A continuous fiber-reinforced hydrogel flexible implant scaffold and its in-situ customized forming method and application

Abstract

The application provides a continuous fiber reinforced hydrogel flexible implant scaffold and an in-situ customized forming method and application thereof, and belongs to the technical field of biological composite materials. The application uses high-performance continuous fibers as structural fibers, continuous hydrogel precursor fibers as a matrix, and constructs a ply fiber bundle structure in a composite manner, and through a flexible guiding three-dimensional profiling weaving forming technology, three-dimensional bionic weaving forming is carried out according to the structure and topographic features of a target tissue, so that a composite fiber preform is formed. Finally, through water absorption and swelling and synergistic crosslinking of the hydrogel precursor fibers in the composite fibers, the transformation of the precursor fibers in the preform into the hydrogel matrix is realized.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of biological composite materials, and particularly relates to a continuous fiber-reinforced hydrogel flexible implant scaffold and an in-situ customized forming method and application thereof. BACKGROUND

[0002] Hydrogel is a kind of gel structure that is soft, wet and biocompatible, while fiber has high mechanical properties and stability. The fiber-reinforced hydrogel constructed by the combination of the two can have both the high strength of fiber and the wet and slippery flexibility of hydrogel, forming a functional composite material with excellent mechanical properties and soft texture, thus having wide application prospects. For example, in the medical field, the fiber-reinforced hydrogel can be used for tissue engineering and drug release systems; in the field of biological engineering, it can be used for the preparation of biological materials and artificial tissues; in the field of environmental protection, it can be used for water treatment and pollution control.

[0003] The flexible implant scaffold is usually made of biocompatible hydrogel material, which is used to support, repair or replace damaged tissues in the human body, restore its physiological functions, and can be applied to skin wound repair, cartilage repair, abdominal patch, pelvic patch, etc. The mechanical properties and stability of hydrogel mainly depend on its crosslinking density, but it is usually difficult to meet the performance requirements of implant scaffolds, so the use of fiber reinforcement is an effective way to improve the structural performance of flexible implant scaffolds. At the same time, the individual customization of implant scaffolds can further improve the matching degree of the scaffold with the surrounding tissue morphology in the implanted area, and improve the implant stability and tissue adaptability.

[0004] In the field of individualized fiber-reinforced hydrogel implants, Chinese patents CN116478423A and CN116650727A disclose the use of carbon fiber, silk fibroin fiber and other fiber materials to composite with hydrogel to construct short fiber-reinforced hydrogel composite materials, which can be used as flexible materials for intelligent wearable sensors and tissue engineering scaffolds. However, due to the use of short fibers in the implant scaffold, the structural performance is still insufficient due to the limited fiber length, which cannot meet the normal physiological functions of human tissues; Chinese patents CN109675115A and CN116983469A propose the use of continuous fiber-reinforced hydrogel composite materials such as nanofibers to improve the mechanical properties and stability of hydrogel materials for artificial blood vessels, bone tissue repair and other fields. However, there is still a problem of poor mechanical strength. SUMMARY

[0005] Therefore, the present application aims to provide a continuous fiber-reinforced hydrogel flexible implant scaffold and an in-situ customized forming method and application thereof. The continuous fiber-reinforced hydrogel flexible implant scaffold prepared by the in-situ customized forming method has good mechanical properties.

[0006] To achieve the above object, the present application provides the following technical solutions.

[0007] The present application provides an in-situ customized forming method of a continuous fiber reinforced hydrogel flexible implant scaffold, comprising the following steps:

[0008] The hydrogel precursor powder is sequentially subjected to swelling and dissolution to obtain a hydrogel precursor spinning solution;

[0009] The hydrogel precursor spinning solution is sequentially subjected to spinning, forming and densification to obtain a continuous hydrogel precursor fiber;

[0010] The continuous hydrogel precursor fiber is plied and twisted with high-performance continuous fibers to obtain a composite fiber yarn;

[0011] The composite fiber yarn is subjected to flexible guiding three-dimensional profiling weaving to obtain a composite fiber preform; the flexible guiding three-dimensional profiling weaving comprises sequentially performing structure design of a braiding structure, braiding guiding path planning, structure weaving and compaction forming;

[0012] The composite fiber preform is sequentially subjected to controllable swelling and cross-linking forming to obtain the continuous fiber reinforced hydrogel flexible implant scaffold.

[0013] Preferably, the material of the hydrogel precursor powder comprises a synthetic high polymer material and / or a natural polysaccharide material, the synthetic high polymer material comprises one or more of polyvinyl alcohol, polyacrylamide, polyacrylic acid and polyethylene oxide, and the natural polysaccharide material comprises chitosan and / or gelatin.

[0014] Preferably, the diameter of the continuous hydrogel precursor fiber is 50-80 μm.

[0015] Preferably, the diameter of the high-performance continuous fiber is not higher than 50 μm.

[0016] Preferably, the high-performance continuous fiber comprises a natural fiber and / or an artificial synthetic fiber, the natural fiber comprises one or more of silk, spider silk and animal hair, and the artificial synthetic fiber comprises one or more of carbon fiber, glass fiber, aramid fiber, ultrahigh molecular polyethylene and polyester fiber.

[0017] Preferably, the volume content of the continuous hydrogel precursor fiber in the composite fiber yarn is 10-50%.

[0018] Preferably, the structure design of the braiding structure comprises design of a guiding column and a guiding template, and the guiding column is made of carbon fiber.

[0019] Preferably, the braiding guiding path planning is a circular path or a rectangular path.

[0020] The application further provides the continuous fiber-reinforced hydrogel flexible implant scaffold prepared by the in-situ customized forming method.

[0021] The application further provides application of the continuous fiber-reinforced hydrogel flexible implant scaffold in preparation of biomedical materials.

[0022] The application provides an in-situ customized forming method of a continuous fiber-reinforced hydrogel flexible implant scaffold, including the following steps: sequentially swelling and dissolving a hydrogel precursor powder to obtain a hydrogel precursor spinning solution; sequentially spinning, forming and densifying the hydrogel precursor spinning solution to obtain a continuous hydrogel precursor fiber; plying and twisting the continuous hydrogel precursor fiber and a high-performance continuous fiber to obtain a composite fiber yarn; performing flexible guiding three-dimensional profiling weaving on the composite fiber yarn to obtain a composite fiber preform; the flexible guiding three-dimensional profiling weaving includes sequentially performing structure design of a braiding structure, braiding guiding path planning, structure weaving and compaction forming; and sequentially performing controllable swelling and cross-linking forming on the composite fiber preform to obtain the continuous fiber-reinforced hydrogel flexible implant scaffold.

[0023] Compared with the prior art, the application has the following beneficial effects:

[0024] The application provides an in-situ customized forming method of a continuous fiber-reinforced hydrogel flexible implant scaffold, including the following steps: sequentially swelling and dissolving a hydrogel precursor powder to obtain a hydrogel precursor spinning solution; sequentially spinning, forming and densifying the hydrogel precursor spinning solution to obtain a continuous hydrogel precursor fiber; plying and twisting the continuous hydrogel precursor fiber and a high-performance continuous fiber to obtain a composite fiber yarn; performing flexible guiding three-dimensional profiling weaving on the composite fiber yarn to obtain a composite fiber preform; the flexible guiding three-dimensional profiling weaving includes sequentially performing structure design of a braiding structure, braiding guiding path planning, structure weaving and compaction forming; and sequentially performing controllable swelling and cross-linking forming on the composite fiber preform to obtain the continuous fiber-reinforced hydrogel flexible implant scaffold. The primary purpose of the application is to realize high-strength continuous fiber and hydrogel precursor fiberization compounding, build a plying fiber bundle structure of composite fibers, and meet the requirements of braiding forming; the second purpose is to provide a three-dimensional braiding customized forming technology of a composite fiber preform, that is, to perform target customized configuration design according to the tissue structure and topographic features of an in-vivo implant region, and perform three-dimensional profiling braiding forming of a biomimetic structure, so as to realize customized biomimetic preparation of the composite fiber preform; and the final purpose is to realize structure forming of a high-performance fiber-reinforced hydrogel based on controllable swelling and collaborative cross-linking of hydrogel precursor fibers in the composite fibers, and realize structure forming of a high-performance fiber-reinforced hydrogel based on controllable swelling and collaborative cross-linking of hydrogel precursor fibers in the composite fibers.

[0025] The application also provides the continuous fiber-reinforced hydrogel flexible implant scaffold prepared by the in-situ customized forming method. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 A flow chart of the in-situ customized forming method of the continuous fiber-reinforced hydrogel flexible implant scaffold of the application;

[0027] Figure 2 A structural schematic diagram and a sectional view of the composite fiber yarn, wherein 1 is a high-performance continuous fiber, and 2 is a continuous hydrogel precursor fiber;

[0028] Figure 3 A three-dimensional structural schematic diagram of the composite fiber preform, wherein 1 is a high-performance continuous fiber, and 2 is a continuous hydrogel precursor fiber;

[0029] Figure 4 A structural schematic diagram of the continuous fiber-reinforced hydrogel flexible implant scaffold, wherein 1 is a high-performance continuous fiber, and 2 is a hydrogel. DETAILED DESCRIPTION

[0030] The application provides an in-situ customized forming method of a continuous fiber-reinforced hydrogel flexible implant scaffold, including the following steps:

[0031] Swelling and dissolving the hydrogel precursor powder in sequence to obtain a hydrogel precursor spinning solution;

[0032] Spinning, forming and densifying the hydrogel precursor spinning solution in sequence to obtain a continuous hydrogel precursor fiber;

[0033] Plying and twisting the continuous hydrogel precursor fiber and a high-performance continuous fiber to obtain a composite fiber yarn;

[0034] Flexibly guiding three-dimensional profile weaving the composite fiber yarn to obtain a composite fiber preform; the flexible guiding three-dimensional profile weaving includes, in sequence, structural design of a braiding structure, planning of a braiding guiding path, structural weaving and compaction forming;

[0035] Controllably swelling and cross-linking forming the composite fiber preform in sequence to obtain the continuous fiber-reinforced hydrogel flexible implant scaffold.

[0036] The in-situ customized forming method of the present application comprises: (1) hydrogel precursor fiberization technology, (2) high-performance continuous fiber-continuous hydrogel precursor fiber composite forming method, (3) composite fiber preform three-dimensional structure customized forming method, (4) continuous high-performance fiber three-dimensional reinforced hydrogel composite forming method based on fiber gelation in the composite fiber preform.

[0037] Figure 1 Flow chart of the in-situ customized forming method of the continuous fiber reinforced hydrogel flexible implant scaffold of the present application.

[0038] In the present application, the raw materials used are all commercially available products in the art unless otherwise specified.

[0039] In the present application, the hydrogel precursor powder is sequentially swelled and dissolved to obtain a hydrogel precursor spinning solution.

[0040] In the present application, the material of the hydrogel precursor powder preferably comprises synthetic high molecular materials and / or natural polysaccharide materials, the synthetic high molecular materials preferably comprise one or more of polyvinyl alcohol (PVA), polyacrylamide (PAM), polyacrylic acid (PAA) and polyethylene oxide (PEO), and the natural polysaccharide materials preferably comprise chitosan (CS) and / or gelatin (GEL).

[0041] In the present application, the swelling and dissolution preferably comprise the following steps: dispersing the hydrogel precursor powder in deionized water (according to a mass fraction of 15% to 25%, more preferably 20%) in a 60°C constant temperature water bath for 1 to 2 hours (preferably 1 hour), and then heating to 80 to 90°C (preferably 85°C) and fully stirring for 2 to 2.5 hours (preferably 2 hours) for the dissolution, to obtain the hydrogel precursor spinning solution.

[0042] After obtaining the hydrogel precursor spinning solution, the hydrogel precursor spinning solution is sequentially spun, formed and densified to obtain a continuous hydrogel precursor fiber in the present application.

[0043] In the present application, the hydrogel precursor spinning solution preferably further comprises vacuum degassing before spinning. The present application does not have special limitations on the specific parameters of the vacuum degassing, which can be adopted in a manner well known to those skilled in the art.

[0044] In the present application, the spinning is preferably carried out in a spinning kettle, and the hydrogel precursor spinning solution is added to the spinning kettle and spun out from the spinneret.

[0045] In the present application, the temperature of the forming is preferably 40 to 60°C, more preferably 45 to 50°C, and the time is preferably 5 to 15 seconds, more preferably 10 to 13 seconds.

[0046] In the present application, the forming is preferably carried out in a forming coagulation bath.

[0047] In the present application, the forming coagulation bath is prepared by mixing sodium sulfate solution with mass concentration of 400-500 g / L (preferably 450 g / L) and sodium hydroxide solution with 3-5 g / L (preferably 5 g / L) at a volume ratio of 1:1.

[0048] The present application preferably densifies the nascent gel fiber obtained by the forming to obtain the continuous hydrogel precursor fiber.

[0049] In the present application, the densification preferably comprises the following steps: drying the nascent gel fiber in 20-25 °C air for 10-20 min (preferably 10 min) through 2 stretching guide rollers to obtain a hydrogel precursor fiber yarn.

[0050] After obtaining the hydrogel precursor fiber yarn, the present application preferably naturally air-dries the hydrogel precursor fiber yarn and then places it in an oven at 60-80 °C (more preferably 80 °C) for 1-2 h (more preferably 1 h) to obtain the continuous hydrogel precursor fiber.

[0051] In the present application, the diameter of the continuous hydrogel precursor fiber is preferably 50-80 μm, and more preferably 60-70 μm.

[0052] After obtaining the continuous hydrogel precursor fiber, the present application plying and twisting the continuous hydrogel precursor fiber with high-performance continuous fibers to obtain a composite fiber yarn.

[0053] In the present application, the diameter of the high-performance continuous fiber is preferably not higher than 50 μm.

[0054] In the present application, the high-performance continuous fiber preferably comprises natural fibers and / or artificial synthetic fibers, the natural fibers preferably comprising one or more of silk, spider silk, and animal hair, and the artificial synthetic fibers preferably comprising one or more of carbon fiber, glass fiber, aramid fiber, ultrahigh molecular polyethylene, and polyester fiber.

[0055] In the present application, the diameter of the high-performance continuous fiber is preferably not higher than 50 μm.

[0056] In the present application, the volume content of the continuous hydrogel precursor fiber in the composite fiber yarn is preferably 10-50%, and more preferably 20-30%, and the volume content of the high-performance continuous fiber determines the fiber volume ratio of the final fiber-reinforced hydrogel composite material, and the volume content of the continuous hydrogel precursor fiber is limited within the aforementioned range according to the requirements of implant tissue repair and replacement applications.

[0057] In the present application, the plying and twisting preferably comprises the following steps: pre-tensioning on the continuous hydrogel precursor fiber and high-performance continuous fiber respectively, the pre-tensioning is independently more preferably 0.3-1 cN / tex (most preferably 0.4-0.6 cN / tex), using a filament bundle twisting device, based on S-twist direction, two fiber bundles are combined and twisted in a number ratio of preferably 1:1-1:5 (more preferably 1:1), forming a twisted single yarn, the twist value of the twisted single yarn is more preferably 10-30 T / m (most preferably 15-20 T / m), then, 2-4 twisted single yarns are combined and twisted based on Z-twist direction, the twist value is the same as that of the twisted single yarn, forming a balanced composite fiber yarn, i.e. the composite fiber yarn.

[0058] Figure 2 It is a schematic diagram and a sectional view of the composite fiber yarn of the present application, wherein 1 is a high-performance continuous fiber, and 2 is a continuous hydrogel precursor fiber.

[0059] After obtaining the composite fiber yarn, the present application performs flexible guiding three-dimensional profile weaving on the composite fiber yarn to obtain a composite fiber preform; the flexible guiding three-dimensional profile weaving comprises, in sequence, structure design of a braiding structure, braiding guiding path planning, structure weaving and compaction molding.

[0060] In the present application, the three-dimensional structure customization molding method of the composite fiber preform determines the final topographic features of the hydrogel and the structural features of the high-performance continuous fiber inside; the present application proposes to use a flexible guiding three-dimensional profile weaving method to construct a three-dimensional fiber preform.

[0061] In the present application, the structure design of the braiding structure preferably comprises design of a guiding column and a guiding template, the guiding column is made of carbon fiber, the guiding column serves as a longitudinal reinforcing material, the diameter of the carbon fiber is preferably 1-5 mm, the spacing is preferably 3-10 mm, and the weaving density is preferably 10-30 tex.

[0062] The present application performs bionic design of the fiber-reinforced preform structure based on the natural physiological structural features of the implantation region in vivo, designs the structure and performance requirements according to the topographic features of the required implant, designs a 3D model of the product through computer three-dimensional software, and designs the guiding column, the guiding template and the weaving path.

[0063] In the present application, the weaving direction of the flexible guiding three-dimensional profile weaving is preferably 0°-360°.

[0064] In the present application, the weaving guide path planning is preferably a circular path or a rectangular path. The present application arranges guide posts on a guide template according to the cross-sectional profile of the composite fiber preform, and fixes the guide template on a weaving platform; the installation accuracy of the guide template is calibrated to 0.1 mm ± 0.01 mm using a gauge; and the weaving needle and the fiber are selected and installed.

[0065] In the present application, the structure weaving preferably includes the following steps: moving the weaving needle to the starting position of the platform, compiling the weaving path program, downloading it to the motion control card, and executing it; first performing target direction weaving, adjusting the moving direction of the weaving needle in real time according to the path design, and the adjustment range is preferably 0°-360°; after completing one layer of weaving, the weaving needle is preferably raised by 0.5-1 mm (more preferably 0.5 mm), and the next layer of weaving is performed, alternating back and forth.

[0066] In the present application, the moving speed of the weaving needle is preferably 10-50 mm / s, and more preferably 20-30 mm / s; and the rotation speed of the platform is preferably 10° / s.

[0067] In the present application, the compaction molding is preferably performed in the 0° and 90° directions.

[0068] After the compaction molding is completed, the present application preferably further includes performing post-processing, which preferably includes the following steps: removing the guide template from the weaving platform, removing the obtained preform in the post-processing area, and trimming the woven three-dimensional structure and replacing the fiber with the guide post according to the design requirements, to obtain the composite fiber preform.

[0069] In the present application, the gap between the woven fiber bundles of the composite fiber preform is preferably 0.1-0.5 mm, for water absorption and swelling of the hydrogel precursor fiber.

[0070] Figure 3 A schematic diagram of the three-dimensional structure of the composite fiber preform, wherein 1 is a high-performance continuous fiber, and 2 is a continuous hydrogel precursor fiber.

[0071] After obtaining the composite fiber preform, the present application sequentially performs controllable swelling and cross-linking molding on the composite fiber preform to obtain the continuous fiber-reinforced hydrogel flexible implant scaffold.

[0072] The gelation of the precursor fiber in the composite fiber preform is the core of the construction of the hydrogel matrix in the fiber-reinforced hydrogel composite material, that is, through the controllable swelling of the hydrogel precursor fiber, a large number of water molecules are absorbed into the molecular structure of the polymer, and then through a synergistic cross-linking strategy (including chemical cross-linking and physical cross-linking), the water molecules are locked into the molecular chain to form a stable hydrogel three-dimensional network structure, maintaining the gel state.

[0073] In the present application, the controllable swelling preferably comprises the following steps: immersing the composite fiber preform in water.

[0074] In the present application, the mass ratio of the composite fiber preform to water is preferably 1:3-1:10, more preferably 1:5-1:7.

[0075] In the present application, the water is preferably deionized water.

[0076] In the present application, the immersion time is preferably 1-6h, more preferably 3-5h, and the temperature is preferably 30-60℃. The present application does not have special limitations on the immersion time, and the water gel precursor in the composite fiber preform is completely swollen to realize in-situ compounding of the swelling structure and the high-performance fiber preform.

[0077] In the present application, the cross-linking molding is preferably physical cross-linking or chemical cross-linking.

[0078] In the present application, the physical cross-linking is preferably freeze-thaw method, which preferably comprises the following steps: freezing cross-linking at-20℃ environment for 6-24h (more preferably 12-18h), then thawing at 4℃ environment for 6-24h (more preferably 12-18h), and repeating the cycle for 3-6 times, to form a composite fiber reinforced water gel stable structure through physical cross-linking.

[0079] In the present application, the chemical cross-linking preferably comprises the following steps: during the immersion process, adding a chemical cross-linking agent in deionized water according to the water gel precursor powder mass ratio of 1:0.3-1:0.9 (more preferably 1:0.5), then adding a sodium hydroxide solution with a mass concentration of 100-150g / L (more preferably 100g / L) to adjust the pH value of the water gel according to the water gel precursor powder mass ratio of 1:0.2-1:1 (more preferably 1:0.5-1:0.7), and stirring uniformly and reacting at room temperature for 2h.

[0080] After the chemical cross-linking is completed, the obtained cross-linking product is preferably taken out and washed with deionized water until the washing liquid is neutral, to obtain a composite fiber reinforced water gel stable structure formed through chemical cross-linking.

[0081] In the present application, the chemical cross-linking agent preferably comprises boric acid and / or epichlorohydrin, more preferably epichlorohydrin.

[0082] The present application also provides a continuous fiber reinforced water gel flexible implant scaffold prepared by the in-situ customized molding method.

[0083] Figure 4 FIG. 1 is a structural schematic diagram of a continuous fiber reinforced water gel flexible implant scaffold, wherein 1 is a high-performance continuous fiber, and 2 is a water gel.

[0084] The application further provides the use of the continuous fiber-reinforced hydrogel flexible implant scaffold in the preparation of biomedical materials.

[0085] In the application, the biomedical materials preferably include drug carrier release materials, tissue engineering scaffold materials, medical dressing materials and abdominal patch materials.

[0086] The application is not particularly limited in the specific mode of the use, and a mode well known to those skilled in the art can be adopted.

[0087] The technical solutions in the application will be clearly and completely described below in combination with the embodiments in the application. Apparently, the described embodiments are only some of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative efforts fall within the protection scope of the application.

[0088] Embodiment 1:

[0089] a) Main material: glass fiber, polyvinyl alcohol

[0090] b) Polyvinyl alcohol hydrogel precursor fiberization:

[0091] (1) Take polyvinyl alcohol powder to prepare a solution with a mass fraction of 20% in a 60℃ constant-temperature water bath kettle and magnetically stir for 1h to swell, and then heat to 85℃ and magnetically stir for 2h to completely dissolve to prepare a hydrogel precursor spinning solution.

[0092] (2) Mix a 450g / L sodium sulfate solution with a 5g / L sodium hydroxide solution in a volume ratio of 1:1 to prepare a molding coagulation bath.

[0093] (3) Add the spinning solution into a spinning kettle for vacuum degassing. After the spinning solution is sprayed out of the spinneret, it stays in the 50℃ molding coagulation bath for 10s to generate nascent gel fibers, and then passes through two stretching guide rollers to dry and densify in the air to form a hydrogel precursor fiber sliver.

[0094] (4) After the hydrogel precursor fiber sliver is naturally air-dried, it is placed in an 80℃ oven for drying for 1h to complete the hydrogel precursor fiberization.

[0095] c) Glass fiber-hydrogel precursor fiber composite molding:

[0096] (1) Pre-apply a tension of 0.5cN / tex on the hydrogel precursor fiber and the glass fiber.

[0097] (2) Using long filament bundle twisting machine, based on S twist direction, two fiber bundles are twisted at a twist value of 20T / m to form twisted single yarn; then, four twisted single yarns are twisted and combined based on Z twist direction at the same twist value as single yarn to form balanced composite fiber yarn.

[0098] (3) The volume content of glass fiber in the composite fiber yarn is 20%.

[0099] d) Customized molding of the three-dimensional structure of the composite fiber preform:

[0100] (1) Through computer three-dimensional software, according to the topographic features and physiological structure of the implant target, a 3D model of the implant is designed, and the positions of the composite fiber guide column, the guide template and the weaving path are planned.

[0101] (2) According to the cross-sectional profile of the designed implant, the guide column is arranged on the guide template, the guide column has a diameter of 2mm and a spacing of 8mm, and the fiber ratio of the weaving fiber is 0.2:1, and then the guide template is fixed on the weaving platform.

[0102] (3) The installation accuracy of the guide template is calibrated to 0.1mm±0.01mm using a measuring tool; the weaving needle and fiber are selected and installed.

[0103] (4) Move the weaving needle to the starting position, take a rectangular weaving path, and weave in the 90° direction, with a weaving needle moving speed of 20mm / s and a fiber weaving density of 5 roots.

[0104] (5) After completing one layer of weaving, the weaving needle is raised by 0.5mm, the weaving platform is rotated at a speed of 10° / s, and weaving in the 0° direction is performed, with the same weaving parameters as in the 90° direction.

[0105] (6) After completing the 0° direction weaving, the 90° direction weaving is performed again according to the above parameters, and the weaving is alternately and reciprocally performed until 10 layers of weaving are completed.

[0106] (7) After the weaving is completed, a compaction program is used to perform compaction operation in the 0° and 90° directions.

[0107] (8) After the preform is removed from the guide template, edge trimming and subsequent processing of fiber replacing the guide column are performed according to the design requirements.

[0108] (9) The fiber gap of the woven composite fiber preform is 0.3mm.

[0109] e) Gelation molding of the composite fiber preform:

[0110] (1) Physical cross-linking strategy

[0111] (2) According to the weight ratio of hydrogel powder used 1:5, take deionized water, add to the constant temperature water bath pot of 60℃.

[0112] (3) The composite fiber preform is immersed in deionized water for 3h, so that the hydrogel precursor in the composite fiber preform is completely swollen, and the swelling structure is in-situ compounded with the high-performance fiber preform.

[0113] (4) According to the freeze-thaw method, freeze at-20℃ environment for 8h, then thaw at 4℃ environment for 6h, and cycle for 3 times, to form a stable structure of composite fiber reinforced hydrogel by physical crosslinking, and complete the fiberization molding of the preform.

[0114] Example 2:

[0115] a) Main material: glass fiber, polyvinyl alcohol

[0116] b) Fiberization of polyvinyl alcohol hydrogel precursor: same as example 1-b).

[0117] c) Glass fiber-hydrogel precursor fiber composite molding: same as example 1-c).

[0118] d) Three-dimensional structure customization molding of composite fiber preform: same as example 1-d).

[0119] e) Gelation molding of composite fiber preform:

[0120] (1) Chemical crosslinking strategy

[0121] (2) According to the weight ratio of hydrogel powder used 1:5, take deionized water.

[0122] (3) In deionized water, according to the weight ratio of hydrogel powder used 1:0.5, add dropwise epoxy chloropropane solution. Then according to the weight ratio of hydrogel powder 1:0.6, dropwise add 10wt% sodium hydroxide solution, after stirring uniformly, get the crosslinking agent for gel chemical crosslinking.

[0123] (4) The composite fiber preform is immersed in the crosslinking agent for room temperature reaction for 2h. The hydrogel precursor in the composite fiber preform is completely swollen and crosslinked.

[0124] (5) After the reaction is completed, the fiber reinforced hydrogel is taken out and washed with deionized water until the washing liquid is neutral, and the swelling structure is in-situ compounded with the high-performance fiber preform.

[0125] Example 3:

[0126] a) Main material: glass fiber, chitosan

[0127] b) Fiberization of chitosan hydrogel precursor:

[0128] (1) Take chitosan powder as 20% solution mass fraction in 60°C constant temperature water bath and magnetic stirring with deionized water for 1h, so that it swells, then heated to 85°C and magnetic stirring for 2h, completely dissolved to prepare hydrogel precursor spinning solution.

[0129] (2) The mass concentration of 450g / L sodium sulfate solution and 5g / L sodium hydroxide solution are mixed to prepare the forming coagulation bath.

[0130] (3) The spinning solution is added to the spinning kettle for vacuum degassing. After the spinning solution is sprayed from the spinneret, it stays in the 50°C forming coagulation bath for 10s to generate nascent gel fiber, and then passes through two stretching guide rollers to dry and densify in the air to form hydrogel precursor fiber sliver.

[0131] (4) After the hydrogel precursor fiber sliver is naturally dried, it is placed in an 80°C oven for 1h to complete the hydrogel precursor fiber formation.

[0132] c) Glass fiber-hydrogel precursor fiber composite forming: same as example 1-c).

[0133] d) Composite fiber preform three-dimensional structure customization forming: same as example 1-d).

[0134] e) Composite fiber preform gelation forming: same as example 1-e).

[0135] Example 4:

[0136] a) Main material: glass fiber, polyacrylamide

[0137] b) Polyacrylamide hydrogel precursor fiber formation:

[0138] (1) Take polyacrylamide powder as 20% solution mass fraction in 60°C constant temperature water bath and magnetic stirring with deionized water for 1h, so that it swells, then heated to 85°C and magnetic stirring for 2h, completely dissolved to prepare hydrogel precursor spinning solution.

[0139] (2) The mass concentration of 450g / L sodium sulfate solution and 5g / L sodium hydroxide solution are mixed to prepare the forming coagulation bath.

[0140] (3) The spinning solution is added to the spinning kettle for vacuum degassing. After the spinning solution is sprayed from the spinneret, it stays in the 50°C forming coagulation bath for 10s to generate nascent gel fiber, and then passes through two stretching guide rollers to dry and densify in the air to form hydrogel precursor fiber sliver.

[0141] (4) After the hydrogel precursor fiber sliver is naturally dried, it is placed in an 80°C oven for 1h to complete the hydrogel precursor fiber formation.

[0142] c) Glass fiber-hydrogel precursor fiber composite forming: same as example 1-c).

[0143] d) Composite fiber preform three-dimensional structure custom forming: same as example 1-d).

[0144] e) Composite fiber preform gelation forming: same as example 1-e).

[0145] Example 5:

[0146] a) Host material: silk, polyvinyl alcohol

[0147] b) Polyvinyl alcohol hydrogel precursor fiberization: same as example 1-b).

[0148] c) Silk fiber-hydrogel precursor fiber composite forming:

[0149] (1) Pre-tension of 0.5 cN / tex on the hydrogel precursor fiber and the silk fiber.

[0150] (2) Using a filament bundle twisting machine, twist two fiber bundles based on S twist direction with a twist value of 20 T / m to form twisted single yarns; then, twist and combine 4 twisted single yarns based on Z twist direction with the same twist value as the single yarn to form balanced composite fiber yarns.

[0151] (3) The volume content of silk fiber in the composite fiber yarns is 20%.

[0152] d) Composite fiber preform three-dimensional structure custom forming: same as example 1-d).

[0153] e) Composite fiber preform gelation forming: same as example 1-e).

[0154] Example 6:

[0155] a) Host material: silk, chitosan

[0156] b) Chitosan hydrogel precursor fiberization: same as example 3-b).

[0157] c) Silk fiber-hydrogel precursor fiber composite forming: same as example 5-c).

[0158] d) Composite fiber preform three-dimensional structure custom forming: same as example 1-d).

[0159] e) Composite fiber preform gelation forming: same as example 1-e).

[0160] Example 7:

[0161] a) Host material: silk, polyacrylamide

[0162] b) Polyacrylamide hydrogel precursor fiberization: same as example 4-b).

[0163] c) Silk fiber-hydrogel precursor fiber composite molding: same as example 5-c).

[0164] d) Composite fiber preform three-dimensional structure customized molding: same as example 1-d).

[0165] e) Composite fiber preform gelation molding: same as example 1-e).

[0166] Comparative Example 1:

[0167] The same as example 1, the only difference is that no fiber is added.

[0168] Comparative Example 2:

[0169] The same as example 3, the only difference is that no fiber is added.

[0170] Comparative Example 3:

[0171] The same as example 4, the only difference is that no fiber is added.

[0172] The preparation process of examples 1-7 and comparative examples 1-3 and the performance of the high-strength continuous fiber-reinforced hydrogel prepared are tested, the compression performance of the fiber-reinforced hydrogel and the hydrogel monomer is measured and analyzed by compression test, then the fiber-reinforced hydrogel and the hydrogel monomer are directly contacted with the cell culture medium by direct contact method, and the cytotoxicity is evaluated by the tetrazolium bromide method (MTT) method. The results are shown in Table 1.

[0173] Table 1 Preparation process and test results of examples 1-7 and comparative examples 1-3

[0174]

[0175] From Table 1, it can be seen that:

[0176] 1. The present application proposes a flexible implant scaffold with high mechanical properties and specific matching, which is composed of high-strength continuous fibers as reinforcing structure and high molecular hydrogel as matrix, effectively avoiding the problems of insufficient mechanical properties, poor durability and insufficient structural stability caused by single material of traditional hydrogel, and compared with short fiber-reinforced hydrogel, it has better fracture toughness and surface smoothness.

[0177] 2. The flexible continuous fiber reinforced composite material in-situ forming method proposed in the application is based on hydrogel precursor fiberization and high-strength continuous fiber twisting to form a composite fiber bundle structure, and a flexible guiding three-dimensional profiling weaving technology is used to realize customized forming of a composite fiber preform based on a target implantation area, and finally, a customized composite fiber reinforced hydrogel stable structure is constructed by means of controllable swelling and cross-linking of the hydrogel precursor fibers.

[0178] 3. The composite fiber reinforced hydrogel proposed in the application can be specifically designed according to the biological medical application direction and actual demand through a three-dimensional customized forming process, and a customized flexible hydrogel material completely matched with the composite fiber reinforced hydrogel is prepared.

[0179] The above description is only the preferred embodiments of the present application, and does not limit the present application in any form. It should be noted that for ordinary skilled persons in the art, some improvements and refinements can be made without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. An in-situ customized molding method of a continuous fiber-reinforced hydrogel flexible implant scaffold, characterized in that, The method comprises the following steps: swelling and dissolving the hydrogel precursor powder in sequence to obtain a hydrogel precursor spinning solution; spinning, molding and densifying the hydrogel precursor spinning solution in sequence to obtain a continuous hydrogel precursor fiber; plying and twisting the continuous hydrogel precursor fiber and high-performance continuous fibers to obtain a composite fiber yarn; flexibly guiding three-dimensional profile weaving the composite fiber yarn to obtain a composite fiber preform; the flexible guiding three-dimensional profile weaving comprises structural design of a braiding structure, braiding guiding path planning, structural weaving and compaction molding in sequence; controllably swelling and crosslinking the composite fiber preform in sequence to obtain the continuous fiber-reinforced hydrogel flexible implant scaffold.

2. The in situ custom molding method of claim 1, wherein, The material of the hydrogel precursor powder comprises synthetic high molecular materials and / or natural polysaccharide materials; the synthetic high molecular materials comprise one or more of polyvinyl alcohol, polyacrylamide, polyacrylic acid and polyethylene oxide; and the natural polysaccharide materials comprise chitosan and / or gelatin.

3. The in-mould customisation method according to claim 1 or 2, wherein, The diameter of the continuous hydrogel precursor fiber is 50-80 μm.

4. The in situ custom molding process of claim 1, wherein, The diameter of the high-performance continuous fiber is not higher than 50 μm.

5. The method of claim 1 or 4, wherein, The high-performance continuous fiber comprises natural fibers and / or artificial synthetic fibers; the natural fibers comprise one or more of silk, spider silk and animal hair; and the artificial synthetic fibers comprise one or more of carbon fiber, glass fiber, aramid fiber, ultrahigh molecular polyethylene and polyester fiber.

6. The in situ custom molding process of claim 1 wherein, The volume content of the continuous hydrogel precursor fiber in the composite fiber yarn is 10-50%.

7. The in situ custom molding process of claim 1 wherein, The structural design of the braiding structure comprises design of a guiding column and a guiding template; and the guiding column is made of carbon fiber.

8. The in situ custom molding process of claim 1 wherein, The braiding guiding path planning is a circular path or a rectangular path.

9. The continuous fiber-reinforced hydrogel flexible implant scaffold obtained by the in-situ customized forming method according to any one of claims 1-8.

10. Application of the continuous fiber-reinforced hydrogel flexible implant scaffold according to claim 9 in preparation of biomedical materials.

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