn. 25) The assembly of any one of embodiments 21 to 24, wherein the orientation coefficient of the monofilament fibers is less than 50%. 26) An assembly according to any one of embodiments 21 to 25, wherein the monofilament fiber has an essentially circular cross section and a cross-sectional diameter of 1.6 to 3.1 mm. 27) The assembly according to any one of embodiments 21 to 26, wherein the mass of the monofilament fiber is 50 to 1,500 g. 28) The assembly of any one of embodiments 21-27, wherein the monofilament fiber is solid at ambient temperature but fluid at an elevated temperature, the fluid having an MFI value of about 2.5-30 g / 10 min, and the elevated temperature is an operating temperature of an additive manufacturing process. 29) An assembly according to any one of embodiments 21 to 28, wherein the multiaxial polymer is USP Class VI biocompatible. 30) An assembly according to any one of embodiments 21 to 29, wherein the multiaxial polymer has the formula M(B)3. 31) An assembly according to any one of embodiments 21 to 29, wherein the multiaxial polymer has the formula M(B)2. 32) The assembly of any one of embodiments 21-31, wherein M comprises at least 10% by weight of the polymer. 33) The assembly of any one of embodiments 21-32, wherein B comprises at least 50% by weight of the polymer. 34) The assembly of any one of embodiments 21-33, wherein 1-20 mol % of the repeating units in M ​​are the polymerization product of at least one of glycolide and lactide. 35) The assembly of any one of embodiments 21-34, wherein 1-20 mol % of the repeating units in B are the polymerization product of at least one of trimethylene carbonate and ε-caprolactone. 36) An assembly of any one of embodiments 21-35, wherein M includes repeating units of trimethylene carbonate and ε-caprolactone. 37) A monofilament fiber comprising a multiaxial polymer of formula M(B)2 or M(B)3, wherein M comprises a plurality of repeat units from the polymerization of a first monomer, where at least 70 mol % of the repeat units in M ​​are the polymerization product of at least one of trimethylene carbonate and ε-caprolactone, and B comprises a plurality of repeat units from the polymerization of a second monomer, where at least 70 mol % of the repeat units in B are the polymerization product of at least one of glycolide and lactide. 38) The monofilament fiber of embodiment 37, having a monomer content of less than 2% by weight. 39) The monofilament fiber according to embodiment 37 or 38, which is undrawn. 40) The monofilament fiber according to any one of embodiments 37 to 39, having an orientation coefficient of less than 50%. 41) A monofilament fiber according to any one of embodiments 37 to 40, having an essentially circular cross section and a cross-sectional diameter of 1.6 to 3.1 mm. 42) The monofilament fiber of any one of embodiments 37-40, which is solid at ambient temperature but fluid at an elevated temperature, the fluid having an MFI value of about 2.5-30 g / 10 min, the elevated temperature being an operating temperature of an additive manufacturing process. 43) A monofilament fiber according to any one of embodiments 37 to 42, wherein the multiaxial polymer is USP Class VI biocompatible. 44) The monofilament fiber of any one of embodiments 37-43, wherein the multiaxial polymer has the formula M(B)3. 45) The monofilament fiber of any one of embodiments 37-43, wherein the multiaxial polymer has the formula M(B)2. 46) The monofilament fiber according to any one of embodiments 37-45, wherein M is at least 10% by weight of the polymer weight. 47) The monofilament fiber according to any one of embodiments 37 to 46, wherein B represents at least 40% by weight of the polymer weight. 48) The monofilament fiber of any one of embodiments 37-47, wherein 1-20 mol % of the repeating units in M ​​are the polymerization product of at least one of glycolide and lactide. 49) The monofilament fiber of any one of embodiments 37-48, wherein 1-20 mol % of the repeating units in B are the polymerization product of at least one of trimethylene carbonate and ε-caprolactone. 50) The monofilament fiber of any one of embodiments 37-49, wherein M comprises repeating units of trimethylene carbonate and ε-caprolactone. 51) A method of additive manufacturing comprising: a. melting the monofilament fiber according to any one of embodiments 37 to 50 to obtain a molten form of the fiber; b. depositing the molten form to obtain an initial article; and c. Cooling the initial article to room temperature to form a three-dimensional solid article. The method includes: 52) A method of additive manufacturing comprising: a. placing the assembly according to any one of embodiments 21 to 36 in an additive manufacturing printer; b. melting the monofilament fiber in a printer to obtain a molten form of the fiber; c. depositing the molten form to obtain an initial article; and d. Cooling the initial article to room temperature to form a three-dimensional solid article. The method includes:

[0056] Melting point The monofilament compositions of the present disclosure are thermoplastics that are solid at room temperature, can be heated to a fluid molten state, and return to a solid state upon cooling. In one embodiment, the compositions of the present disclosure are solid at ambient temperatures, e.g., 20-25°C, but are fluid at elevated temperatures, which are the operating temperatures of additive manufacturing processes. The operating temperatures used by different additive manufacturing processes vary, and are typically in the range of 50-450°C. In various embodiments, the compositions of the present disclosure become fluid at a temperature that may be referred to as the melting point of the composition, which may be greater than, and includes, about 50°C, or about 75°C, or about 100°C, or about 125°C, or about 150°C, or about 175°C, or about 200°C, or about 225°C, or about 250°C, or about 275°C, or about 300°C, or about 325°C, or about 350°C, or about 375°C, or about 400°C, or about 425°C, or about 450°C, depending on the composition. For example, in one embodiment, the melting point of the composition of the present disclosure is greater than about 50° C., e.g., about 50-100° C., or about 50-150° C., or about 50-200° C. In another embodiment, the melting point of the composition of the present disclosure is greater than about 75° C., e.g., about 75-125° C., or about 75-150° C., or about 75-175° C., or about 75-200° C., or about 75-225° C. As used herein, a temperature of "about° X" refers to temperature X, where X is the specified temperature, ±5° C. of the specified temperature, i.e., the specified temperature ±5° C. of the specified temperature. The melting point of the composition of the present disclosure may be measured according to ASTM or ISO standard procedures. For example, ASTM D7138-16 may be used to measure the melting temperature of synthetic fibers. As another example, ASTM D3418 describes the measurement of melting point using differential scanning calorimetry (DSC).

[0057] Melt Flow Index A monofilament composition may be characterized in terms of its melt flow properties, such as its melt flow index (MFI) or melt flow rate (MFR), when in the molten state, e.g., above its melting point. The melt flow index (MFI) is a useful test for measuring the flow properties of a material. This test can be applied to viscous fluids, including crystalline, semi-crystalline, or amorphous thermoplastic materials, and can measure the flow rate of a material under given temperature and pressure conditions, usually expressed as the mass (g) per minute that a particular composition flows through an opening of a given size. This test is a non-specific analysis of the flow properties of a material and is useful for determining the effect of temperature and pressure on a composition. For FFF and FDM, it is desirable to determine the appropriate temperature range to obtain an MFI value of about 2.5 to 30 g / 10 min, which will be the preferred FFF or FDM processing temperature for a given composition. ASTM and ISO have published standard procedures for measuring melt flow. See, for example, ISO 1133, JIS K 7210, and ASTM D1238 for common methods. In one embodiment, melt flow is measured according to ISO 1122-1 Procedure A. In another embodiment, melt flow is measured according to ASTM A1238 Procedure A. In another embodiment, melt flow is measured according to ISO 1122-2. In another embodiment, melt flow is measured according to ASTM D1238. Instron Corporation (Norwood, Massachusetts, USA) sells instruments that can be used to measure melt flow according to these procedures, such as the CEAST Melt Flow Testers MF10, MF20, and MF30. Zwick Roell AG (Ulm, Germany) also manufactures and sells suitable melt flow testers. Thus, the compositions of the present disclosure may be optionally characterized in terms of their MFI. The MFI generally corresponds to the viscosity of the fluid composition, with the higher the MFI, the less viscous the composition. Although compositions of a wide range of viscosities are available for additive manufacturing, certain MFI values ​​are particularly suitable, which are achieved by the compositions of the present disclosure. In one embodiment, the compositions of the present disclosure have an MFI value of about 2.5 to 30 g / 10 min at temperatures above the melting temperature of the composition and within the operating temperature of the additive manufacturing process, e.g., FFF. In various embodiments, the compositions of the present disclosure are characterized by an MFI, in grams measured in 10 minutes, of about 2.5-30, or about 2.5-25, or about 2.5-20, or about 2.5-15, or about 2.5-10, or about 5-30, or about 5-25, or about 5-20, or about 5-15, or about 10-30, or about 10-25, or about 10-15, or about 15-30, or about 15-25, or about 15-20, or about 20-30, or about 25-30. As used herein, about X-Yg refers to ±10% of X and Y, respectively, e.g., about 2.5g refers to 2.25-2.75g, and about 30g refers to 27-33g. In one aspect, the present disclosure provides filaments having dimensions and properties that are amenable to use in additive manufacturing. As discussed in detail herein, the filaments may be characterized by dimensions such as compositeness, diameter, and length, and / or properties such as tensile modulus, crystallinity, and flexibility.

[0058] Complexity Generally, the filaments can be monofilaments or multifilaments: a monofilament is a yarn consisting of a single filament, whereas a multifilament is a yarn made by twisting together two or more filaments, resulting in bifilaments, trifilaments, etc., depending on the number of filaments used to form the multifilament. The filaments of the present disclosure may be characterized as being monofilaments, i.e., the filament is a single filament rather than multiple filaments wound or braided together to form a multifilament configuration, also referred to as a mono-filament or monofilament.

[0059] cross section In one embodiment, the filament has a circular cross section. That is, the filament is cylindrical. Therefore, the filament may be described as having a diameter. In one embodiment, the diameter of the monofilament is in the range of 1.5 to 3.5 mm. In one embodiment, the diameter is 1.75 mm. In another embodiment, the diameter is 3.0 mm. In one embodiment, the diameter does not vary significantly with the length of the filament. For example, the diameter may be selected from a range of 1.5 to 3.5 mm, and the variation in diameter is ±0.1 mm or less with the length of the monofilament. In one embodiment, the diameter does not vary by more than 0.1 mm, for example, the diameter may be described as 3.0 ±0.1 mm. In another embodiment, the diameter does not vary by more than 0.05 mm, for example, the diameter may be described as 1.75 ±0.05 mm.

[0060] Mass and length In one embodiment, the filament is cut at a useful length, the useful length corresponding to a useful mass. The useful mass of the monofilament of the present disclosure is about 50-1,500 g for additive manufacturing. Parts printed by additive manufacturing can vary in mass, and the length of the monofilament advantageously provides sufficient mass to produce the entire part, but is not so long that the monofilament is retained in the printer for a long period of time before it is completely consumed. Since the monofilament in the printer degrades, for example, by oxidation and hydrolysis, from a stability standpoint, it is preferred that the monofilament is not retained in the printer for a long period of time that a significant amount of degradation occurs. With these considerations in mind, the present disclosure provides single (unbroken) lengths of monofilament with a mass of about 50-1,500, or 200-1,500, and in other embodiments, with a mass of about 800-1,200 g, or about 1,000 g, i.e., 950-1050 g. The present disclosure provides a method of forming a monofilament, comprising cutting the monofilament into lengths each having a mass of about 1,000 g. The monofilaments of the present disclosure may be characterized by their length. In one embodiment, the length of the monofilament is less than 500 m. In one embodiment, the length of the monofilament is less than 400 m. In one embodiment, the length of the monofilament is in the range of 10 to 500 m, and in another embodiment, the length of the monofilament is in the range of 10 to 400 m. In one embodiment, the length of the monofilament is 250 to 350 m.

[0061] Tensile Modulus The filaments of the present disclosure may be characterized by their tensile modulus. A suitable Young's modulus is at least 3 MPa and up to 4 GPa or more. The lower limit is suitable for producing parts with high elasticity and compliance, which is desired for many interface and tissue contacting structures. Materials with high modulus are selected for structural performance in high strength applications.

[0062] Crystalline The filaments of the present disclosure may be characterized by their crystallinity. Materials with varying total crystallinity may be useful in various products, with soft, ductile materials such as elastomers typically having low crystallinity. Such materials may have a total crystallinity of less than 5%. Highly crystalline materials such as PLLA or PEEK may be useful for rigid support structures where structural and mechanical strength are critical. Another characteristic of crystallinity relates to the presence of crystalline orientation along the fiber axis. Most typically, structural and fiber monofilaments are used as oriented yarns to maximize tensile strength, an important consideration for the design and utility of a particular monofilament. Orientation is achieved after monofilament extrusion by a heating step followed by a drawing step (also called "drawing") to align the crystallites along the filament axis. This increases the strength and stiffness of the fiber in that direction, but has the concomitant effect of decreasing the mechanical properties of the filament in the transverse direction. In one embodiment, the monofilaments of the present disclosure may be characterized as "undrawn" or "undrawn" in that they have not undergone a drawing step and therefore do not have the high crystallinity that results from a drawing step. Techniques for measuring crystalline orientation include, for example, wide-angle X-ray diffraction, birefringence, linear dichroism, and, in a technique particularly useful for fibers, acoustic velocity. Acoustic velocity correlates the degree of stretch with the relative speed of sound propagating through the filament and is expressed as the orientation factor (OF). OF can be expressed in various ways. OF can be measured on a "0" to "1" scale, with "0" indicating no orientation and "1" indicating perfect crystalline orientation. OF can also be expressed as a percentage, i.e., 0-100% instead of 0-1. OF can also be expressed as a multiple of an unoriented sample, e.g., 1.5 times the velocity of an unoriented control. In general, however, OF is an indication of the degree of molecular orientation or alignment of the polymer chains in the fiber or filament, with a higher number or percentage indicating a greater degree of alignment.

[0063] In many fiber filaments, the orientation factor can be, or desirably is, greater than 0.75, 0.85, 0.90, or even 0.95. Conversely, monofilaments used in additive manufacturing processes according to the present disclosure do not require the same tension, and instead have the advantage that less energy is typically required to melt unoriented filaments, combined with mechanical isotropy. Although the monofilaments of the present disclosure may have a somewhat lower degree of orientation as a result of the extrusion process, because the monofilaments are undrawn, the orientation factor of the monofilaments is relatively low, e.g., less than 0.50, 0.40, 0.30, 0.20, or 0.10. A relatively low OF is advantageous for filaments of the present disclosure suitable for melt extrusion processes such as FFF, because lower orientation generally means lower crystallinity, which means less heat is needed to transform the monofilament into a liquid state, and furthermore, the heat applied to the monofilament transforms the solid filament into a liquid state suitable for 3D printing more quickly and effectively. Thus, in one embodiment, the orientation factor of the monofilament of the present disclosure is less than 50%, in another embodiment, the orientation factor of the monofilament is less than 40%, in another embodiment, the orientation factor of the monofilament is less than 30%, in yet another embodiment, the orientation factor of the monofilament is less than 20%, and in yet another embodiment, the orientation factor of the monofilament is less than 10%. In each of these embodiments, the monofilament may be further characterized as an undrawn monofilament.

[0064] flexibility The filaments of the present disclosure may be characterized by their flexibility. The monofilament should not be so stiff (inflexible) that it breaks or breaks when wound onto a spool. Conversely, the monofilament should not be so flexible that it will not move forward when pushing the trailing portion of the monofilament. That is, if a piece of monofilament is laid straight and flat on a flat surface and the proximal end of the monofilament is pushed towards the distal end of the monofilament, the distal end should move forward the same distance as the proximal end of the monofilament is pushed. If the solid monofilament is too flexible, it will not have the rigidity to push the molten monofilament out of the heating chamber. As an indication of the ability of a filament to be pushed through a printer, a column buckling test can be performed, which measures the filament's resistance to buckling under axial compression (sometimes referred to as buckling strength). Buckling tests performed on filamentary materials involve placing the material vertically and clamping the top and bottom regions of the filament to be tested for buckling strength. The monofilament of the present disclosure may be held in place using two Bowden tubes extending along a single shared longitudinal axis with a 1 cm gap between the end of one Bowden tube and the end of the other Bowden tube. An interstitial monofilament is created by placing one monofilament inside the two Bowden tubes such that the 1 cm of interstitial monofilament between the two tubes is unsupported and exposed to environmental conditions. Bowden tubes are used in many FFF printing devices and are cylindrical with an inner diameter of about 2.0 mm. A monofilament with a width of about 1.75 mm must pass through the Bowden tube during the printing process. A mechanical testing machine may be used to bring the two Bowden tubes close together to observe the effect of axial compression on the interstitial filament while obtaining load and displacement information during testing. In buckling tests carried out with various filaments, the resistance (load) increases in the fiber direction until it reaches a peak, at which point buckling occurs, causing the monofilament to bend and act like a hinge, at which point the load begins to decrease. This change from resistance to buckling usually occurs before 5 mm of axial compression is reached. Once this peak resistance is reached, the filament becomes more likely to twist or bend rather than resist the applied compressive force.

[0065] A column buckling test was performed using monofilaments that print well in 3D printing and sample materials that print poorly or cannot be printed with existing Bowden tube printers or direct drive printers. This test identified a preferred minimum load that correlates with a "printable" monofilament. This value is at least 1N. Monofilaments that offer little or no resistance to the two ends of the Bowden tube moving together, i.e., less than about 1N in this column buckling test, were difficult to use in either Bowden tube printers or direct drive printers. This lack of proper operation is due to the low stiffness of the filament, which leads to column buckling and insufficient filament feeding. Thus, in one embodiment, the monofilament of the present disclosure exhibits a resistance of at least 1 N when subjected to a long column buckling test. The monofilament of the present disclosure may be characterized as having a buckling strength of at least 1 N. In another embodiment, the monofilament of the present disclosure exhibits a resistance of at least 1 N when a force is applied along the longitudinal axis of a 1 cm length of the monofilament. In one embodiment, a 1 cm length of the monofilament of the present disclosure having a width or diameter of 1.5 to 3.0 mm, e.g., 1.75±0.05 mm, exhibits a resistance of at least 1 N when subjected to this long column buckling test. In another embodiment, a 1 cm length of the monofilament of the present disclosure having a width or diameter of 1.5 to 3.0 mm, e.g., 1.75±0.05 mm, exhibits a resistance of at least 1 N when a force is applied along the longitudinal axis of a length of the monofilament of 3 cm or more, the 1 cm length being unconstrained, and at least 1 cm of monofilament is present at both ends of the unconstrained 1 cm monofilament, and the unconstrained 1 cm monofilament resists compression along its longitudinal axis.

[0066] water content In one aspect, the multiaxial polymer of formula M(B)2 or M(B)3 is dehydrated to obtain a low moisture polymer, which is then formed into a monofilament. In various embodiments, the dehydration step results in a multiaxial polymer with a moisture content of less than 100 ppm, or less than 200 ppm, or less than 300 ppm, or less than 400 ppm, or less than 500 ppm, or less than 600 ppm, or less than 700 ppm, or less than 800 ppm, or less than 900 ppm. To obtain a dehydrated polymer, the polymer may be ground into a powder and then placed in a vacuum oven for the desired time, temperature, and vacuum. Multiaxial polymers with low moisture content are advantageous for forming the monofilaments of the present disclosure, since the presence of moisture can cause polymer degradation during the monofilament formation process.

[0067] Monomer Content The multiaxial polymer of the present disclosure is conveniently prepared from an initiator and a monomer, where the monomer polymerizes to form the repeating units of the M and B portions of the multiaxial polymer. After the preparation of the M(B)2 or M(B)3 polymer, there is usually some unreacted (unpolymerized) monomer in the mixture containing the desired multiaxial polymer. In one embodiment of the present disclosure, the unreacted monomer is removed from contact with the multiaxial polymer. For example, the product mixture or a portion thereof containing the unreacted monomer and the multiaxial polymer may be placed in a vacuum oven at a suitable temperature and vacuum for a suitable time to evaporate and remove the monomer from the multiaxial polymer. Alternatively, the residual monomer may be removed using a solvent extraction process. In some embodiments, the residual monomer in contact with the multiaxial polymer in the monofilament of the present disclosure is less than 5% by weight, or less than 4% by weight, or less than 3% by weight, or less than 2% by weight, or less than 1% by weight. For example, in one embodiment, the present disclosure provides a monofilament fiber having a monomer content of less than 2% by weight. Such a monofilament fiber may be prepared from a multiaxial polymer having a monomer content of less than 2% by weight as disclosed herein. Since the presence of residual monomer in contact with the multiaxial polymer can cause decomposition of the multiaxial polymer during the heating step, thereby allowing the multiaxial polymer to become incorporated into the monofilament fiber body, residual monomer is advantageously removed from the multiaxial polymer prior to monofilament formation.

[0068] compound In one aspect, the present disclosure provides a compounded composition for use in making monofilaments. The compounded composition contains a polymer as described herein in a mixture with one or more additives. The additives impart desirable properties to the composition. Exemplary additives include antioxidants, stabilizers, viscosity modifiers, extrusion aids, lubricants, plasticizers, colorants and pigments, and active pharmaceutical ingredients. In some cases, the additives may serve one or more of the above functions. In various embodiments, the total of the additives is less than 10% by weight, or less than 9% by weight, or less than 8% by weight, or less than 7% by weight, or less than 6% by weight, or less than 5% by weight, or less than 4% by weight, or less than 3% by weight, or less than 2% by weight, or less than 1% by weight, based on the total weight of the composition consisting of the polymer and the additives. Exemplary antioxidants that can be used to minimize process and heat-induced oxidation include primary antioxidants, such as hindered phenols, and secondary antioxidants, such as thioethers.Suitable antioxidants are biocompatible in the amounts used in the composition.For medical applications, biocompatible antioxidants are preferred, such as vitamin E. Exemplary colorants that impart color to the manufactured part are optionally biocompatible in the amounts used in the composition. For medical applications, biocompatible colorants are preferred. Exemplary biocompatible colorants include D&C Violet#2, D&C Blue#6, D&C Green#6 (Phthalocyaninato(2-)) copper, as well as colorants listed in FDA 21 CFR Parts 73 and 74. The colorant should be used in an amount effective to achieve the desired appearance. For example, about 0.05% by weight of D&C Violet#2 can be used to produce a violet device. In one embodiment, the colorant is an FDA approved colorant present in the composition at a concentration of 0.01-0.5% by weight, and in other embodiments, the concentration of the colorant is 0.1-0.5% by weight, or 0.2-0.5% by weight, or 0.3-0.5% by weight, or 0.4-0.5% by weight. In one embodiment, the concentration of the colorant does not exceed about 0.5% by weight.

[0069] Exemplary viscosity modifiers that generally reduce the viscosity of the composition in molten form include oils, low molecular weight polymers and oligomers, monomers, and solvents. The use of viscosity modifiers reduces the energy required to melt the composition and improves flow and layer adhesion during the printing process. In one embodiment, PEG with a molecular weight of about 1,000 is included in the continuous phase at 0.5% by weight. When the main component of the continuous phase is poly(lactide), the addition of 0.5% by weight of PEG with a molecular weight of 1,000 results in a composition that can be processed in the FFF process at a temperature 15° C. lower than the corresponding monofilament without the viscosity modifier. In one embodiment, the composition of the present disclosure contains a viscosity modifier that is a polyethylene glycol with a molecular weight of less than 5,000, and the viscosity modifier is present in the composition at a concentration of less than 1% by weight of the composition. Various ingredients can be used to increase the viscous flow of the composition, such as plasticizers like oils, surfactants, organic solvents, e.g. water, monomers, low molecular weight polymers, and oligomers, the last three of which can optionally remain in the polymer as unreacted residues, whose presence can be useful in downstream processes such as extrusion or FFF printing. Optionally, the additive may be in the form of a microparticle. For example, in some specifications, the microparticle is identified as a microsphere with a regular, smooth wall. These microspheres may be created, for example, by an emulsification process or by a variety of other techniques used to create microspheres. Alternatively, the microparticle may include a collection of irregularly shaped microparticles. Irregularly shaped microparticles may include particles with smooth surfaces, rough surfaces, or a combination thereof. The microparticles may include particles with jagged edges. Irregularly shaped microparticles may be created by milling techniques such as jet milling, cryomilling, or ball milling, which reduce the size of the microparticles to a diameter suitable for the application.

[0070] Assembly The present disclosure provides articles, sometimes referred to as assemblies, that can be sold commercially and that provide convenient, purchased compositions that can be usefully used in additive manufacturing processes. The monofilaments described herein may be wound on a spool and used in additive manufacturing. The monofilaments are about 300-400 m long and have a mass of about 1 kg. In one embodiment, the composition of the present disclosure, i.e., the monofilaments, have a density of about 1.4 g / cm 3 Thus, a length of about 250 to 350 meters of monofilament is usefully placed on a spool and is provided in accordance with one embodiment of the present disclosure. In one embodiment, the monofilament of the present disclosure is wound on a spool to provide an exemplary assembly. The spool can be of the type that includes a core that supports the monofilament and two flanges that together function to hold the monofilament on the core. In one aspect, the spool is stable to a temperature of at least 90°C. In one aspect, the spool of the present disclosure is used in an additive manufacturing process and is exposed to high temperatures during the printing process. To maintain dimensional stability during the additive manufacturing process, the spool of the present disclosure can be stable to a temperature of at least 90°C, or at least 100°C, or at least 110°C, or at least 120°C, or at least 130°C, or at least 140°C, or at least 150°C. If the spool is not sufficiently thermally stable, the spool will deform as the temperature increases, and the deformed spool can interfere with the printing process and in some cases stop the printing process completely. The spool must also be stable against the release of vapors such as plasticizers that can contaminate the monofilament, e.g., the spool must not release organic vapors at high temperatures. Thus, in the kits and assemblies of the present disclosure, the spools can be thermally stable up to a temperature of at least 90° C. Suitable materials for constructing spools for the kits and assemblies of the present disclosure include acrylonitrile-butadiene-styrene (ABS) copolymers, polycarbonate, and mixtures thereof. As noted herein, the monofilaments of the present disclosure may be cut to lengths of about 1 kg, and the present disclosure provides spools containing this amount of monofilament, in other embodiments, the spools contain any of the other cut amounts of monofilament discussed herein.

[0071] In one embodiment, the present disclosure provides an assembly comprising a monofilament fiber wound on a spool, the monofilament fiber comprising a triaxial polymer of formula M(B), where M is the polymerization product of a first monomer, the first monomer comprising at least one monomer selected from trimethylene carbonate and ε-caprolactone, and B is the polymerization product of a second monomer, the second monomer comprising at least one monomer selected from glycolide, lactide, and caprolactone. Optionally, the assembly may be further described using one or more of the following criteria: the spool is stable to a temperature of at least 90° C.; the triaxial polymer is USP Class VI biocompatible; the monomer content of the triaxial polymer is less than 2% by weight; M of the triaxial polymer comprises at least 5% by weight of the total mass of the M(B)3 polymer; B comprises the polymerization products of glycolide, lactide, and caprolactone; the Tg of the triaxial polymer is less than 25° C.; the monofilament fiber is undrawn; the orientation factor of the monofilament fiber is less than 50%; the monofilament fiber is essentially circular in cross section and has a cross-sectional diameter of 1.7 to 2.9 mm; the monofilament fiber has a mass of 50 to 1,500 g; and the monofilament fiber is solid at ambient temperature but fluid at an elevated temperature, the fluid having an MFI value of about 2.5 to 30 g / 10 min, the elevated temperature being the operating temperature of the additive manufacturing process.For example, the disclosure provides an assembly including a monofilament fiber wound on a spool, the monofilament fiber comprising a triaxial polymer of formula M(B)3, M being a polymerization product of a first monomer, the first monomer comprising at least one monomer selected from trimethylene carbonate and ε-caprolactone, and B being a polymerization product of a second monomer, the second monomer comprising at least one monomer selected from glycolide, lactide, and caprolactone, the spool being stable to a temperature of at least 90° C., the triaxial polymer being USP Class VI biocompatible, the monomer content of the triaxial polymer being less than 2% by weight, M of the triaxial polymer comprising at least 5% by weight of the total weight of the M(B)3 polymer, B comprising the polymerization product of glycolide, lactide, and caprolactone, the monofilament fiber being undrawn, the orientation factor of the monofilament fiber being less than 50%, the monofilament fiber being essentially circular in cross section, and the cross-sectional diameter being between 1.7 and 2.9 mm.

[0072] In one embodiment, the disclosure provides an assembly comprising a monofilament fiber wound on a spool, the monofilament fiber comprising a polymer, the polymer being selected from a linear polymer of formula M(B)2 and a triaxial polymer of formula M(B)3, optionally where M is a prepolymer having a Tg less than 25° C., and where M comprises at least 5% by weight of the total weight of the polymer. In another embodiment, the disclosure provides an assembly comprising a monofilament fiber wound on a spool, the monofilament fiber comprising a polymer, the polymer being selected from a linear polymer of formula M(B)2 and a triaxial polymer of formula M(B)3, optionally where B is an end-grafted polymer having a Tg less than 25° C., and where B comprises at least 5% by weight of the total weight of the polymer. Optionally, either of these two embodiments may be further described using one or more of the following criteria: M is a prepolymer comprising the reaction product of monomers selected from trimethylene carbonate and ε-caprolactone; B is a terminal graft polymer comprising the reaction product of monomers selected from the group consisting of glycolide, lactide, trimethylene carbonate, ε-caprolactone, and dioxanone; at least 50 mol % of all residues in B are selected from the polymerization of monomers selected from trimethylene carbonate, ε-caprolactone, and dioxanone; less than 100 mol % of all residues in B are selected from the polymerization of monomers selected from glycolide and lactide. Optionally, the monofilament comprises a linear polymer of formula M(B), where M is a prepolymer comprising the reaction product of monomers selected from trimethylene carbonate and ε-caprolactone, and B is a terminal graft polymer comprising the reaction product of monomers selected from glycolide, lactide, trimethylene carbonate, ε-caprolactone, and dioxanone, and at least 50 mol % of all residues in B are selected from the polymerization of monomers selected from trimethylene carbonate, ε-caprolactone, and dioxanone.Optionally, the monofilament comprises a multiaxial polymer of formula M(B)3, where M is a prepolymer comprising the reaction product of a monomer selected from trimethylene carbonate and ε-caprolactone, and B is a terminal graft polymer comprising the reaction product of a monomer selected from glycolide, lactide, trimethylene carbonate, ε-caprolactone, and dioxanone, and at least 50 mol% of the total residues in B are selected from the polymerization of a monomer selected from trimethylene carbonate, ε-caprolactone, and dioxanone. In these embodiments, optionally, M is a homopolymer comprising the polymerization product of trimethylene carbonate; or optionally, M is a homopolymer comprising the polymerization product of ε-caprolactone; or optionally, M is a copolymer comprising the polymerization product of trimethylene carbonate and ε-caprolactone. In these embodiments, optionally, B comprises the polymerization product of glycolide, lactide, and caprolactone. Optionally, M comprises a polymer having repeat units, 20 mol % of which are low crystalline or non-crystalline, e.g., the low crystalline or non-crystalline repeat units are a polymerization product of a monomer selected from ε-caprolactone and trimethylene carbonate. In the assembly, the polymer of the monofilament can be a USP Class VI biocompatible polymer; and / or the polymer has a monomer content of less than 2% by weight (or another value disclosed herein); and / or the monofilament fiber is undrawn; and / or the monofilament fiber has an orientation factor of less than 50%; and / or the monofilament fiber has a constant diameter within the range of 1.6-3.1 mm±0.1 mm; and / or the mass of the monofilament fiber on the spool is between 50 and 1,500 g. Optionally, in two embodiments, the monofilament is a solid at ambient temperature but a fluid at an elevated temperature, the fluid having an MFI value of about 2.5-30 g / 10 min, the elevated temperature being an operating temperature of the additive manufacturing process. Optionally, in two embodiments, the monofilament has a columnar buckling resistance of at least 1N.

[0073] kit In one embodiment, the present disclosure provides a kit including an assembly in a pouch and, optionally, instructions for use. The assembly includes a monofilament fiber wound on a spool as discussed herein. The instructions, if present, may disclose the use of the assembly in an additive manufacturing process. Optionally, the pouch may also include some desiccant. In one embodiment, the monofilaments of the present disclosure are packaged and stored in a non-degrading environment. This is particularly important for monofilaments that contain components susceptible to air or moisture-induced degradation. Such monofilaments include bioabsorbable monofilaments, i.e., monofilaments made from bioabsorbable materials such as the M(B)2 and M(B)3 multiaxial polymers of the present disclosure, which are particularly susceptible to moisture-induced degradation. Whether the monofilaments are bioabsorbable or not, it is beneficial to store them in an inert atmosphere. Thus, the non-degrading environment can be one in which either or both of the moisture content and oxygen content are controlled. In one embodiment, the storage conditions include a dry environment with controlled moisture content, and in various embodiments, the moisture content is controlled to less than 1,000 ppm, or less than 800 ppm, or less than 700 ppm, or less than 600 ppm, or less than 400 ppm. The inert environment can be achieved by replacing the ambient air with a nitrogen-enriched atmosphere. Alternatively, the inert environment can be achieved by placing the monofilaments in an oxygen-impermeable packaging material and then sealing the packaging under reduced pressure. This method also reduces the amount of moisture the monofilament is exposed to during storage. Optionally, a desiccant, such as a bag of silica, may be placed in the packaging with the monofilament.

[0074] The pouch in this kit weighs 0.02g / 100in 2The pouches of the kits of the present disclosure may be characterized as having a low moisture vapor transmission rate (MVTR) of 0.02 g / 100 in or less. Moisture vapor transmission rate (MVTR) or water vapor transmission rate (WVTR) is a measure of the permeability of a material to moisture vapor, and is essentially a measure of the permeability of a water vapor barrier material. MVTR may be measured according to ASTM F1249 or ASTM E96. In some embodiments, the pouches of the kits of the present disclosure have an MVTR of 0.02 g / 100 in or less. 2 / 24h or less, or 0.002g / 100in 2 / 24h or less, or 0.001g / 100in 2 / 24h or less, or 0.0006g / 100in 2 / 24h or less. This measurement is performed at about 37.8°C (100°F) and 90% relative humidity. When the monofilament fiber is formed from a moisture sensitive polymer, such as the M(B)2 and M(B)3 polymers of the present disclosure, the use of a pouch with a low MVTR in the kit of the present disclosure is beneficial. In one embodiment, the pouch is a multi-layer pouch. In one embodiment, the multi-layer pouch includes a layer that includes a metal, such as a metal-fused polymer (e.g., polyethylene terephthalate (PET)) film or a metal foil, such as aluminum foil. In one embodiment, the kit includes a spool that is stable to a temperature of at least 100° C. and a pouch that is at least one of the following: a moisture vapor transmission rate (MVTR) of 0.002 g / 100 in 2 / Resistant to moisture for less than 24h; sealed; contains metal foil. In one embodiment, the present disclosure provides a packaged monofilament. The packaged monofilament is wound on a spool, and the spool with the monofilament is placed in a foil pouch. The foil pouch is sealed under vacuum or after replacing the ambient atmosphere with an inert atmosphere (e.g., nitrogen or dry air). Thus, the present disclosure provides a sealed package, such as a foil pouch containing the monofilament wound on a spool, the foil pouch having a reduced amount of moisture and / or oxygen compared to environmental conditions. Optionally, the pouch contains a single spool. Optionally, about 1 kg of a single monofilament is wound on a single spool.

[0075] Also, in one embodiment, the present disclosure provides a method of making assemblies and kits, comprising: providing a composition as described herein, e.g., a monofilament composition as described herein, obtaining the composition in molten form; extruding the composition in molten form to form a monofilament, the monofilament formed exhibiting no significant orientation to the monofilament, i.e., an undrawn monofilament; winding the undrawn monofilament onto a spool to form an assembly; and packaging the spool with the monofilament, e.g., in a foil pouch, to provide a kit. The packaging can be very airtight so that the monofilament is not exposed to moisture or oxidative conditions of the ambient atmosphere. The packaging can be, e.g., a foil pouch, where packaging involves placing the monofilament into the foil pouch. The monofilament can have any of the properties described herein, e.g., composition, diameter, length, color, orientation factor, buckling strength, etc. For example, the monofilament can be cut to lengths of less than 400 m when attached to the spool. As another example, the monofilament may be formed from a composition that includes a water soluble component, such as PEG (polyethylene glycol, an additive), and a bioabsorbable polymer phase, such as PDO, that is essentially insoluble in water after part formation while the additive is dissolved in water. For example, in one aspect, the disclosure provides a kit including an assembly in a pouch and, optionally, instructions for use. The assembly includes a monofilament fiber as described herein wound on a spool. If present, the instructions may disclose use of the assembly in an additive manufacturing process. In any embodiment, the kit may be described by one or more of the following: the spool is stable (e.g., does not melt or deform, or outgas, or leach organic compounds such as plasticizers) up to a temperature of at least 90° C.; the pouch has a moisture vapor transmission rate (MVTR) of 0.002 g / 100 in 2 / 24h or less; the pouch is a sealed pouch; the pouch contains metal foil.

[0076] In one embodiment, the disclosure provides a kit, in which a spooled monofilament fiber comprises a triaxial polymer of formula M(B)3, where M is a polymerization product of a first monomer, the first monomer being selected from at least one of trimethylene carbonate and ε-caprolactone, and B is a polymerization product of a second monomer, the second monomer being selected from at least one of glycolide, lactide, and ε-caprolactone. Optionally, the kit may be described using one or more of the following criteria (e.g., any two, or any three, or any four, or any five, etc.): the triaxial polymer is USP Class VI biocompatible; the monomer content of the triaxial polymer is less than 2% by weight, or less than 1.5% by weight, or less than 1% by weight, or less than 0.5% by weight; M of the triaxial polymer accounts for at least 5% by weight of the total weight of the M(B)3 polymer; B is a polymerization product of glycolide, lactide, and caprolactone. the Tg of the triaxial polymer is less than 25°C; the monofilament fiber is undrawn; the orientation factor of the monofilament fiber is less than 50%; the monofilament fiber is essentially circular in cross section and has a cross-sectional diameter of 1.7-2.9 mm; the monofilament fiber has a mass of 50-1,500 g; the monofilament fiber is solid at ambient temperature but fluid at an elevated temperature, the fluid having an MFI value of about 2.5-30 g / 10 min, the elevated temperature being an operating temperature of an additive manufacturing process.

[0077] In one embodiment, the disclosure provides a kit, the kit comprising a monofilament wound on a spool (i.e., assembled) and contained in a pouch, and optionally instructions for use of said monofilament in a method of additive manufacturing. In the assembly in the kit, the monofilament fiber comprises a polymer, the polymer being selected from a linear polymer of formula M(B)2 and a triaxial polymer of formula M(B)3, optionally M being a prepolymer having a Tg of less than 25°C, and M comprising at least 5% by weight of the total weight of the polymer. In another embodiment, the assembly in the kit comprises a monofilament fiber wound on a spool, the monofilament fiber comprises a polymer, the polymer being selected from a linear polymer of formula M(B)2 and a triaxial polymer of formula M(B)3, optionally B being an end-grafted polymer having a Tg of less than 25°C, and B comprising at least 5% by weight of the total weight of the polymer. Optionally, these two kit embodiments may be further described using one or more of the following criteria: M is a prepolymer comprising the reaction product of monomers selected from trimethylene carbonate and ε-caprolactone; B is a terminally grafted polymer comprising the reaction product of monomers selected from the group consisting of glycolide, lactide, trimethylene carbonate, ε-caprolactone, and dioxanone; at least 50 mol % of all residues in B are selected from the polymerization of monomers selected from trimethylene carbonate, ε-caprolactone, and dioxanone; less than 100 mol % of all residues in B are selected from the polymerization of monomers selected from glycolide and lactide. Optionally, the monofilament comprises a linear polymer of formula M(B), where M is a prepolymer comprising the reaction product of monomers selected from trimethylene carbonate and ε-caprolactone, and B is a terminal graft polymer comprising the reaction product of monomers selected from glycolide, lactide, trimethylene carbonate, ε-caprolactone, and dioxanone, and at least 50 mol % of all residues in B are selected from the polymerization of monomers selected from trimethylene carbonate, ε-caprolactone, and dioxanone.Optionally, the monofilament comprises a linear polymer of formula M(B)3, where M is a prepolymer comprising the reaction product of a monomer selected from trimethylene carbonate and ε-caprolactone, and B is a terminal graft polymer comprising the reaction product of a monomer selected from glycolide, lactide, trimethylene carbonate, ε-caprolactone, and dioxanone, and at least 50 mole % of the total residues in B are selected from the polymerization of a monomer selected from trimethylene carbonate, ε-caprolactone, and dioxanone. In these embodiments, optionally, M is a homopolymer comprising the polymerization product of trimethylene carbonate; or optionally, M is a homopolymer comprising the polymerization product of ε-caprolactone; or optionally, M is a copolymer comprising the polymerization product of trimethylene carbonate and ε-caprolactone. In these embodiments, optionally, B comprises the polymerization product of glycolide, lactide, and caprolactone. Optionally, M comprises a polymer having repeat units, 20 mol % of which are low crystalline or non-crystalline, e.g., the low crystalline or non-crystalline repeat units are a polymerization product of a monomer selected from ε-caprolactone and trimethylene carbonate. In the assembly, the polymer of the monofilament can be a USP Class VI biocompatible polymer; and / or the monomer content of the polymer is less than 2% by weight (or another value disclosed herein); and / or the monofilament fiber is undrawn; and / or the orientation factor of the monofilament fiber is less than 50%; and / or the monofilament fiber has a constant diameter within the range of 1.7-2.9 mm±0.1 mm; and / or the mass of the monofilament fiber on the spool is 50-1,500 g. Optionally, in these two embodiments, the monofilament is a solid at ambient temperature but a fluid at an elevated temperature, the fluid having an MFI value of about 2.5-30 g / 10 min, the elevated temperature being an operating temperature of the additive manufacturing process. Optionally, in both of these embodiments, the monofilament has a columnar buckling resistance of at least 1N.

[0078] The present disclosure provides the following additional exemplary embodiments of the present disclosure, which are numbered as follows: 1) A monofilament comprising a polymer, the polymer being selected from a biaxial polymer of formula M(B)2 and a triaxial polymer of formula M(B)3, M being a prepolymer comprising a plurality of repeating units and optionally having a Tg of less than 25°C, and M comprising at least 5% by weight of the total weight of the polymer. 2) A monofilament comprising a polymer, the polymer being selected from a biaxial polymer of formula M(B)2 and a triaxial polymer of formula M(B)3, B being a terminally grafted polymer comprising a plurality of repeating units and optionally having a Tg of less than 25°C, and B comprising at least 5% by weight of the total weight of the polymer. 3) The monofilament of embodiment 1 or 2, wherein M is a prepolymer comprising a plurality of repeating units, the repeating units comprising the polymerization product of a monomer selected from trimethylene carbonate and ε-caprolactone. 4) The monofilament of embodiment 3, wherein M comprises a plurality of repeating units, the repeating units comprising the polymerization product of at least one of trimethylene carbonate and ε-caprolactone, and the repeating units additionally comprising the polymerization product of one or both of δ-valerolactone and ε-decalactone. 5) The monofilament of embodiment 3, wherein M comprises a plurality of repeating units, the repeating units comprising the polymerization products of each of trimethylene carbonate, ε-caprolactone, and glycolide. 6) The monofilament of embodiment 3, wherein M comprises a plurality of repeating units, the repeating units comprising the polymerization products of each of trimethylene carbonate, ε-caprolactone, and lactide. 7) The monofilament according to any one of embodiments 1 to 6, wherein B is a terminal graft polymer comprising a plurality of repeating units, the repeating units comprising a polymerization product of a monomer, the monomer being selected from the group consisting of glycolide, lactide, trimethylene carbonate, ε-caprolactone, and dioxanone. 8) The monofilament of embodiment 7, wherein B is a terminally grafted polymer comprising a plurality of repeating units, the repeating units comprising the polymerization products of each of trimethylene carbonate and glycolide. 9) The monofilament of embodiment 7, wherein B is a terminal graft polymer comprising a plurality of repeating units, the repeating units comprising the polymerization products of each of trimethylene carbonate, ε-caprolactone, and lactide. 10) The monofilament according to any one of embodiments 1 to 9, wherein B comprises a plurality of repeating units and at least 50 mol % of the total repeating units in B are selected from the polymerization of glycolide and / or lactide. 11) The monofilament according to any one of embodiments 1 to 10, wherein B comprises a plurality of repeating units and at least 100 mol % of all repeating units in B are selected from the polymerization of glycolide and / or lactide. 12) A monofilament according to any one of embodiments 1 to 11, comprising a biaxial polymer of formula M(B)2, wherein M is a prepolymer comprising a plurality of repeat units, the repeat units comprising a polymerization product of trimethylene carbonate and / or ε-caprolactone, and B is a terminal graft polymer, wherein at least 50 mol % of all repeat units in B are selected from polymerization products of glycolide and / or lactide, and less than 50 mol % of all repeat units in B are selected from polymerization products of trimethylene carbonate and / or ε-caprolactone. 13) The monofilament according to any one of the preceding embodiments, comprising a triaxial polymer of formula M(B), wherein M is a prepolymer comprising a plurality of repeat units, the repeat units comprising a polymerization product of a monomer selected from trimethylene carbonate and / or ε-caprolactone, and B is a terminal graft polymer, wherein at least 50 mol % of the total repeat units in B are selected from the polymerization of a monomer selected from glycolide and lactide, and wherein less than 50 mol % of the total repeat units in B are selected from the polymerization of a monomer selected from trimethylene carbonate and ε-caprolactone. 14) The monofilament according to any one of embodiments 1 to 13, wherein M is a homopolymer by polymerization of trimethylene carbonate. 15) The monofilament according to any one of embodiments 1 to 13, wherein M is a homopolymer resulting from the polymerization of ε-caprolactone. 16) The monofilament according to any one of the preceding embodiments, wherein M is a copolymer comprising the polymerization product of trimethylene carbonate and ε-caprolactone. 17) The monofilament according to any one of the preceding embodiments, wherein B comprises a polymerization product of glycolide and trimethylene carbonate, and optionally also a polymerization product of lactide and / or ε-caprolactone. 18) The monofilament according to any one of the preceding embodiments, wherein B comprises a polymerization product of lactide and trimethylene carbonate, and optionally also a polymerization product of glycolide and / or ε-caprolactone. 19) A monofilament according to any one of embodiments 1 to 18, wherein the polymer is USP Class VI biocompatible. 20) The monofilament according to any one of embodiments 1 to 19, in which the monomer content of the polymer is less than 2% by mass. 21) The monofilament of embodiment 1 or 2, wherein M comprises a polymer having repeating units, at least 20 mol % of the repeating units being low crystalline or non-crystalline. 22) The monofilament of embodiment 21, wherein the low crystalline or non-crystalline repeating unit is the polymerization product of a monomer selected from ε-caprolactone and trimethylene carbonate. 23) The monofilament according to any one of embodiments 1 to 22, aM comprises a plurality of repeating units, and at least 70 mol % of the repeating units in M ​​are the polymerization product of at least one of trimethylene carbonate and ε-caprolactone; and bB comprises a plurality of repeating units, and at least 70 mol % of the repeating units in B are the polymerization product of at least one of glycolide and lactide. Monofilament. 24) The monofilament according to any one of embodiments 1 to 23, wherein M represents at least 10% by weight of the polymer weight. 25) The monofilament according to any one of the preceding embodiments, wherein B represents at least 40% by weight of the polymer. 26) The monofilament according to any one of embodiments 1 to 25, wherein 1 to 20 mol % of the repeating units in M ​​are the polymerization product of at least one of glycolide and lactide. 27) The monofilament according to any one of embodiments 1 to 26, wherein 1 to 20 mol % of the repeating units in B are a polymerization product of at least one of trimethylene carbonate and ε-caprolactone. 28) The monofilament according to any one of embodiments 1 to 27, wherein M comprises repeating units of trimethylene carbonate and ε-caprolactone. 29) The monofilament according to any one of embodiments 1 to 28, wherein the Tg of the multiaxial polymer is less than 25° C. 30) The monofilament according to any one of embodiments 21 to 29, which is undrawn. 31) The monofilament according to any one of embodiments 1 to 30, having an orientation coefficient of less than 50%. 32) The monofilament according to any one of embodiments 1 to 31, having a constant diameter within the range of 1.6 to 3.1 mm ± 0.1 mm. 33) The monofilament according to any one of embodiments 1 to 33, having a mass of 50 to 1,500 g. 34) The monofilament of any one of embodiments 1 to 34, which is solid at ambient temperature but fluid at an elevated temperature, the fluid having an MFI value of about 2.5 to 30 g / 10 min, the elevated temperature being an operating temperature of an additive manufacturing process. 35) The monofilament according to any one of embodiments 1 to 35, having a columnar buckling resistance of at least 1 N. 36) An assembly comprising a monofilament according to any one of embodiments 1 to 35 wound on a spool. 37) A kit comprising a monofilament according to any one of embodiments 1 to 35 wound on a spool and packaged in a pouch, optionally together with instructions for use of the monofilament or assembly in a method of additive manufacturing. 38) A method of additive manufacturing comprising: a. melting the monofilament fiber according to any one of embodiments 1 to 35 to obtain a molten form of the fiber; b. depositing the molten form to obtain an initial article; and c. Cooling the initial article to room temperature to form a three-dimensional solid article. The method includes: 39) A printed article produced by the method of embodiment 38. 40) A method of additive manufacturing comprising: a. placing the assembly of embodiment 36 into an additive manufacturing printer and feeding the monofilament fiber to the printer; b. melting the monofilament fiber in a printer to obtain a molten form of the fiber; c. depositing the molten form to obtain an initial article; and d. Cooling the initial article to room temperature to form a three-dimensional solid article. The method includes: 41) A printed article produced by the method of embodiment 40.

[0079] Additive Manufacturing The monofilaments described herein, as well as the assemblies and kits described herein, may be used in a method of additive manufacturing. For example, in one embodiment, the present disclosure provides a method of additive manufacturing, comprising melting the monofilaments described herein to obtain a molten monofilament, stacking multiple layers of the molten monofilament one by one to obtain a desired shape according to additive manufacturing, and then cooling the molten monofilament of the desired shape to room temperature to form a three-dimensional solid article. The method may also be described as using a kit of the present disclosure, which may include, for example, a monofilament described herein and instructions for using the monofilament in a method of additive manufacturing. Alternatively, the kit may include, for example, an assembly described herein and instructions for using the assembly in a method of additive manufacturing. In one embodiment, the present disclosure provides a method of additive manufacturing comprising melting a monofilament fiber as described herein to obtain a molten form of the fiber; depositing the molten form to obtain an initial article having a desired shape; and cooling the initial article to room temperature to form a three-dimensional solid article.

[0080] In a method of additive manufacturing, the monofilament fiber comprises a polymer, the polymer being selected from a linear polymer of formula M(B)2 and a triaxial polymer of formula M(B)3. Optionally, M is a prepolymer having a Tg less than 25° C., where M comprises at least 5% by weight of the total weight of the polymer, and / or optionally, B is a terminal graft polymer having a Tg less than 25° C., where B comprises at least 5% by weight of the total weight of the polymer. Optionally, the method of additive manufacturing may be further described using one or more of the following criteria: M is a prepolymer comprising the reaction product of monomers selected from trimethylene carbonate and ε-caprolactone; B is a terminal graft polymer comprising the reaction product of monomers, the monomers being selected from the group consisting of glycolide, lactide, trimethylene carbonate, ε-caprolactone, and dioxanone; at least 50 mol% of all residues in B are selected from the polymerization of monomers selected from trimethylene carbonate, ε-caprolactone, and dioxanone; less than 100 mol% of all residues in B are selected from the polymerization of monomers selected from glycolide and lactide. Optionally, the monofilament comprises a linear polymer of formula M(B), where M is a prepolymer comprising the reaction product of monomers selected from trimethylene carbonate and ε-caprolactone, and B is a terminal graft polymer comprising the reaction product of monomers selected from glycolide, lactide, trimethylene carbonate, ε-caprolactone, and dioxanone, and at least 50 mol % of all residues in B are selected from the polymerization of monomers selected from trimethylene carbonate, ε-caprolactone, and dioxanone. Optionally, the monofilament comprises a multiaxial polymer of formula M(B), where M is a prepolymer comprising the reaction product of monomers selected from trimethylene carbonate and ε-caprolactone, and B is a terminal graft polymer comprising the reaction product of monomers selected from glycolide, lactide, trimethylene carbonate, ε-caprolactone, and dioxanone, and at least 50 mol % of all residues in B are selected from the polymerization of monomers selected from trimethylene carbonate, ε-caprolactone, and dioxanone.In these embodiments, optionally, M is a homopolymer comprising the polymerization product of trimethylene carbonate; or optionally, M is a homopolymer comprising the polymerization product of ε-caprolactone; or optionally, M is a copolymer comprising the polymerization product of trimethylene carbonate and ε-caprolactone. In these embodiments, optionally, B comprises the polymerization product of glycolide, lactide, and caprolactone. Optionally, M comprises a polymer having repeat units, 20 mole % of which are low crystalline or non-crystalline, e.g., the low crystalline or non-crystalline repeat units are the polymerization product of monomers selected from ε-caprolactone and trimethylene carbonate. In the assembly, the polymer of the monofilament can be a USP Class VI biocompatible polymer; and / or the polymer has a monomer content of less than 2% by weight (or another value disclosed herein); and / or the monofilament fiber is undrawn; and / or the orientation factor of the monofilament fiber is less than 50%; and / or the monofilament fiber has a constant diameter within the range of 1.7-2.9 mm ±0.1 mm; and / or the mass of the monofilament fiber on the spool is between 50 and 1,500 g. Optionally, in these two embodiments, the monofilament is a solid at ambient temperature but a fluid at an elevated temperature, the fluid having an MFI value of about 2.5-30 g / 10 min, the elevated temperature being an operating temperature of the additive manufacturing process. Optionally, in these two embodiments, the monofilament has a long column buckling resistance of at least 1 N.

[0081] In one embodiment, the monofilament fiber of the present disclosure (also referred to herein simply as monofilament) may be useful in additive manufacturing processes, where printing is performed by creating multiple layers one on top of the other, i.e., by laying down one layer of molten polymer and then laying down another layer of molten polymer on some or all of the previously laid layer (the previous layer is fully or partially solidified before the next layer is laid down). Each layer may be considered to form the XY plane of the finished product, and the multiple layers together form the Z plane of the finished product. As mentioned elsewhere herein, in additive printing, the strength of the article in the Z direction may be less, and often significantly less, than the strength of the article in the XY direction. That is, the multiple layers in the Z direction are not as tightly held together as the layers in the XY direction. This problem is particularly noticeable when the XY plane is made of a relatively large amount of polymer, and therefore it takes a long time to completely print a layer in the XY direction. In this case, the first printed part of the XY plane may be completely solidified by the time the last printed part of the XY plane is completed. Thus, when the next layer is laid down (deposited on the previously laid down layer), the molten polymer is laid down on top of the cooled and fully solidified polymer and does not adhere well to the previously laid down layer. The present disclosure addresses this issue by providing a monofilament fiber that has thermal and crystallization properties (based on the selection of repeat units in M ​​and B) that advantageously allow adjacent layers to adhere strongly to each other (e.g., as measured by ultimate stress testing) even if a relatively long time (referred to herein as dwell time) passes between the first formed portion of the XY plane of the underlying layer being made and the molten polymer being laid down on top of the first formed portion of the XY plane of the underlying layer. In one embodiment, additive manufacturing printing according to the present disclosure deposits the molten polymer (of the monofilament) onto the uncrystallized surface of the previously laid down layer.

[0082] In one embodiment, the present disclosure provides a printed article in which the ultimate stress between the XY layers is substantially unaffected by the length of the dwell time, at least for up to 1 minute of dwell time. Thus, even if the printed part (also referred to herein as the article) has a wide XY plane, and therefore at least a portion of the XY plane undergoes complete or significant cooling before the adjacent XY plane is laid down, the monofilament of the present disclosure, when used in an additive manufacturing process, provides consistent adhesion between adjacent XY planes. In one embodiment, the strength of the printed part in the Z direction is ±10% or less over a 60 second dwell time, e.g., does not change (e.g., decrease) by more than 10% compared to a dwell time of only a few seconds. For example, compared to PLA (polylactide) or polyglycolide monofilaments, or copolymers of lactide and glycolide (PLGA), the monofilament of one embodiment of the present disclosure made from the multiaxial polymer described herein has an increased working time available during the additive manufacturing printing process, so that changes in working time have minimal impact on the strength of the printed part. In one embodiment, the ultimate stress of a printed part in the Z direction is essentially the same (within 10%) as the ultimate stress in the XY direction, at least when there is zero dwell time in forming the printed part. Thus, even in the absence of significant dwell times, monofilaments of the present disclosure made from multiaxial polymers form printed parts that have essentially the same strength in the Z direction as they do in the XY plane (as measured by ultimate stress). In one embodiment, the present disclosure provides a printed part in which the ultimate stress of the printed part in the Z direction (also referred to as the height build direction) is within 20%, or within 15%, or within 10%, or within 5% of the ultimate stress of the printed part measured in the XY direction. This is a significant advantage since additive manufacturing printing processes inherently involve a time lag for the addition of each XY layer, and printing large items or multiple parts one layer at a time increases the time to add layers. To improve the strength consistency and increase the mechanical isotropy of the printed part, there is a critical need for increased working time headroom between layers, which is provided by the present disclosure.

[0083] Below, some exemplary embodiments of the present disclosure are briefly described. 1) A monofilament comprising a linear polymer of formula M(B)2, wherein M comprises a polymer that accounts for at least 5% by weight of the total weight of the M(B)2 polymer and has a Tg of less than 25°C, and B is a terminal graft polymer comprising a plurality of repeat units. 2) The monofilament of embodiment 1, wherein B comprises a polymer having repeating units, at least 20 mol % of the repeating units being low crystalline or non-crystalline. 3) A monofilament comprising a linear polymer of formula M(B)2, where B comprises a polymer that accounts for at least 5% by weight of the total weight of the M(B)2 polymer and has a Tg of less than 25°C, and M is a prepolymer comprising a plurality of repeating units. 4) The monofilament of embodiment 3, wherein M comprises a polymer having repeating units, at least 20 mol % of the repeating units being low crystalline or non-crystalline. 5) Monofilaments comprising a triaxial polymer of formula M(B)3, where M comprises at least 5% by weight of the total weight of the M(B)3 polymer and has a Tg of less than 25°C. 6) The monofilament of embodiment 5, wherein B comprises a polymer having repeating units, at least 20 mol % of the repeating units being low crystalline or non-crystalline. 7) Monofilament comprising a triaxial polymer of formula M(B)3, where B represents at least 5% by weight of the total weight of the M(B)3 polymer and comprises a polymer having a Tg of less than 25°C. 8) The monofilament of embodiment 7, wherein M comprises a polymer having repeating units, at least 20 mol % of the repeating units being low crystalline or non-crystalline. 9) A monofilament comprising a linear polymer of formula M(B)2, where B comprises a polymer having repeating units, at least 20 mol % of the repeating units being low crystalline or amorphous. 10) The monofilament of embodiment 9, wherein M comprises a polymer that accounts for at least 5% by weight of the total weight of the M(B)2 polymer and has a Tg of less than 25° C. 11) A monofilament comprising a linear polymer of formula M(B)2, where M comprises a polymer having repeating units, at least 20 mol % of the repeating units being low crystalline or amorphous. 12) The monofilament of embodiment 11, wherein B comprises a polymer that accounts for at least 5% by weight of the total weight of the M(B)2 polymer and has a Tg of less than 25° C. 13) A monofilament comprising a triaxial polymer of formula M(B)3, where B comprises a polymer having repeating units, at least 20 mol % of the repeating units being low crystalline or amorphous. 14) The monofilament of embodiment 13, wherein M comprises a polymer that accounts for at least 5% by weight of the total weight of the M(B)3 polymer and has a Tg of less than 25° C. 15) A monofilament comprising a triaxial polymer of formula M(B)3, where M comprises a polymer having repeating units, at least 20 mol % of the repeating units being low crystalline or amorphous. 16) The monofilament of embodiment 15, wherein B comprises a polymer that accounts for at least 5% by weight of the total weight of the M(B)3 polymer and has a Tg of less than 25° C. 17) The monofilament of any one of embodiments 1 to 16, wherein M comprises a polymer selected from the group consisting of poly(trimethylene carbonate), poly(lactide), and poly(trimethylene carbonate-co-lactide). 18) The monofilament according to any one of embodiments 1 to 16, wherein M comprises a polyether, such as poly(ethylene oxide), or a polyester, such as polyethylene succinate or polypropylene succinate. 19) The monofilament according to any one of embodiments 1 to 16, wherein at least 20 mol % of the low crystalline or non-crystalline repeating units are polymerized residues of monomers selected from CAP and TMC. 20) The monofilament of embodiment 19, wherein the at least 20 mol% is less than 100 mol%. 21) The monofilament according to embodiment 19, wherein the at least 20 mol% is less than 90 mol%, i.e., 20 to 90 mol%. 22) The monofilament according to embodiment 19, wherein the at least 20 mol% is less than 80 mol%, i.e., 20 to 80 mol%. 23) The monofilament of embodiment 19, wherein the low crystalline or non-crystalline repeating unit is a polymerized residue of a monomer selected from lactide, glycolide, and polydioxanone. 24) The monofilament according to any one of the preceding embodiments, wherein B comprises a residue selected from the polymerization of a monomer selected from glycolide, lactide, TMC, CAP, and dioxanone. 25) The monofilament of embodiment 24, wherein at least 50% of the residues in B are selected from the polymerization of a monomer selected from TMC, CAP, and dioxanone. 26) The monofilament of embodiment 24, wherein residues selected from the polymerization of glycolide and lactide account for less than 100% of the residues in B. 27) The monofilament according to any one of embodiments 1 to 26, which is solid at ambient temperature but fluid at elevated temperatures, which are the operating temperatures of the additive manufacturing process, having an MFI value of about 2.5 to 30 g / 10 min. 28) The monofilament according to any one of embodiments 1 to 26, which has an orientation coefficient of less than 50% and is undrawn. 29) The monofilament according to any one of embodiments 1 to 26, having a diameter in the range of 1 to 5 mm. 30) The monofilament according to any one of embodiments 1 to 26, having a columnar buckling resistance of at least 1 N. 31) A method of additive manufacturing comprising: a. melting the monofilament according to any one of embodiments 1 to 30 to obtain a molten monofilament; and b. Cooling the molten monofilament to room temperature to form a three-dimensional solid article. The method includes: 32) A kit comprising a monofilament according to any one of embodiments 1 to 30 and instructions for use of said monofilament in a method for additive manufacturing. 33) A kit comprising an assembly as described herein, e.g., a monofilament wound on a spool, and instructions for using the assembly in a method of additive manufacturing. The following examples are presented for purposes of illustration and not limitation. EXAMPLES

[0084] Improved working time of lactide copolymer Monofilaments for additive manufacturing were prepared from polymers X1, X2, and X3. X1 is a reference polymer and is 100% polylactide, i.e., a homopolymer of lactide, where all repeat units are the polymerization product of lactide. X2 (available from Poly-Med, Anderson, South Carolina, USA) is also a reference polymer and is a triaxial polymer of formula M(B)3, where M is a homopolymer of trimethylene carbonate, i.e., all repeat units in M ​​are formed by polymerization of trimethylene carbonate monomers, and B is the polymerization product of a mixture of lactide and trimethylene carbonate end grafts. X3 (Poly-Med, Anderson, SC, USA) is a polymer used to make the monofilaments of the present disclosure and is a biaxial polymer of formula M(B)2, where M is a plurality of repeating units, about 88 mol % of these repeating units in M ​​are the polymerization product of each of trimethylene carbonate and ε-caprolactone, and about 12 mol % of these repeating units are the polymerization product of lactide, i.e., prepolymer M is made by polymerization of a mixture of trimethylene carbonate (TMC), ε-caprolactone (CAP), and lactide monomers, with TMC and CAP together being about 88 mol % of the reactants. The B end graft in X3 is similarly a plurality of repeat units, where about 90 mol % of the repeat units in B are the polymerization product of lactide and about 10 mol % are the polymerization product of a mixture of trimethylene carbonate and ε-caprolactone, i.e., the end graft is made by polymerization of a mixture of trimethylene carbonate, ε-caprolactone, and lactide monomers, with lactide making up 90 mol % of the reactants.

[0085] For each monofilament preparation, the base polymer was dried to low moisture content, typically less than 700 ppm moisture in the monofilament. The dried polymer was then extruded using a custom-built 3 / 4 inch single screw extruder to yield monofilaments with a diameter of 1.75 mm. The filaments were analyzed for molecular weight by intrinsic viscosity (IV) of a dilute solution at 0.1% by weight in chloroform and by DSC at a heating rate of 20°C / min. m (melting temperature) and ΔH f(Heat of fusion data) was obtained. Characterization results are shown in Table 1. N / A means data not available. [Table 1] Monofilaments listed in Table 1 were used to form articles in the shape of three-dimensional orthotopes (square prisms, rectangular prisms, or right-angled parallelepipeds, or columns for convenience herein; see FIG. 1 ) with dimensions 5 mm (X-direction) × 5 mm (Y-direction) × 7 cm (Z-direction). To form the articles, FDM printing was performed using an F306 printer (Fusion3, Raleigh, NC, USA) equipped with a Bowden tube print head with a 0.4 mm nozzle. Printing conditions were adjusted by adding layer dwell time (measured in seconds) at the center of the Z-direction, i.e., after printing 3.5 cm of the total 7 cm of the column in the Z-direction. Parts were printed with 100% infill, no outline, and a straight infill pattern. Layer dwells were adjusted between 0 and 600 seconds. In the printed articles, each layer of print (i.e., each XY plane) was printed at a thickness of 0.2 mm.

[0086] Figure 1 shows the geometry of the printed parts, specifically the test columns, which were used to evaluate layer adhesion. The column samples were annealed to complete the crystallization of the parts, i.e., to allow the test columns to fully crystallize, and the mechanical properties of the printed parts were evaluated by tensile testing using a universal mechanical testing machine equipped with pneumatic grips and a 5 kN load cell to measure the ultimate stress (measured in MPa) and ultimate elongation (measured in % elongation to failure). The test results are summarized in Table 2 and are graphically depicted in Figure 2. The Y-axis is plotted as percent retention from dwell time = 0 (i.e., no dwell time). [Table 2] The melting point of each material was lower than the nozzle temperature. The molten material transferred heat to the top printed layer, partially melting it, the extent of which depended on the thermal dynamics of the solidified substrate. Figure 2 plots the ultimate stress data from Table 2. From Figure 2, it can be seen that parts printed with X1 had a greater than 50% reduction in breaking strength compared to parts printed with no pause at 30 seconds pause. Similarly, the ultimate stress of X2 was reduced by 66% at 30 seconds pause compared to parts printed with no pause. In contrast, the ultimate stress of parts printed with X3 remained essentially stable at either 30 or 60 seconds pause and did not decrease significantly even after 600 seconds (10 minutes) of pause. That is, the Z-direction strength of the printed parts did not change by more than 10% over the 60 seconds pause (e.g., after 30 seconds pause, the ultimate stress changed by only 1.7% (28.8-29.3) / 28.8×100=1.7%, i.e., less than 10%) and did not change by more than 20% over the 600 seconds pause. This is a significant achievement, as the printing process inherently involves a time lag for each additional layer, and printing large items or multiple parts one layer at a time increases the time it takes to add layers. There is a critical need to increase the working time headroom between layers to improve the strength consistency and mechanical isotropy of printed parts.

[0087] [Table 3] Improved layer adhesion can be engineered to improve the isotropy of the polymer, which is desirable for predictable and uniform part performance. Ideally, materials processed by 3D printing will exhibit the same strength properties in the print build direction ("Z height") as in the lateral direction ("XY plane"), represented by 100% Z height retention. Lower retention indicates weaker layer adhesion and significantly reduced strength. Thus, monofilaments formed from X3, at least when printed with no downtime, resulted in printed parts where the ultimate stress in the Z direction (28.8 MPa) was essentially the same (within 10%) as the ultimate stress in the XY direction (27.1 MPa). The crystallization behavior of the materials listed in Table 1 was measured by DSC. In the heating / cooling mode of DSC, each sample was first melted at 200°C, and then the sample was cooled to the test temperature, i.e., 80°C or 100°C. The test temperature was selected at which the material exhibited an extended isothermal point that mimicked the working temperature. By examining the crystallization behavior at the test temperature, the time from melting to isothermal crystallization can be confirmed. In this test, X3 showed a peak crystallization event 33 minutes after the start of cooling from an isothermal hold at 80°C (see Figure 3), and a peak crystallization event 13.5 minutes after the start of cooling from an isothermal hold at 100°C (see Figure 4). In comparison, X1 showed a peak crystallization event after only 6.5 minutes from an isothermal hold at 100°C (see Figure 5), proving a significantly shorter working time compared to X3. In Figures 3-5, the samples were first heated from 20°C to 200°C at a rate of 20°C / min, and then cooled to the test temperature. The samples were treated with isothermal holds for extended periods and the crystallization events were analyzed as shown in Figures 3-5. EXAMPLES

[0088] Layer Adhesion Testing with Glycolide-Based Copolymers Additive manufacturing monofilaments were prepared from X4 (Poly-Med, Anderson, SC, USA), a triaxial block copolymer M(B)3 containing a flexible trimethylene carbonate (TMC) / caprolactone (CAP) / glycolide (GLY) (42 mol% TMC; 45 mol% CAP; 13 mol% GLY among the repeat units in M) terpolymeric central block (M) end-grafted with B, where B is the polymerization product (copolymer) of a mixture of glycolide (GLY) and trimethylene carbonate (TMC) (approximately 89 mol% GLY and 11 mol% TMC in each B). For comparison, additive manufacturing filaments were prepared from X5 (reference polymer). X5 is a random linear copolymer containing 95% glycolide and 5% l-lactide, X6 (reference polymer; Poly-Med, Anderson, SC, USA) is a triaxial block copolymer containing 86.5% glycolide and 13.5% trimethylene carbonate (the core (M) is a homopolymer formed from trimethylene carbonate and accounts for 13.5% of the polymer's mass), but the end grafts (B3, which together account for 86.5% of the polymer's mass) are made only from glycolide and therefore crystallize very rapidly, and X7 (Poly-Med, Anderson, SC, USA) is a triaxial block copolymer in which the end grafts together account for 98% of the polymer's mass (the end grafts contain 93% glycolide and 5% caprolactone based on the total mass of the M(B)3 polymer) and the core, a homopolymer of trimethylene carbonate, accounts for 2% of the mass of the MB3 polymer. The monofilaments were prepared according to the procedure described in Example 1. The properties of the obtained monofilaments are shown in Table 4 as in Table 1. [Table 4]

[0089] FDM printing was performed using a HYDRA640 printer (Hyrel 3D, Atlanta, GA, USA) equipped with a modular direct-drive printhead with a 0.4 mm nozzle. Columns with the geometry shown in Figure 1 were printed, and printing conditions were adjusted by adding pauses in the middle layers of the part to test the effect of time between printed layers on mechanical performance. Parts were printed with 100% infill, no outline, and straight infill patterns. Layer pauses were adjusted between 0 and 600 seconds. The melting point of each material was lower than the nozzle temperature. This molten material transfers heat to the top printed layer, partially melting the top printed layer, but the extent of melting depends on the thermal dynamics of the solidified substrate. In the printed parts, each layer was printed at 0.2 mm thickness. The column samples were annealed at 80 °C to allow for full crystallization, and the mechanical properties of the printed parts were evaluated using tensile tests using a universal mechanical testing machine equipped with pneumatic grips and a 5 kN load cell. A summary of the test results is shown in Table 5 and Figure 6. [Table 5] The data in Table 5 and the graph in Figure 6 show that the average ultimate stress of the X5 parts decreased by 23% after 60 seconds, while the strength of the X4 parts decreased by only 4%, indicating that the significant increase in working time has minimal effect on the strength properties.

[0090] Additional mechanical testing was performed on the materials in Table 4 with results shown in Table 6. The ply adhesion tests performed were similar to the procedure in ASTM D1876 (also known as the T-peel test), but with shorter than standard length specimens, the load was analyzed and compared to the tensile strength in two directions. Table 6 shows the average peel load over 60 mm and the results were averaged over five specimens tested. [Table 6] From the data presented in the graphs of Figures 2 and 6, it can be seen that monofilament fibers formed from either X4 or X3 exhibited superior performance characteristics for use in additive manufacturing, whereas monofilament fibers formed from either X1 or X7 did not. In Table 6, this difference is also reflected in the ratio of the average peel stress (MPa) to the ultimate tensile stress (MPa), expressed as a percentage in the far right column. In accordance with the present disclosure, monofilament is advantageous in additive manufacturing processes when it is in the form of a polymer having a peel stress equivalent of at least 10%.

[0091] X4 was also evaluated by DSC to understand the crystallization kinetics during the printing process. To do this, monofilaments of X4 were 3D printed to create DSC samples, which were then left at room temperature for various times before undergoing DSC evaluation to determine the heat of crystallization (ΔH c ), heat of fusion (ΔH f ), and the peaks of crystallization and melting events (T c and T m ) was analyzed and the data is shown in Table 7 below. [Table 7] X7 samples were analyzed by DSC by heating from 20°C to 240°C at a rate of 20°C / min, then cooling to room temperature at the same rate to measure crystallization time and compare it to the percent crystallization data for X4. In this evaluation, the X7 material recrystallized from the melt within the DSC cycle with a peak temperature of 168°C, with a peak area essentially the same as that of the melt. This means that bulk polymer crystallization of X7 occurred very rapidly upon cooling of the sample, suggesting that it would not perform well in additive manufacturing processes. EXAMPLES

[0092] Buckling Test As an indication of the ability of a monofilament fiber to push itself out of the printer in response to a force applied to the end of the fiber, i.e., whether the monofilament can adequately transmit force along its length, a column buckling test was performed that evaluates the response of the filament to axial compression. Buckling tests performed on filamentary materials were performed by placing the material vertically and clamping the top and bottom regions of the filament to be tested for buckling strength. The monofilament was held in place using two Bowden tubes extending along a single shared longitudinal axis, with a 1 cm gap between the end of one Bowden tube and the end of the other Bowden tube. An interstitial monofilament was created by placing one monofilament inside the two Bowden tubes, leaving the 1 cm of interstitial monofilament unsupported and exposed to environmental conditions between the two tubes. A mechanical testing machine was used to move the two Bowden tubes closer together to observe the effect of axial compression on the interstitial filament while obtaining load and displacement information during testing. The results of this test, performed on monofilaments made from four different polymers, namely X4, X3, X1, and X7, as defined elsewhere herein, are shown in Table 8. [Table 8] From the data in Table 8, it can be seen that X4 has the properties to be used in monofilament form in a direct drive printer for additive manufacturing, since it has a column buckling load of at least 1N. However, since X4 has a column buckling load (N) of less than about 5N, it will not work well in a Bowden tube printer. In contrast, X3, X1, and X7 have relatively high column buckling load values ​​(all greater than 5N), indicating that they have sufficient resistance to axial compression and can be used to form monofilament fibers useful in both direct drive and Bowden tube printers. Thus, in one embodiment, the monofilament of the present disclosure exhibits a resistance of at least 1N when subjected to a column buckling test. The monofilament of the present disclosure may be characterized as having a buckling strength of at least 1N. In another embodiment, the monofilament of the present disclosure exhibits a resistance of at least 1N when a force is applied along the longitudinal axis of a 1 cm length of the monofilament. In one embodiment, a 1 cm length of the disclosed monofilament having a width or diameter of 1.5-3.0 mm, e.g., 1.75±0.05 mm, when subjected to this long column buckling test, exhibits a resistance of at least 1 N. In another embodiment, a 1 cm length of the disclosed monofilament having a width or diameter of 1.5-3.0 mm, e.g., 1.75±0.05 mm, exhibits a resistance of at least 1 N when a force is applied along the longitudinal axis of the monofilament over a length of 3 cm or more, wherein the 1 cm length is unconstrained, and there is at least 1 cm of monofilament on either end of the unconstrained 1 cm length of monofilament, and the unconstrained 1 cm length of monofilament resists compression along its longitudinal axis.

[0093] The present disclosure has been described broadly and generically herein. Each of the narrower species and subgeneric groupings falling within the generic disclosure also forms part of this disclosure. This includes the generic description of the disclosure with a provisos or negative limitation excluding subject matter from the genus concept, regardless of whether the excised material is specifically described herein. It is also to be understood that the singular forms "a," "an," and "the," as used in this specification and the appended claims, include plural references unless the context clearly dictates otherwise, and that the term "X and / or Y" means "X" or "Y," or both "X" and "Y," and that the letter "s" following a noun refers to both the plural and the singular form of that noun. Furthermore, when features or aspects of the invention are described in terms of a Markush group, it is intended, and one of skill in the art will recognize, that the invention is thereby also described in terms of any individual member or any subgroup of members of the Markush group. Applicant also reserves the right to amend this application or claims to specifically refer to any individual member or any subgroup of members of the Markush group. All publications disclosed herein, including patent and non-patent publications, are hereby incorporated by reference in their entirety as if each was individually incorporated. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting. Further, it is to be understood that, unless otherwise defined herein, terms used herein are to be given their conventional meanings known in the relevant art. Throughout this specification, references to "one embodiment" or "an embodiment" and variations thereof mean that a particular feature, structure, or characteristic described in connection with an embodiment is included in at least one embodiment. Thus, the appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout the specification are not necessarily all referring to the same embodiment. Furthermore, particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.

[0094] As used herein and in the appended claims, the singular forms "a," "an," and "the" include plural references, i.e., one or more, unless the content and context clearly dictate otherwise. It should also be noted that the conjunctions "and" and "or" are generally used in a broad sense to include "and / or," unless the content and context clearly dictate inclusiveness or exclusivity. Thus, the use of alternative words (e.g., "or") should be understood to mean either one, both, or a combination of the alternative words. In addition, when described herein as "and / or," the "and" and "or" configurations are intended to encompass embodiments including all of the associated items or concepts, as well as one or more other alternative embodiments including less than all of the associated items or concepts. Unless the context otherwise requires, in this specification and the claims which follow, the words "comprise", "have", "include" and other synonyms and variations thereof, as well as variations thereof, such as "comprising", are to be construed in an open, inclusive sense, e.g., "including, but not limited to". The term "consisting essentially of" limits the scope of a claim to specified materials or steps or those that do not materially affect the basic and novel characteristics of the claimed invention.

[0095] The headings used herein are merely used to facilitate the reader's review and should not be construed as limiting the invention or claims in any manner. Accordingly, the headings and abstracts of the disclosure provided herein are for convenience only and do not interpret the scope or meaning of the embodiments. Where a range of values ​​is presented herein, it is understood that each intervening value, to the tenth of the unit of the lower limit, between the upper and lower limits of that range, and any other stated or intervening value in that stated range, is encompassed within the invention, unless the context clearly dictates otherwise. Unless any limit is specifically excluded in this stated range, the upper and lower limits of these smaller ranges, which may be independently included in the smaller ranges, are also encompassed within the invention. Where the stated range includes one or both of the upper and lower limits, ranges excluding either or both of those included limits are also included in the invention. For example, any concentration range, percentage range, ratio range, or integer range provided herein should be understood to include any integer value within the stated range, and fractions thereof, as appropriate (such as tenths and hundredths of integers), unless otherwise indicated. Also, any numerical range described herein relating to physical characteristics, such as polymer subunits, size, or thickness, should be understood to include any integer within the stated range, unless otherwise indicated. As used herein, the term "about" means ±20% of the indicated range, value, or structure, unless otherwise indicated.

[0096] All U.S. patents, U.S. patent application publications, U.S. patent applications, foreign patents, foreign patent applications, and non-patent literature referenced herein and / or listed in the Application Data Sheet are incorporated herein by reference in their entirety. Such documents may be incorporated by reference, for example, for the purpose of describing and disclosing the materials and methods described in the publications that may be used in connection with the presently described invention. The publications described in this specification and herein are presented solely as having been disclosed prior to the filing date of this application. Nothing in this specification is intended to be an admission that the inventors are not entitled to antedate any publications referenced by prior invention. All patents, publications, scientific articles, websites, and other documents and materials referenced or mentioned in this specification are indicative of the level of skill of those skilled in the art to which this invention pertains, and each such referenced document and material is hereby incorporated by reference in its entirety to the same extent as if it were individually incorporated by reference or set forth in its entirety herein. Applicant reserves the right to physically incorporate into this specification all materials and information from any such patents, publications, scientific articles, websites, electronically available information, and other referenced materials or documents.

[0097] In general, the terms used in the following claims should not be construed to limit the claims to the specific embodiments disclosed in the specification and the claims, but should be construed to include all possible embodiments along with the full scope of equivalents to which such claims are entitled. Accordingly, the claims are not limited by this disclosure. Further, the specification portion of this patent includes all claims. Moreover, all claims, including all original claims as well as all claims from any priority document, are hereby incorporated by reference in their entirety into the description portion of this specification, and applicants reserve the right to physically incorporate any such claims into the description portion or other portions of this application. Thus, for example, under no circumstances may this patent be construed as failing to provide a description to a claim based on a contention that the exact wording of a claim is not recited in those exact words in the description portion of this patent. The claims are to be interpreted according to law. However, even if ease or difficulty in interpreting any claim or any portion thereof is asserted or recognized, under no circumstances can the adjustment or modification of the claim or any portion thereof during the prosecution or filing of the application leading to this patent be construed as a waiver of any equivalents thereof that do not form part of the prior art. Other non-limiting embodiments are within the scope of the following claims. This patent may not be construed as being limited to the specific examples or non-limiting embodiments or methods specifically and / or explicitly disclosed herein. Under no circumstances may this patent be construed as being limited by statements made by any examiner or other employee of the Patent and Trademark Office, unless such statements have been specifically and unconditionally and expressly adopted by the applicant in the reply. Yet another aspect of the present invention may be as follows. [1] A kit including an assembly in a pouch, the assembly including a monofilament fiber wound on a spool, the monofilament fiber having the formula M(B): 2 Or M(B) 3 The multiaxial polymer comprises a) M is a copolymer comprising a plurality of repeating units, at least 70 mole percent of the repeating units in M ​​being the polymerization product of at least one of trimethylene carbonate and ε-caprolactone; and b) B is a homopolymer or copolymer comprising a plurality of repeating units, at least 70 mole percent of the repeating units in B being the polymerization product of at least one of glycolide and lactide. kit. [2] The kit described in [1], wherein the spool is stable up to a temperature of at least 90°C. [3] The water vapor transmission rate (MVTR) of the pouch is 0.002 g / 100 in 2 The kit according to claim 1, wherein the period is 24 hours. [4] The kit described in [1] above, wherein the pouch is a sealed pouch. [5] The kit described in [1], wherein the pouch comprises multiple layers, and at least one of the multiple layers comprises a metal foil. [6] The kit described in [1], wherein the monomer content of the monofilament fiber is less than 2% by mass. [7] The kit described in [1] above, wherein the monofilament fiber is undrawn. [8] The kit described in [1], wherein the orientation coefficient of the monofilament fiber is less than 50%. [9] The kit according to [1], wherein the monofilament fiber has an essentially circular cross section and a diameter of the cross section is 1.6 to 3.1 mm.

[10] The kit according to [1], wherein the mass of the monofilament fiber is 50 to 1,500 g.

[11] The kit described in [1], wherein the monofilament fiber is solid at ambient temperature but fluid at elevated temperature, the fluid having an MFI value of about 2.5 to 30 g / 10 min, and the elevated temperature is an operating temperature of an additive manufacturing process.

[12] The kit described in [1], wherein the multiaxial polymer is USP Class VI biocompatible.

[13] The multiaxial polymer is represented by the formula M(B): 3 The kit according to claim 1, comprising:

[14] The multiaxial polymer is represented by the formula M(B): 2 The kit according to claim 1, comprising:

[15] The kit according to [1], wherein M accounts for at least 10% by mass of the polymer.

[16] The kit according to [1], wherein B accounts for at least 50% by mass of the polymer.

[17] The kit according to [1] above, wherein 1 to 20 mol % of the repeating units in M ​​are a polymerization product of at least one of glycolide and lactide.

[18] The kit according to [1] above, wherein 1 to 20 mol % of the repeating units in B are a polymerization product of at least one of trimethylene carbonate and ε-caprolactone.

[19] The kit according to [1] above, wherein M comprises repeating units of trimethylene carbonate and ε-caprolactone.

[20] The kit described in [1], further comprising instructions for using the assembly in an additive manufacturing method.

[21] An assembly comprising a monofilament fiber wound on a spool, the monofilament fiber having the formula M(B) 2 Or M(B) 3 wherein M is a copolymer comprising a plurality of repeating units, at least 70 mol % of the repeating units in M ​​being the polymerization product of at least one of trimethylene carbonate and ε-caprolactone, and B is a homopolymer or a copolymer and comprises a plurality of repeating units, at least 70 mol % of the repeating units in B being the polymerization product of at least one of glycolide and lactide.

[22] Formula M(B) 2 Or M(B) 3 wherein M is a copolymer comprising a plurality of repeating units, at least 70 mol % of the repeating units in M ​​being the polymerization product of at least one of trimethylene carbonate and ε-caprolactone, and B is a homopolymer or a copolymer comprising a plurality of repeating units, at least 70 mol % of the repeating units in B being the polymerization product of at least one of glycolide and lactide.

[23] A method for additive manufacturing, comprising: a) melting the monofilament fiber according to

[22] to obtain a molten form of the fiber; b) depositing said molten form to obtain an initial article; and c) cooling the initial article to room temperature to form a three-dimensional solid article. The method includes:

[24] A monofilament comprising a polymer, the polymer having the formula M(B) 2 and linear polymers of formula M(B) 3 wherein M is a prepolymer comprising a plurality of repeating units and optionally having a Tg of less than 25° C., M comprises at least 5% by weight of the total weight of said polymer, and B is a terminal graft polymer comprising a plurality of repeating units.

[25] A monofilament comprising a polymer, the polymer having the formula M(B) 2 and linear polymers of formula M(B) 3 wherein B is a terminal graft polymer comprising a plurality of repeating units and optionally having a Tg of less than 25° C., B comprises at least 5% by weight of the total weight of said polymer, and M is a prepolymer comprising a plurality of repeating units.

[26] The monofilament according to

[24] or

[25] , wherein M is a prepolymer containing a plurality of repeating units, and the repeating units contain a polymerization product of a monomer selected from trimethylene carbonate and ε-caprolactone.

[27] The monofilament according to

[26] , wherein M comprises a plurality of repeating units, the repeating units comprising at least one polymerization product of trimethylene carbonate and ε-caprolactone, and additionally comprising at least one polymerization product of δ-valerolactone and ε-decalactone.

[28] The monofilament according to

[26] , wherein M comprises a plurality of repeating units, and the repeating units comprise polymerization products of trimethylene carbonate, ε-caprolactone, and glycolide.

[29] The monofilament according to

[26] above, wherein M comprises a plurality of repeating units, and the repeating units comprise polymerization products of trimethylene carbonate, ε-caprolactone, and lactide.

[30] The monofilament according to

[24] or

[25] , wherein B is a terminal graft polymer comprising a plurality of repeating units, the repeating units comprising a polymerization product of a monomer, the monomer being selected from the group consisting of glycolide, lactide, trimethylene carbonate, ε-caprolactone, and dioxanone.

[31] The monofilament according to

[30] , wherein B is a terminal graft polymer containing a plurality of repeating units, the repeating units containing polymerization products of trimethylene carbonate and glycolide.

[32] The monofilament according to

[30] , wherein B is a terminal graft polymer containing a plurality of repeating units, and the repeating units contain polymerization products of trimethylene carbonate, ε-caprolactone, and lactide.

[33] The monofilament according to

[24] or

[25] , wherein B comprises a plurality of repeating units, and at least 50 mol% of all of the repeating units in B are selected from the polymerization of a monomer selected from glycolide and lactide.

[34] The monofilament according to

[24] or

[25] , wherein B comprises a plurality of repeating units, and less than 100 mol% of all of the repeating units in B are selected from the polymerization of a monomer selected from glycolide and lactide.

[35] The above formula M(B) 2 The monofilament according to

[24] or

[25] , comprising a biaxial polymer of the formula: M is a prepolymer comprising a plurality of repeating units, the repeating units comprising a polymerization product of a monomer selected from trimethylene carbonate and ε-caprolactone, and B is a terminal graft polymer, at least 50 mol % of all repeating units in B are selected from the polymerization of a monomer selected from glycolide and lactide, and less than 50 mol % of all repeating units in B are selected from the polymerization of a monomer selected from trimethylene carbonate and ε-caprolactone.

[36] The above formula M(B) 3 The monofilament according to

[24] or

[25] , comprising a triaxial polymer of the formula: M is a prepolymer comprising a plurality of repeating units, the repeating units comprising a polymerization product of a monomer selected from trimethylene carbonate and ε-caprolactone, and B is a terminal graft polymer, at least 50 mol % of all repeating units in B are selected from the polymerization of a monomer selected from glycolide and lactide, and less than 50 mol % of all repeating units in B are selected from the polymerization of a monomer selected from trimethylene carbonate and ε-caprolactone.

[37] The monofilament according to

[24] or

[25] , wherein the polymer is USP Class VI biocompatible.

[38] The monofilament according to

[24] or

[25] , wherein the monomer content of the polymer is less than 2 mass%.

[39] The monofilament according to

[24] or

[25] above, wherein M is a homopolymer obtained by polymerization of trimethylene carbonate.

[40] The monofilament according to

[24] or

[25] above, wherein M is a homopolymer obtained by polymerization of ε-caprolactone.

[41] The monofilament according to

[24] or

[25] above, wherein M is a copolymer comprising a polymerization product of trimethylene carbonate and ε-caprolactone.

[42] The monofilament according to

[24] or

[25] , wherein B comprises a polymerization product of glycolide and trimethylene carbonate, and optionally also comprises a polymerization product of lactide and / or ε-caprolactone.

[43] The monofilament according to

[24] or

[25] , wherein B comprises a polymerization product of lactide and trimethylene carbonate, and optionally also comprises a polymerization product of glycolide and / or ε-caprolactone.

[44] The monofilament according to

[24] or

[25] , wherein M comprises a polymer having repeating units, and at least 20 mol % of the repeating units are low crystalline or non-crystalline.

[45] The monofilament according to

[32] , wherein the low crystalline or non-crystalline repeating unit is a polymerization product of a monomer selected from ε-caprolactone and trimethylene carbonate.

[46] The monofilament according to

[24] or

[25] , a) M comprises a plurality of repeating units, and at least 70 mole percent of the repeating units in M ​​are the polymerization product of at least one of trimethylene carbonate and ε-caprolactone; and b) B comprises a plurality of repeating units, and at least 70 mole % of the repeating units in B are the polymerization product of at least one of glycolide and lactide. Monofilament.

[47] The monofilament according to

[24] or

[25] , wherein M accounts for at least 10% by mass of the polymer.

[48] ​​The monofilament according to

[24] or

[25] , wherein B accounts for at least 50% by mass of the polymer.

[49] The monofilament according to

[24] or

[25] above, wherein 1 to 20 mol % of the repeating units in M ​​are a polymerization product of at least one of glycolide and lactide.

[50] The monofilament according to

[24] or

[25] above, wherein 1 to 20 mol % of the repeating units in B are a polymerization product of at least one of trimethylene carbonate and ε-caprolactone.

[51] The monofilament according to

[24] or

[25] above, wherein M contains repeating units of trimethylene carbonate and ε-caprolactone.

[52] The monofilament according to

[24] or

[25] , wherein the Tg of the multiaxial polymer is less than 25°C.

[53] The monofilament according to

[24] or

[25] above, which is undrawn.

[54] The monofilament according to

[24] or

[25] , having an orientation coefficient of less than 50%.

[55] The monofilament according to

[24] or

[25] , having a constant diameter within the range of 1.6 to 3.1 mm ± 0.1 mm.

[56] The monofilament according to

[24] or

[25] above, having a mass of 50 to 1,500 g.

[57] The monofilament according to

[24] or

[25] , which is solid at ambient temperature but fluid at elevated temperature, the fluid having an MFI value of about 2.5 to 30 g / 10 min, and the elevated temperature being the operating temperature of an additive manufacturing process.

[58] The monofilament according to

[24] or

[25] above, having a column buckling resistance of at least 1 N.

[59] An assembly comprising the monofilament according to any one of

[24] to

[58] above wound on a spool.

[60] A kit comprising the monofilament according to any one of

[24] to

[58] above, wound on a spool and contained in a pouch, optionally together with instructions for use of the monofilament in an additive manufacturing method.

[61] A method for additive manufacturing, comprising the steps of: a) melting the monofilament fiber according to any one of

[24] to

[58] to obtain a molten form of the fiber; b) depositing said molten form to obtain an initial article; and c) cooling the initial article to room temperature to form a three-dimensional solid article. The method includes:

[62] A printed article produced by the method of

[61] above.

[63] A kit including an assembly in a pouch, the assembly including a monofilament fiber wound on a spool, the monofilament fiber having the formula M(B): 2 Or M(B) 3 The multiaxial polymer comprises a) M comprises a plurality of repeating units, and at least 50 mole percent of the repeating units in M ​​are the polymerization product of at least one of trimethylene carbonate and ε-caprolactone; and b) B comprises a plurality of repeating units, and at least 50 mole % of the repeating units in B are the polymerization product of at least one of glycolide and lactide. kit.

[64] An assembly comprising a monofilament fiber wound on a spool, the monofilament fiber having the formula M(B) 2 Or M(B) 3 wherein M comprises a plurality of repeating units and at least 50 mol % of the repeating units in M ​​are the polymerization product of at least one of trimethylene carbonate and ε-caprolactone, and B comprises a plurality of repeating units and at least 50 mol % of the repeating units in B are the polymerization product of at least one of glycolide and lactide.

[65] Formula M(B) 2 Or M(B) 3 wherein M comprises a plurality of repeating units, at least 50 mol % of the repeating units in M ​​being a polymerization product of at least one of trimethylene carbonate and ε-caprolactone, and B comprises a plurality of repeating units, at least 50 mol % of the repeating units in B being a polymerization product of at least one of glycolide and lactide.

[66] A method for additive manufacturing, comprising: a) melting the monofilament fiber according to

[65] to obtain a molten form of the fiber; b) depositing said molten form to obtain an initial article; and c) cooling the initial article to room temperature to form a three-dimensional solid article. The method includes:

[67] A three-dimensional object created by the method of

[23] or

[66] .

[68] The article according to

[67] , having X, Y, and Z directions, wherein the Z is a build direction, the X and Y directions are perpendicular to the Z direction, and the ultimate stress of the article measured in the Z direction is within 20% of the ultimate stress of the article measured in either the X or Y direction.

Claims

1. A kit including an assembly in a pouch, the assembly including a monofilament fiber wound on a spool, the monofilament fiber having a formula M(B): 2 Or M(B) 3 The multiaxial polymer includes a) M is a copolymer comprising a plurality of repeating units, at least 70 mole percent of the repeating units in M ​​being the polymerization product of at least one of trimethylene carbonate and ε-caprolactone; and b) B is a homopolymer or copolymer comprising a plurality of repeating units, at least 70 mole percent of the repeating units in B being the polymerization product of at least one of glycolide and lactide. kit.

2. 10. The kit of claim 1, wherein the spool is stable to a temperature of at least 90°C.

3. The pouch has a moisture vapor transmission rate (MVTR) of 0.002 g / 645.16 cm 2 The kit of claim 1, wherein the period is 24 hours.

4. The kit of claim 1 , wherein the pouch is a sealed pouch.

5. The kit of claim 1 , wherein the pouch comprises multiple layers, at least one of the multiple layers comprising a metal foil.

6. 2. The kit of claim 1, wherein the monofilament fiber has a monomer content of less than 2% by weight.

7. The kit of claim 1 , wherein the monofilament fiber is undrawn.

8. 2. The kit of claim 1, wherein the monofilament fiber has an orientation factor of less than 50%.

9. 2. The kit of claim 1, wherein the monofilament fiber has a circular cross section and a diameter of the cross section is between 1.6 and 3.1 mm.

10. The kit according to claim 1, wherein the mass of the monofilament fiber is 50 to 1,500 g.

11. 2. The kit of claim 1, wherein the monofilament fiber is solid at ambient temperature but fluid at elevated temperature, the fluid having an MFI value of 2.5-30 g / 10 min, the elevated temperature being an operating temperature of an additive manufacturing process, the ambient temperature being 20-25° C., and the elevated temperature being 50-450° C.

12. The kit of claim 1 , wherein the multiaxial polymer is USP Class VI biocompatible.

13. The multiaxial polymer has the formula M(B): 3 The kit of claim 1 , comprising:

14. The multiaxial polymer has the formula M(B): 2 The kit of claim 1 , comprising:

15. M comprises at least 10% by weight of the polymer; or B accounts for at least 50% by weight of the polymer; or 2. The kit of claim 1, wherein 1 to 20 mole percent of the repeating units in M ​​are the polymerization product of at least one of glycolide and lactide.

16. 1 to 20 mole percent of the repeating units in B are the polymerization product of at least one of trimethylene carbonate and ε-caprolactone; or 2. The kit of claim 1, wherein M comprises repeating units of trimethylene carbonate and ε-caprolactone.

17. 1. An assembly comprising a monofilament fiber wound on a spool, the monofilament fiber having the formula M(B) 2 Or M(B) 3 wherein M is a copolymer comprising a plurality of repeating units, at least 70 mole percent of the repeating units in M ​​being the polymerization product of at least one of trimethylene carbonate and ε-caprolactone, and B is a homopolymer or a copolymer and comprises a plurality of repeating units, at least 70 mole percent of the repeating units in B being the polymerization product of at least one of glycolide and lactide.

18. Formula M(B) 2 Or M(B) 3 wherein M is a copolymer comprising a plurality of repeating units, at least 70 mol % of the repeating units in M ​​being the polymerization product of at least one of trimethylene carbonate and ε-caprolactone, and B is a homopolymer or a copolymer and comprises a plurality of repeating units, at least 70 mol % of the repeating units in B being the polymerization product of at least one of glycolide and lactide.

19. 20. The monofilament fiber of claim 18, wherein M is a prepolymer comprising a plurality of repeating units and having a Tg less than 25°C, M comprises at least 5% by weight of the total weight of said polymer, and B is an end-grafted polymer comprising a plurality of repeating units.

20. 20. The monofilament fiber of claim 18, wherein B is a terminally grafted polymer comprising a plurality of repeating units and having a Tg less than 25°C, B comprises at least 5% by weight of the total weight of said polymer, and M is a prepolymer comprising a plurality of repeating units.

21. 1. A method of additive manufacturing comprising: a) melting the monofilament fiber according to any one of claims 18 to 20 to obtain a molten form of said fiber; b) depositing said molten form to obtain an initial article; and c) cooling said initial article to room temperature to form a three-dimensional solid article. The method includes:

22. 21. The monofilament fiber according to any one of claims 18 to 20, wherein M is a prepolymer comprising a plurality of repeating units, the repeating units comprising a polymerization product of a monomer selected from trimethylene carbonate and ε-caprolactone, or M comprises a plurality of repeating units, the repeating units comprising a polymerization product of at least one of trimethylene carbonate and ε-caprolactone, and additionally comprising a polymerization product of at least one of δ-valerolactone and ε-decalactone, or comprising a polymerization product of each of trimethylene carbonate, ε-caprolactone, and glycolide, or comprising a polymerization product of each of trimethylene carbonate, ε-caprolactone, and lactide.

23. 21. The monofilament fiber according to any one of claims 18 to 20, wherein B is a terminal graft polymer comprising a plurality of repeating units, the repeating units comprising a polymerization product of a monomer, the monomer being selected from the group consisting of glycolide, lactide, trimethylene carbonate, ε-caprolactone, and dioxanone, and B is a terminal graft polymer comprising a plurality of repeating units, the repeating units comprising a polymerization product of each of trimethylene carbonate and glycolide, or a polymerization product of each of trimethylene carbonate, ε-caprolactone, and lactide.

24. 21. The monofilament fiber of any one of claims 18 to 20, wherein B comprises a plurality of repeating units, and less than 100 mol% of all of the repeating units in B are selected from the polymerization of monomers selected from glycolide and lactide.

25. The monofilament fiber of any one of claims 18 to 20, wherein the polymer is USP Class VI biocompatible.

26. The monofilament fiber according to any one of claims 18 to 20, wherein the monomer content of the polymer is less than 2% by weight.

27. The monofilament fiber according to any one of claims 18 to 20, wherein M is a homopolymer obtained by polymerization of trimethylene carbonate or ε-caprolactone.

28. The monofilament fiber of any one of claims 18 to 20, wherein M is a copolymer comprising the polymerization product of trimethylene carbonate and ε-caprolactone.

29. 21. The monofilament fiber of any one of claims 18 to 20, wherein B comprises a polymerization product of glycolide and trimethylene carbonate, and also comprises a polymerization product of lactide and / or ε-caprolactone.

30. 21. The monofilament fiber of any one of claims 18 to 20, wherein B comprises a polymerization product of lactide and trimethylene carbonate, and also comprises a polymerization product of glycolide and / or ε-caprolactone.

31. 21. The monofilament fiber of any one of claims 18 to 20, wherein M comprises a polymer having repeating units, at least 20 mol% of the repeating units being low crystalline or non-crystalline.

32. M comprises a plurality of repeating units, and at least 70 mole percent of the repeating units in M ​​are the polymerization product of at least one of trimethylene carbonate and ε-caprolactone; and 21. The monofilament fiber of any one of claims 18 to 20, wherein B comprises a plurality of repeating units, and at least 70 mol % of the repeating units in B are the polymerization product of at least one of glycolide and lactide.

33. 21. The monofilament fiber of any one of claims 18 to 20, wherein M comprises at least 10% by weight of the polymer.

34. The monofilament fiber according to any one of claims 18 to 20, wherein B accounts for at least 50% by weight of the polymer.

35. 21. The monofilament fiber of any one of claims 18 to 20, wherein 1 to 20 mole percent of the repeating units in M ​​are the polymerization product of at least one of glycolide and lactide.

36. 21. The monofilament fiber according to any one of claims 18 to 20, wherein 1 to 20 mol % of the repeating units in B are a polymerization product of at least one of trimethylene carbonate and ε-caprolactone.

37. The monofilament fiber of any one of claims 18 to 20, wherein M comprises repeating units of trimethylene carbonate and ε-caprolactone.

38. The monofilament fiber according to any one of claims 18 to 20, wherein the Tg of the multiaxial polymer is less than 25°C.

39. A monofilament fiber described in any one of claims 18 to 20, wherein the monofilament is undrawn.

40. A monofilament fiber described in any of claims 18 to 20, wherein the monofilament has an orientation coefficient of less than 50%.

41. A monofilament fiber according to any one of claims 18 to 20, wherein the monofilament has a constant diameter within the range of 1.6 to 3.1 mm ± 0.1 mm.

42. A monofilament fiber described in any of claims 18 to 20, wherein the monofilament has a mass of 50 to 1,500 g.

43. A monofilament fiber described in any of claims 18 to 20, wherein the monofilament is solid at ambient temperature but fluid at an elevated temperature, said fluid having an MFI value of 2.5 to 30 g / 10 min, and said elevated temperature being the operating temperature of an additive manufacturing process.

44. A monofilament fiber as described in any one of claims 18 to 20, wherein the monofilament has a columnar buckling resistance of at least 1 N.

45. 45. An assembly comprising the monofilament fiber of any one of claims 18 to 20 or 22 to 44 wound on a spool.

46. 45. A kit comprising the monofilament fiber of any of claims 18-20 or 22-44 wound on a spool and contained in a pouch together with instructions for use of said monofilament fiber in a method of additive manufacturing.

47. 1. A method of additive manufacturing comprising: a) melting the monofilament fiber according to any one of claims 18 to 20 or 22 to 44 to obtain a molten form of said fiber; b) depositing said molten form to obtain an initial article; and c) cooling said initial article to room temperature to form a three-dimensional solid article. The method includes:

48. 22. The method of claim 21 , wherein the three dimensional solid article has X, Y, and Z directions, wherein Z is a build direction, the X and Y directions are perpendicular to the Z direction, and wherein the ultimate stress of the article measured in the Z direction is within 20% of the ultimate stress of the article measured in either the X or Y directions.

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