A UHMWPE composite fiber with functional coating and preparation method thereof

Abstract

The present invention relates to the field of fiber materials, and discloses a UHMWPE composite fiber with a functional coating and a preparation method thereof. The composite fiber comprises a UHMWPE fiber bundle with a three-dimensional woven structure, and a phenolamine co-deposition modification layer, an inorganic functional nanoparticle deposition layer, and a silk fibroin / polylysine cross-linked porous layer sequentially coated on the surface of the fiber bundle. The present invention sequentially deposits phenolamine and NPs on the surface of the UHMWPE fiber bundle with a three-dimensional woven structure, then constructs a silk fibroin coating with a microporous structure on the surface of the inorganic functional nanoparticle deposition layer to coat the NPs to improve the stability of the NPs, and then self-assembles polylysine with an antibacterial effect with the silk fibroin through electrostatic adsorption, and finally forms a silk fibroin / polylysine cross-linked porous layer after cross-linking. The UHMWPE composite fiber of the present invention has excellent mechanical properties, stability, antibacterial properties and bone regeneration promoting properties.

Description

Technical Field

[0001] The present invention relates to the field of fiber materials, and in particular to a UHMWPE composite fiber with a functional coating and a preparation method thereof. Background Art

[0002] Orthopedic surgery is one of the most common types of clinical surgery. For fracture treatments and other procedures, medical devices such as bone implant screws are often used for fixation, offering advantages such as reliable fixation and minimal invasiveness. However, screw fixation increases trauma to the skin and surrounding soft tissue at the surgical site and may also exacerbate local postoperative swelling, increase the risk of postoperative infection, and lead to poor surgical outcomes. Fixing bone tissue through suturing avoids trauma to healthy physiological areas surrounding the bone tissue, offering advantages such as low cost and a reduced chance of secondary trauma.

[0003] Surgical sutures are one of the commonly used medical consumables and are widely used in the fields of wound suturing, tissue apposition, lumen ligation and implant fixation. There are many types of medical surgical sutures. The sutures currently developed include natural sutures (silk thread, catgut) and artificial sutures (polyglycolide, polyglycolide lactide, polyamide, polyolefin and polyester, etc.). However, the strength of the above sutures is poor and cannot provide sufficient tension during the healing process, so they cannot be used as bone sutures. Ultra-high molecular weight polyethylene (UHMWPE) fiber refers to polyethylene fiber with a molecular weight of 1 million to 5 million, which has the advantages of high strength, good wear resistance, small tissue reaction and biological inertness. Patent CN202210089120.8 discloses a high-strength, easy-to-suture non-absorbable medical suture and its preparation method. The medical suture is made of a core layer woven from ultra-high molecular weight polyethylene fibers and coated with a silicone rubber-based cortex, which can give the suture a smoother surface, thereby reducing the friction between it and the tissue, making it easier for the suture to pass through the tissue and tighten. Patent CN202210187597.X discloses a medical antibacterial UHMWPE suture and its preparation method. The suture includes a UHMWPE fiber braided wire and a liquid-swellable antibacterial coating coated on the surface of the UHMWPE fiber braided wire; the antibacterial coating is a cross-linked network composed of polydimethylsiloxane and povidone iodine, and the iodine is complexed on polyvinyl pyrrolidone and slowly released, so that the suture has good antibacterial effect and antibacterial durability in the body. The above-mentioned UHMWPE suture achieves antibacterial function through a composite antibacterial coating, but it cannot promote bone regeneration and accelerate bone healing. In order to meet the demand for bone sutures in orthopedic surgery, how to improve the strength of the suture and give the suture biological function is one of the ways to solve the above problems. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention provides a UHMWPE composite fiber with a functional coating and a preparation method thereof. The present invention sequentially deposits phenolamine and NPs on the surface of a UHMWPE fiber bundle with a three-dimensional woven structure, then constructs a silk fibroin coating with a microporous structure on the surface of the inorganic functional nanoparticle deposition layer to coat the NPs to improve the stability of the NPs, and then self-assembles polylysine with an antibacterial effect and silk fibroin through electrostatic adsorption, and finally forms a silk fibroin / polylysine cross-linked porous layer after cross-linking. The UHMWPE composite fiber of the present invention has excellent mechanical properties, stability, antibacterial properties and bone regeneration-promoting properties, and can be used as a bone suture.

[0005] The specific technical solutions of the present invention are:

[0006] In the first aspect, the present invention provides a UHMWPE composite fiber with a functional coating, comprising a UHMWPE fiber bundle with a three-directional woven structure, and a phenolamine co-deposition modification layer, an inorganic functional nanoparticle deposition layer, and a silk fibroin / polylysine cross-linked porous layer sequentially coated on the surface of the UHMWPE fiber bundle; the inorganic functional nanoparticles (NPs) have the function of promoting osteoblast differentiation and promoting bone regeneration.

[0007] The present invention sequentially coats the surface of the UHMWPE fiber bundle with a phenolamine co-deposition modification layer, an inorganic functional nanoparticle deposition layer, and a silk fibroin / polylysine cross-linked porous layer.

[0008] UHMWPE fiber is a polymer material with high strength, high abrasion resistance, low tissue reactivity, and biological inertness. Weaving it into a three-dimensional braid allows multiple UHMWPE fibers to form a fiber bundle, further enhancing the mechanical strength required by composite fibers. Furthermore, the macroscopically shaped, concave and convex surface of the three-dimensional braid prevents slippage of the composite fibers during use, thereby enhancing their robustness.

[0009] The phenolamine co-deposition modification layer enriches the surface of the UHMWPE fiber bundle with active groups, effectively addressing the chemical inertness of the UHMWPE fiber and facilitating subsequent surface modification. The presence of the phenolamine co-deposition modification layer also further enhances the mechanical strength of the fiber bundle, making it more suitable for the preparation of composite fibers.

[0010] NPs deposited on the fiber surface can continuously release bioactive functional ions (calcium ions, phosphate particles, or silicate ions, etc.), thereby promoting osteoblast differentiation and bone regeneration. However, simple deposition methods are not conducive to the stable compounding of NPs and composite fibers, and once the external environment changes, the bioactive NPs are easily detached. The phenolamine co-deposited modified layer of the present invention has abundant catechol groups and has strong adhesion. It can compound with NPs through strong interactions such as multiple hydrogen bonds, π bonds, and complex bonds, thereby stably attaching NPs to the surface of the UHMWPE fiber bundle.

[0011] As a biomacromolecule, silk fibroin is a natural polymer with excellent biocompatibility. The coating of silk fibroin not only improves the biocompatibility of the UHMWPE fiber bundle, but also coats NPs between the silk fibroin coating and the phenolamine co-deposition modified layer, thereby improving the composite stability of NPs and making NPs less likely to fall off. The present invention forms a polylysine layer on the surface of the silk fibroin coating by electrostatic adsorption, which can give the composite fiber an excellent antibacterial effect. Finally, the silk fibroin is cross-linked with the polylysine and phenolamine co-deposition modified layer to form a silk fibroin / polylysine cross-linked porous layer, which can further improve the mechanical properties and stability of the coating, and the coating has a microporous structure, which is conducive to the release of active ions of NPs.

[0012] Preferably, the inorganic functional nanoparticles are one or more combinations of nano-hydroxyapatite and nano-bioactive glass.

[0013] In a second aspect, the present invention provides a method for preparing a UHMWPE composite fiber, comprising the following steps:

[0014] The UHMWPE fibers are woven into a three-way woven structure UHMWPE fiber bundle.

[0015] (2) The UHMWPE fiber bundle is immersed in a Tris solution containing catechol and 1,6-hexanediamine and shaken for reaction, and then taken out, washed with water, and dried to obtain a phenolamine co-precipitation modified UHMWPE fiber bundle.

[0016] Phenolamine co-deposition, through Michael addition or Schiff base reaction, forms a coating rich in active groups on the surface of UHMWPE fiber bundles with catechol and 1,6-hexanediamine. This effectively addresses the chemical inertness of UHMWPE fibers and facilitates subsequent surface modification. The presence of this coating also further enhances the mechanical strength of the fiber bundles, making them more suitable for the preparation of composite fibers.

[0017] (3) The UHMWPE fiber bundle modified by phenolamine co-deposition is immersed in a dispersion containing 1.5-3 g / 100 mL of inorganic functional nanoparticles (NPs) at a bath ratio of 1 g: (2200-2900) mL and stirred, and then taken out, washed with water, and dried to obtain a UHMWPE fiber bundle with inorganic functional nanoparticles deposited.

[0018] As mentioned above, a simple deposition method will not be conducive to the stable compounding of NPs and composite fibers. Once the external environment changes, it is easy to cause the biologically active NPs to fall off. The phenolamine co-deposition modified layer of the present invention has rich catechol groups and has strong adhesion. It can be compounded with NPs through strong interactions such as multiple hydrogen bonds, π bonds, and complex bonds, thereby making NPs stably attached to the surface of the UHMWPE fiber bundle. It should be noted that the deposition amount of NPs needs to be reasonably controlled. If too much is deposited, the phenolamine co-deposition modified layer will be over-covered, resulting in the subsequent silk fibroin being unable to be compounded with the phenolamine co-deposition modified layer through chemical cross-linking, thereby causing the silk fibroin coating to fall off easily. Too few NPs will reduce the biological activity of the composite fiber, which is not conducive to promoting bone regeneration.

[0019] (4) The UHMWPE fiber bundle with inorganic functional nanoparticles deposited thereon is immersed in a silk fibroin solution, taken out, and the fiber bundle is placed in anhydrous ethanol for modification, taken out, and dried to obtain a UHMWPE fiber bundle with a silk fibroin coating.

[0020] The coating of silk fibroin not only improves the biocompatibility of the UHMWPE fiber bundle, but also coats the NPs between the silk fibroin coating and the phenolamine co-deposition modification layer, thereby improving the composite stability of the NPs and making the NPs less likely to fall off. It should be noted that there is an α-helical structure in silk fibroin, so it has a certain water solubility. The coating formed by silk fibroin will also be partially soluble in water, resulting in the loss of the physical structure of the coating. In order to change the properties of the silk fibroin coating, the present invention immerses the UHMWPE fiber bundle in anhydrous ethanol after forming the silk fibroin coating, so that the α-helical conformation of the silk fibroin is converted into a water-insoluble β-folded conformation.

[0021] (5) The UHMWPE fiber bundle with silk fibroin coating was placed in a polylysine (PLL) aqueous solution with a concentration of 0.01-0.1 mol / L at a bath ratio of 1 g: (2200-2900) mL, a crosslinking agent was added, the reaction was stirred in the dark, the fiber was taken out, and freeze-dried to obtain a UHMWPE composite fiber with a functional coating.

[0022] Silk fibroin has an isoelectric point of pH 4, negatively charged under neutral conditions; polylysine has an isoelectric point of pH 10, positively charged under neutral conditions. Therefore, PLL can bind to the silk fibroin coating through electrostatic adsorption, imparting excellent antibacterial properties to the composite fiber. Further cross-linking can be performed to crosslink the carboxyl groups in the silk fibroin with the amino groups in the co-deposited modified layer of polylysine and phenolamine, improving the coating's mechanical properties and stability. However, during research, the present invention discovered that while cross-linking increases the density of the coating, excessive density is detrimental to the release of active ions from the inner NP layer. To address this issue, the present invention incorporates a freeze-drying process. This process involves immersing the UHMWPE fiber bundle in the PLL aqueous solution, causing the silk fibroin coating to absorb water and swell due to its inherent hydrophilicity. By freeze-drying the swollen silk fibroin coating, the present invention achieves a coating rich in microporous structure, facilitating the efficient release of active ions from the NPs through the microporous channels, thereby stimulating bone tissue regeneration. Furthermore, the amount of PLL layer must be appropriately controlled. If the concentration or bath ratio of PLL is too high, the micropores may be blocked and ion release channels may not be formed. If the concentration or bath ratio of PLL is too low, the antibacterial effect will be insignificant.

[0023] In summary, the present invention is based on a UHMWPE fiber bundle with a three-dimensional braided structure. It uses the principle of phenolamine co-deposition to allow catechol and 1,6-hexanediamine to self-polymerize on the surface of the UHMWPE fiber, introducing a phenolamine co-deposition modification layer containing active groups; then, functional NPs are deposited by utilizing the complexation between phenolic hydroxyl groups and metal ions; on this basis, silk fibroin and polylysine are sequentially coated and then cross-linked to form a functional coating. The phenolamine co-deposition method can introduce active groups such as phenolic hydroxyl groups, amino groups, and quinone groups on the biologically inert surface of the UHMWPE fiber, while at the same time making the fiber surface rough, providing favorable attachment conditions for subsequent coating modification. The NPs deposited on the fiber surface can continuously release bioactive functional ions (calcium ions, phosphate particles, or silicate ions, etc.), thereby promoting osteoblast differentiation and bone regeneration. The two biomacromolecules, silk fibroin and polylysine, are self-assembled and deposited on the UHMWPE fiber surface under the action of electrostatic adsorption. At the same time, the cross-linking treatment can stably compound the silk fibroin and polylysine on the fiber surface. The porous cross-linked silk fibroin / polylysine layer encapsulates the NPs, effectively preventing them from falling off. The contact bactericidal effect of polylysine, combined with the sustained release of bioactive ions, addresses bacterial infection and bone regeneration issues during orthopedic surgery.

[0024] Preferably, in step (1), a 32-spindle vertical braiding machine is used to add axial yarn fibers along the braiding curling direction to obtain a three-way braided structure UHMWPE fiber bundle at a certain gear ratio and rotation speed.

[0025] As a further preference, in step (1), the number of axial yarn fibers in the three-way braided UHMWPE fiber bundle is 10-40; the gear ratio is: driving wheel: driven wheel) = (30-44): 88, and the rotation speed is 40-80 rpm.

[0026] Preferably, in step (2), the pH of the Tris solution containing catechol and 1,6-hexanediamine is 8-10.

[0027] Preferably, in step (2), the concentration of catechol is 0.25-0.35 g / 100 mL, the concentration of 1,6-hexanediamine is 0.2-0.5 g / 100 mL, and the bath ratio of the UHMWPE fiber bundle to the Tris solution containing catechol and 1,6-hexanediamine is 1 g: (2200-2900) mL.

[0028] Preferably, in step (2), the oscillation reaction time is 20-30 hours, and the drying temperature is 30-50°C.

[0029] Preferably, in step (3), the average particle size of the inorganic functional nanoparticles is 50-200 nm.

[0030] Preferably, in step (3), the stirring time is 2-4 hours and the drying temperature is 30-50°C.

[0031] Preferably, in step (4), the silk fibroin extraction method is as follows: at 50-60° C., 1 g of degummed silk is dissolved in a 9.0-9.3 mol / L LiBr solution in a ratio of 1 g: (40-50) mL, the solution is centrifuged and dialyzed for 2-4 days, the water is changed every 4-6 hours, and the solution is freeze-dried to obtain the silk fibroin.

[0032] As a further preference, in step (4), the centrifugal speed is 3000-5000 r / min, the centrifugal time is 10-15 min, and the molecular weight cut-off of the dialysis bag used for dialysis is 7000-10000 Mw.

[0033] Preferably, in step (4), the concentration of the silk fibroin solution is 4-8 wt %, the solvent is formic acid or hexafluoroisopropanol, the bath ratio of the UHMWPE fiber bundle on which the inorganic functional nanoparticles are deposited to the silk fibroin solution is 1 g: (2300-2900) mL, and the immersion time is 15-30 min.

[0034] Too high a concentration of silk fibroin solution and too long a soaking time can easily make the silk fibroin coating too thick, causing the NPs to be over-coated, thereby reducing the efficiency of NPs in releasing active ions.

[0035] Preferably, in step (4), the ratio of the fiber bundle to anhydrous ethanol is 1 g: (1000-1500) mL, and the modification time in anhydrous ethanol modification is 4-8 h.

[0036] Preferably, in step (5), the cross-linking agent comprises N-hydroxysuccinimide, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and genipin solution.

[0037] As a further preference, in step (5), the ratio of the UHMWPE fiber bundle with silk fibroin coating, N-hydroxysuccinimide, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and genipin solution is 1 g: (6.0-8.0) g: (4.0-6.0) g: (10-25) mL, wherein the concentration of the genipin solution is 0.8-1.2 wt%.

[0038] Preferably, in step (5), the stirring reaction time is 30-60 min.

[0039] Compared with the prior art, the present invention has the following technical effects:

[0040] (1) The present invention uses UHMWPE fibers, which have high strength, high wear resistance, low tissue reactivity, and biological inertness, as a base material and weaves them into a three-dimensional braided structure. Compared with conventional bone sutures, this suture can better meet the special mechanical performance requirements of bone sutures. At the same time, the concave-convex surface formed by the three-dimensional braided structure can also prevent the composite fibers from slipping during use, thereby improving the firmness of the composite fibers.

[0041] (2) The present invention constructs a phenolamine co-deposition modification layer on the surface of the UHMWPE fiber bundle, enriching the fiber bundle surface with active groups. This effectively addresses the chemical inertness of the UHMWPE fibers and facilitates subsequent surface modification of the fibers. Furthermore, the presence of the phenolamine co-deposition modification layer further enhances the mechanical strength of the fiber bundle, making the UHMWPE fiber bundle more suitable for the preparation of composite fibers.

[0042] (3) The present invention constructs an inorganic functional nanoparticle deposition layer on the surface of the phenolamine co-deposition modified layer. The deposited NPs can continuously release bioactive functional ions, thereby promoting osteoblast differentiation and bone regeneration. In addition, the phenolamine co-deposition modified layer of the present invention has abundant catechol groups and strong adhesion. It can form complexes with NPs through strong interactions such as multiple hydrogen bonds, π bonds, and complex bonds, thereby stably adhering the NPs to the surface of the UHMWPE fiber bundle.

[0043] (4) The present invention constructs a silk fibroin / polylysine cross-linked porous layer on the surface of the inorganic functional nanoparticle deposition layer. Among them, silk fibroin not only improves the biocompatibility of the UHMWPE fiber bundle, but also coats NPs between the silk fibroin coating and the phenolamine co-deposition modification layer, thereby improving the composite stability of NPs. The polylysine layer is formed on the silk fibroin surface by electrostatic adsorption, which can give the composite fiber an excellent antibacterial effect. Finally, the silk fibroin is cross-linked with the polylysine and phenolamine co-deposition modification layer to form a silk fibroin / polylysine cross-linked porous layer, which can further improve the mechanical properties and stability of the coating. In addition, the coating has a microporous structure, which is conducive to the release of active ions of NPs. DETAILED DESCRIPTION

[0044] The present invention will be further described below with reference to the embodiments.

[0045] Overall embodiment

[0046] A UHMWPE composite fiber with a functional coating comprises a UHMWPE fiber bundle with a three-way braided structure, and a phenolamine co-deposition modification layer, an inorganic functional nanoparticle deposition layer (the inorganic functional nanoparticles are nanohydroxyapatite and / or nanobioactive glass), and a silk fibroin / polylysine cross-linked porous layer, which are sequentially coated on the surface of the UHMWPE fiber bundle; the inorganic functional nanoparticles have the function of promoting osteoblast differentiation and bone regeneration.

[0047] A method for preparing a UHMWPE composite fiber with a functional coating comprises the following steps:

[0048] (1) Weaving UHMWPE fibers into a three-way braided UHMWPE fiber bundle: Using a 32-spindle vertical spindle braiding machine, axial yarn fibers (preferably 30 fibers) are added along the braiding curling direction, and a three-way braided UHMWPE fiber bundle is obtained under a certain gear ratio (preferably driving wheel: driven wheel = (30-44) : 88) and a rotation speed (preferably 40-80 rpm).

[0049] (2) Phenolamine co-precipitation modification: The UHMWPE fiber bundle is immersed in a Tris solution (pH 8-10) containing 0.25-0.35 g / 100 mL of catechol and 0.2-0.5 g / 100 mL of 1,6-hexanediamine at a bath ratio of 1 g: (2200-2900) mL, and the mixture is shaken for 20-30 h. The fiber bundle is then washed with water and dried at 30-50°C to obtain a UHMWPE fiber bundle modified by phenolamine co-precipitation.

[0050] (3) The UHMWPE fiber bundle modified by phenolamine co-deposition is immersed in a dispersion containing 1.5-3g / 100mL inorganic functional nanoparticles (average particle size 50-200nm) at a bath ratio of 1g:(2200-2900)mL and stirred for 2-4h. The fiber bundle is taken out, washed with water, and dried at 30-50℃ to obtain a UHMWPE fiber bundle with inorganic functional nanoparticles deposited.

[0051] (4) At 50-60°C, 1 g of degummed silk was dissolved in a 9.0-9.3 mol / L LiBr solution at a ratio of 1 g: (40-50) mL. The solution was centrifuged at 3000-5000 r / min for 10-15 min, placed in a dialysis bag with a molecular weight cutoff of 7000-10000 Mw and dialyzed for 2-4 days. The water was changed every 4-6 h, and the solution was freeze-dried to obtain silk fibroin. The UHMWPE fiber bundle with inorganic functional nanoparticles deposited was placed in a 4-8 wt% silk fibroin solution (solvent: formic acid or hexafluoroisopropanol) at a bath ratio of 1: (2300-2900) for 15-30 min, removed, and the fiber bundle was modified in anhydrous ethanol at a bath ratio of 1 g: (1000-1500) mL for 4-8 h. The fiber bundle was removed and dried to obtain a UHMWPE fiber bundle with a silk fibroin coating.

[0052] (5) The UHMWPE fiber bundle with silk fibroin coating was placed in a polylysine (PLL) aqueous solution with a concentration of 0.01-0.1 mol / L at a bath ratio of 1 g: (2200-2900) mL. 6.0-8.0 g of N-hydroxysuccinimide, 4.0-6.0 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 10-25 mL of 0.8-1.2 wt% genipin solution were added to each 1 g of the UHMWPE fiber bundle with silk fibroin coating. The mixture was stirred in the dark for 30-60 min, taken out, and freeze-dried to obtain a UHMWPE composite fiber with a functional coating.

[0053] Example 1

[0054] (1) Ultra-high molecular weight polyethylene (UHMWPE) fiber weaving: A 32-spindle vertical braiding machine was used to add 30 axial yarn fibers along the braiding curling direction. The gear ratio (driving wheel: driven wheel) was set to 30:88, and a three-way braided UHMWPE fiber bundle was obtained at a rotation speed of 40 rpm.

[0055] (2) Phenolamine co-precipitation modification: 0.7 g of tris(hydroxymethyl)aminomethane hydrochloride) was dissolved in 100 mL of deionized water. After thorough stirring, 1 mol / L dilute hydrochloric acid solution was added to adjust the pH to 9. 0.3 g of catechol and 0.3 g of 1,6-hexanediamine were added and stirred until dissolved. The UHMWPE fiber bundle prepared in step (1) was placed in the solution at a bath ratio of 1 g:2500 mL and reacted under shaking conditions for 24 h. The fiber bundle was then removed, washed with water, and dried at 40°C to obtain a phenolamine co-precipitation modified UHMWPE fiber bundle.

[0056] (3) Deposition of inorganic functional nanoparticles (NPs): 2 g of hydroxyapatite NPs with an average particle size of 200 nm were dispersed in 100 mL of water under ultrasonic conditions for 10 min. The UHMWPE fiber bundle obtained in step (2) was placed in the particle dispersion at a bath ratio of 1 g:2500 mL and stirred at room temperature for 3 h. The fiber bundle was taken out, washed with water, and dried at 40°C to obtain a UHMWPE fiber bundle with NPs deposited.

[0057] (4) Extraction of silk fibroin: Degummed silk was dissolved in 9.3 M LiBr solution at 60°C with a silk to solution ratio (w:v) of 1 g:50 mL. The solution was centrifuged at 3000 rpm for 10 min and packaged in a dialysis bag with a molecular weight cutoff of 7000 and dialyzed for three days. The water was changed every 5 h and the solution was freeze-dried to obtain silk fibroin.

[0058] (5) Coating of UHMWPE Fibers with Silk Fibroin: The silk fibroin prepared in step (4) was dissolved in hexafluoroisopropanol to prepare a 5 wt% silk fibroin aqueous solution. The UHMWPE fiber bundle obtained in step (3) was placed in 100 mL of the silk fibroin solution at a bath ratio of 1 g:2500 mL and soaked for 30 min. The fiber bundle was then placed in anhydrous ethanol at a bath ratio of 1 g:1000 mL for 4 h to obtain a UHMWPE fiber bundle coated with silk fibroin.

[0059] (6) Coating and cross-linking of polylysine (PLL): The UHMWPE fiber bundle obtained in step (5) was placed in 100 mL of a 0.05 M polylysine (PLL) aqueous solution at a bath ratio of 1 g:2500 mL. 6 g of N-hydroxysuccinimide, 4 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 20 mL of a 1 wt% genipin solution were added per 1 g of the fiber bundle. The mixture was stirred in the dark for 30 min, taken out, and freeze-dried to obtain UHMWPE composite fibers.

[0060] Example 2

[0061] (1) Ultra-high molecular weight polyethylene (UHMWPE) fiber weaving: A 32-spindle vertical braiding machine was used to add 30 axial yarn fibers along the braiding curling direction, and the gear ratio (driving wheel: driven wheel) was set to 30:88. A three-way braided UHMWPE fiber bundle was obtained at a rotation speed of 40 rpm.

[0062] (2) Phenolamine co-precipitation modification: 0.7 g of tris(hydroxymethyl)aminomethane hydrochloride) was dissolved in 100 mL of deionized water. After thorough stirring, 1 mol / L dilute hydrochloric acid solution was added to adjust the pH to 9. 0.3 g of catechol and 0.3 g of 1,6-hexanediamine were added and stirred until dissolved. The UHMWPE fiber bundle prepared in step (1) was placed in the solution at a bath ratio of 1 g:2500 mL and reacted under shaking conditions for 24 h. The fiber bundle was then removed, washed with water, and dried at 40°C to obtain a phenolamine co-precipitation modified UHMWPE fiber bundle.

[0063] (3) Deposition of inorganic functional nanoparticles (NPs): 2 g of nano-bioactive glass NPs with an average particle size of 200 nm were dispersed in 100 mL of water under ultrasonic conditions for 10 min. The UHMWPE fiber bundle obtained in step (2) was placed in the particle dispersion at a bath ratio of 1 g:2500 mL and stirred at room temperature for 3 h. After being taken out, the fiber bundle was washed with water and dried at 40°C to obtain a UHMWPE fiber bundle with NPs deposited thereon.

[0064] (4) Extraction of silk fibroin: Degummed silk was dissolved in 9.3 M LiBr solution at 60°C with a silk to solution ratio (w:v) of 1 g:50 mL. The solution was centrifuged at 3000 rpm for 10 min and packaged in a dialysis bag with a molecular weight cutoff of 7000 and dialyzed for three days. The water was changed every 5 h and the solution was freeze-dried to obtain silk fibroin.

[0065] (5) Coating of UHMWPE Fibers with Silk Fibroin: The silk fibroin prepared in step (4) was dissolved in hexafluoroisopropanol to prepare a 5 wt% silk fibroin solution. The UHMWPE fiber bundle obtained in step (3) was placed in 100 mL of the silk fibroin solution at a bath ratio of 1 g:2500 mL and soaked for 30 min. The fiber bundle was then placed in anhydrous ethanol at a bath ratio of 1 g:1000 mL for 4 h to obtain a UHMWPE fiber bundle coated with silk fibroin.

[0066] (6) Coating and cross-linking of polylysine (PLL): The UHMWPE fiber bundle obtained in step (5) was placed in 100 mL of a 0.05 M polylysine (PLL) aqueous solution at a bath ratio of 1 g:2500 mL. 6 g of N-hydroxysuccinimide, 4 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 20 mL of a 1 wt% genipin solution were added per 1 g of the fiber bundle. The mixture was stirred in the dark for 30 min, taken out, and freeze-dried to obtain UHMWPE composite fibers.

[0067] Example 3

[0068] (1) Ultra-high molecular weight polyethylene (UHMWPE) fiber weaving: A 32-spindle vertical braiding machine was used to add 30 axial yarn fibers along the braiding curling direction. The gear ratio (driving wheel: driven wheel) was set to 30:88, and a three-way braided structure UHMWPE fiber bundle was obtained at a rotation speed of 40 rpm.

[0069] (2) Phenolamine co-precipitation modification: 0.7 g of tris(hydroxymethyl)aminomethane hydrochloride) was dissolved in 100 mL of deionized water. After thorough stirring, 1 mol / L dilute hydrochloric acid solution was added to adjust the pH to 9. 0.3 g of catechol and 0.3 g of 1,6-hexanediamine were added and stirred until dissolved. The UHMWPE fiber bundle prepared in step (1) was placed in the solution at a bath ratio of 1 g:2500 mL and reacted under shaking conditions for 24 h. The fiber bundle was then removed, washed with water, and dried at 40°C to obtain a phenolamine co-precipitation modified UHMWPE fiber bundle.

[0070] (3) Deposition of inorganic functional nanoparticles (NPs): 2 g of hydroxyapatite NPs with an average particle size of 200 nm were dispersed in 100 mL of water under ultrasonic conditions for 10 min. The UHMWPE fiber bundle obtained in step (2) was placed in the particle dispersion at a bath ratio of 1 g:2500 mL and stirred at room temperature for 3 h. The fiber bundle was taken out, washed with water, and dried at 40°C to obtain a UHMWPE fiber bundle with NPs deposited.

[0071] (4) Extraction of silk fibroin: Degummed silk was dissolved in 9.3 M LiBr solution at 60°C with a silk to solution ratio (w:v) of 1 g:50 mL. The solution was centrifuged at 3000 rpm for 10 min and packaged in a dialysis bag with a molecular weight cutoff of 7000 and dialyzed for three days. The water was changed every 5 h and the solution was freeze-dried to obtain silk fibroin.

[0072] (5) Coating of UHMWPE Fibers with Silk Fibroin: The silk fibroin prepared in step (4) was dissolved in hexafluoroisopropanol to prepare a 5 wt% silk fibroin solution. The UHMWPE fiber bundle obtained in step (3) was placed in 100 mL of the silk fibroin solution at a bath ratio of 1 g:2500 mL and soaked for 30 min. The fiber bundle was then placed in anhydrous ethanol at a bath ratio of 1 g:1000 mL for 4 h to obtain a UHMWPE fiber bundle coated with silk fibroin.

[0073] (6) Coating and cross-linking of polylysine (PLL): The UHMWPE fiber bundle obtained in step (5) was placed in 100 mL of a 0.02 M polylysine (PLL) aqueous solution at a bath ratio of 1 g:2500 mL. 6 g of N-hydroxysuccinimide, 4 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 20 mL of a 1 wt% genipin solution were added per 1 g of the fiber bundle. The mixture was stirred in the dark for 30 min, taken out, and freeze-dried to obtain UHMWPE composite fibers.

[0074] Example 4

[0075] (1) Ultra-high molecular weight polyethylene (UHMWPE) fiber weaving: A 32-spindle vertical braiding machine was used to add 30 axial yarn fibers along the braiding curling direction. The gear ratio (driving wheel: driven wheel) was set to 30:88, and a three-way braided structure UHMWPE fiber bundle was obtained at a rotation speed of 40 rpm.

[0076] (2) Phenolamine co-precipitation modification: 0.7 g of tris(hydroxymethyl)aminomethane hydrochloride) was dissolved in 100 mL of deionized water. After thorough stirring, 1 mol / L dilute hydrochloric acid solution was added to adjust the pH to 9. 0.3 g of catechol and 0.3 g of 1,6-hexanediamine were added and stirred until dissolved. The UHMWPE fiber bundle prepared in step (1) was placed in the solution at a bath ratio of 1 g:2500 mL and reacted under shaking conditions for 24 h. The fiber bundle was then removed, washed with water, and dried at 40°C to obtain a phenolamine co-precipitation modified UHMWPE fiber bundle.

[0077] (3) Deposition of inorganic functional nanoparticles (NPs): 2 g of hydroxyapatite NPs with an average particle size of 200 nm were dispersed in 100 mL of water under ultrasonic conditions for 10 min. The UHMWPE fiber bundle obtained in step (2) was placed in the particle dispersion at a bath ratio of 1 g:2500 mL and stirred at room temperature for 3 h. The fiber bundle was taken out, washed with water, and dried at 40°C to obtain a UHMWPE fiber bundle with NPs deposited.

[0078] (4) Extraction of silk fibroin: Degummed silk was dissolved in 9.3 M LiBr solution at 60°C with a silk to solution ratio (w:v) of 1 g:50 mL. The solution was centrifuged at 3000 rpm for 10 min and packaged in a dialysis bag with a molecular weight cutoff of 7000 and dialyzed for three days. The water was changed every 5 h and the solution was freeze-dried to obtain silk fibroin.

[0079] (5) Coating of UHMWPE Fibers with Silk Fibroin: The silk fibroin prepared in step (4) was dissolved in hexafluoroisopropanol to prepare an 8 wt% silk fibroin solution. The UHMWPE fiber bundle obtained in step (3) was placed in 100 mL of the silk fibroin solution at a bath ratio of 1 g:2500 mL and soaked for 30 min. The fiber bundle was then removed. The fiber bundle was then placed in anhydrous ethanol at a bath ratio of 1 g:1000 mL for 4 h to obtain a UHMWPE fiber bundle coated with silk fibroin.

[0080] (6) Coating and cross-linking of polylysine (PLL): The UHMWPE fiber bundle obtained in step (5) was placed in 100 mL of a 0.05 M polylysine (PLL) aqueous solution at a bath ratio of 1 g:2500 mL. 6 g of N-hydroxysuccinimide, 4 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 20 mL of a 1 wt% genipin solution were added per 1 g of the fiber bundle. The fiber bundle was taken out and freeze-dried to obtain a UHMWPE composite fiber.

[0081] Comparative Example 1 (no three-way weaving)

[0082] (1) Phenolamine co-precipitation modification: 0.7 g of tris(hydroxymethyl)aminomethane hydrochloride) was dissolved in 100 mL of deionized water. After thorough stirring, 1 mol / L dilute hydrochloric acid solution was added to adjust the pH to 9. 0.3 g of catechol and 0.3 g of 1,6-hexanediamine were added and stirred until dissolved. UHMWPE fibers were placed in the solution at a bath ratio of 1 g:2500 mL and reacted under shaking conditions for 24 h. The fibers were then removed, washed with water, and dried at 40°C to obtain phenolamine co-precipitation-modified UHMWPE fibers.

[0083] (2) Deposition of inorganic functional nanoparticles (NPs): 2 g of hydroxyapatite NPs with an average particle size of 200 nm were dispersed in 100 mL of water under ultrasonic conditions for 10 min. The UHMWPE fiber obtained in step (1) was placed in the particle dispersion at a bath ratio of 1 g:2500 mL and stirred at room temperature for 3 h. The fiber was taken out, washed with water, and dried at 40°C to obtain UHMWPE fibers with NPs deposited.

[0084] (3) Extraction of silk fibroin: Degummed silk was dissolved in 9.3 M LiBr solution at 60°C with a silk to solution ratio (w:v) of 1 g:50 mL. The solution was centrifuged at 3000 rpm for 10 min and packaged in a dialysis bag with a molecular weight cutoff of 7000 and dialyzed for three days. The water was changed every 5 h and the solution was freeze-dried to obtain silk fibroin.

[0085] (4) Coating of UHMWPE Fibers with Silk Fibroin: The silk fibroin prepared in step (3) was dissolved in hexafluoroisopropanol to prepare a 5 wt% silk fibroin solution. The UHMWPE fibers obtained in step (2) were placed in 100 mL of the silk fibroin solution at a bath ratio of 1 g:2500 mL and immersed for 30 min. The fibers were then removed. The fiber bundles were then placed in anhydrous ethanol at a bath ratio of 1 g:1000 mL for 4 h to obtain UHMWPE fibers coated with silk fibroin.

[0086] (5) Coating and cross-linking of polylysine (PLL): The UHMWPE fiber obtained in step (4) was placed in 100 mL of a 0.05 M polylysine (PLL) aqueous solution at a bath ratio of 1 g:2500 mL. 6 g of N-hydroxysuccinimide, 4 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 20 mL of a 1 wt% genipin solution were added per 1 g of fiber. The mixture was stirred in the dark for 30 min, taken out, and freeze-dried to obtain a UHMWPE composite fiber.

[0087] Comparative Example 2 (no phenolamine co-deposition modification)

[0088] (1) Ultra-high molecular weight polyethylene (UHMWPE) fiber weaving: A 32-spindle vertical braiding machine was used to add 30 axial yarn fibers along the braiding curling direction. The gear ratio (driving wheel: driven wheel) was set to 30:88, and a three-way braided structure UHMWPE fiber bundle was obtained at a rotation speed of 40 rpm.

[0089] (2) Deposition of inorganic functional nanoparticles (NPs): 2 g of hydroxyapatite NPs with an average particle size of 200 nm were dispersed in 100 mL of water under ultrasonic conditions for 10 min. The UHMWPE fiber bundle obtained in step (1) was placed in the particle dispersion at a bath ratio of 1 g:2500 mL and stirred at room temperature for 3 h. The fiber bundle was taken out, washed with water, and dried at 40°C to obtain a UHMWPE fiber bundle with NPs deposited.

[0090] (3) Extraction of silk fibroin: Degummed silk was dissolved in 9.3 M LiBr solution at 60°C with a silk to solution ratio (w:v) of 1 g:50 mL. The solution was centrifuged at 3000 rpm for 10 min and packaged in a dialysis bag with a molecular weight cutoff of 7000 and dialyzed for three days. The water was changed every 5 h and the solution was freeze-dried to obtain silk fibroin.

[0091] (4) Coating of UHMWPE Fibers with Silk Fibroin: The silk fibroin prepared in step (3) was dissolved in hexafluoroisopropanol to prepare a 5 wt% silk fibroin solution. The UHMWPE fiber bundle obtained in step (2) was placed in 100 mL of the silk fibroin solution at a bath ratio of 1 g:2500 mL and soaked for 30 min. The fiber bundle was then placed in anhydrous ethanol at a bath ratio of 1 g:1000 mL for 4 h to obtain a UHMWPE fiber bundle coated with silk fibroin.

[0092] (5) Coating and cross-linking of polylysine (PLL): The UHMWPE fiber bundle obtained in step (4) was placed in 100 mL of a 0.05 M polylysine (PLL) aqueous solution at a bath ratio of 1 g:2500 mL. 6 g of N-hydroxysuccinimide, 4 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 20 mL of a 1 wt% genipin solution were added per 1 g of the fiber bundle. The mixture was stirred in the dark for 30 min, taken out, and freeze-dried to obtain UHMWPE composite fibers.

[0093] Comparative Example 3 (no NPs deposition)

[0094] (1) Ultra-high molecular weight polyethylene (UHMWPE) fiber weaving: A 32-spindle vertical braiding machine was used to add 30 axial yarn fibers along the braiding curling direction. The gear ratio (driving wheel: driven wheel) was set to 30:88, and a three-way braided UHMWPE fiber bundle was obtained at a rotation speed of 40 rpm.

[0095] (2) Phenolamine co-precipitation modification: 0.7 g of tris(hydroxymethyl)aminomethane hydrochloride) was dissolved in 100 mL of deionized water. After thorough stirring, 1 mol / L dilute hydrochloric acid solution was added to adjust the pH to 9. 0.3 g of catechol and 0.3 g of 1,6-hexanediamine were added and stirred until dissolved. The UHMWPE fiber bundle prepared in step (1) was placed in the solution at a bath ratio of 1 g:2500 mL and reacted under shaking conditions for 24 h. The fiber bundle was then removed, washed with water, and dried at 40°C to obtain a phenolamine co-precipitation modified UHMWPE fiber bundle.

[0096] (3) Extraction of silk fibroin: Degummed silk was dissolved in 9.3 M LiBr solution at 60°C with a silk to solution ratio (w:v) of 1 g:50 mL. The solution was centrifuged at 3000 rpm for 10 min and packaged in a dialysis bag with a molecular weight cutoff of 7000 and dialyzed for three days. The water was changed every 5 h and the solution was freeze-dried to obtain silk fibroin.

[0097] (4) Coating of UHMWPE Fibers with Silk Fibroin: The silk fibroin prepared in step (3) was dissolved in hexafluoroisopropanol to prepare a 5 wt% silk fibroin solution. The UHMWPE fiber bundle obtained in step (2) was placed in 100 mL of the silk fibroin solution at a bath ratio of 1 g:2500 mL and soaked for 30 min. The fiber bundle was then placed in anhydrous ethanol at a bath ratio of 1 g:1000 mL for 4 h to obtain a UHMWPE fiber bundle coated with silk fibroin.

[0098] (5) Coating and cross-linking of polylysine (PLL): The UHMWPE fiber bundle obtained in step (4) was placed in 100 mL of a 0.05 M polylysine (PLL) aqueous solution at a bath ratio of 1 g:2500 mL. 6 g of N-hydroxysuccinimide, 4 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 20 mL of a 1 wt% genipin solution were added per 1 g of the fiber bundle. The mixture was stirred in the dark for 30 min, taken out, and freeze-dried to obtain UHMWPE composite fibers.

[0099] Comparative Example 4 (Silk fibroin coating not modified by ethanol)

[0100] (1) Ultra-high molecular weight polyethylene (UHMWPE) fiber weaving: A 32-spindle vertical braiding machine was used to add 30 axial yarn fibers along the braiding curling direction. The gear ratio (driving wheel: driven wheel) was set to 30:88, and a three-way braided UHMWPE fiber bundle was obtained at a rotation speed of 40 rpm.

[0101] (2) Phenolamine co-precipitation modification: 0.7 g of tris(hydroxymethyl)aminomethane hydrochloride) was dissolved in 100 mL of deionized water. After thorough stirring, 1 mol / L dilute hydrochloric acid solution was added to adjust the pH to 9. 0.3 g of catechol and 0.3 g of 1,6-hexanediamine were added and stirred until dissolved. The UHMWPE fiber bundle prepared in step (1) was placed in the solution at a bath ratio of 1 g:2500 mL and reacted under shaking conditions for 24 h. The fiber bundle was then removed, washed with water, and dried at 40°C to obtain a phenolamine co-precipitation modified UHMWPE fiber bundle.

[0102] (3) Deposition of inorganic functional nanoparticles (NPs): 2 g of hydroxyapatite NPs with an average particle size of 200 nm were dispersed in 100 mL of water under ultrasonic conditions for 10 min. The UHMWPE fiber bundle obtained in step (2) was placed in the particle dispersion at a bath ratio of 1:2500 and stirred at room temperature for 3 h. The fiber bundle was taken out, washed with water, and dried at 40°C to obtain a UHMWPE fiber bundle with NPs deposited.

[0103] (4) Extraction of silk fibroin: Degummed silk was dissolved in 9.3 M LiBr solution at 60°C with a silk to solution ratio (w:v) of 1 g:50 mL. The solution was centrifuged at 3000 rpm for 10 min and packaged in a dialysis bag with a molecular weight cutoff of 7000 and dialyzed for three days. The water was changed every 5 h and the solution was freeze-dried to obtain silk fibroin.

[0104] (5) Coating of UHMWPE fibers with silk fibroin: The silk fibroin prepared in step (4) was dissolved in hexafluoroisopropanol to prepare a 5 wt% silk fibroin solution. The UHMWPE fiber bundle obtained in step (3) was placed in 100 mL of the silk fibroin solution at a bath ratio of 1 g:2500 mL and soaked for 30 min. The fiber bundle was taken out to obtain a UHMWPE fiber bundle with a silk fibroin coating.

[0105] (6) Coating and cross-linking of polylysine (PLL): The UHMWPE fiber bundle obtained in step (5) was placed in 100 mL of a 0.05 M polylysine (PLL) aqueous solution at a bath ratio of 1 g:2500 mL. 6 g of N-hydroxysuccinimide, 4 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 20 mL of a 1 wt% genipin solution were added per 1 g of the fiber bundle. The mixture was stirred in the dark for 30 min, taken out, and freeze-dried to obtain UHMWPE composite fibers.

[0106] Comparative Example 5 (PLL concentration is too high)

[0107] (1) Ultra-high molecular weight polyethylene (UHMWPE) fiber weaving: A 32-spindle vertical braiding machine was used to add 30 axial yarn fibers along the braiding curling direction. The gear ratio (driving wheel: driven wheel) was set to 30:88, and a three-way braided UHMWPE fiber bundle was obtained at a rotation speed of 40 rpm.

[0108] (2) Phenolamine co-precipitation modification: 0.7 g of tris(hydroxymethyl)aminomethane hydrochloride) was dissolved in 100 mL of deionized water. After thorough stirring, 1 mol / L dilute hydrochloric acid solution was added to adjust the pH to 9. 0.3 g of catechol and 0.3 g of 1,6-hexanediamine were added and stirred until dissolved. The UHMWPE fiber bundle prepared in step (1) was placed in the solution at a bath ratio of 1 g:2500 mL and reacted under shaking conditions for 24 h. The fiber bundle was then removed, washed with water, and dried at 40°C to obtain a phenolamine co-precipitation modified UHMWPE fiber bundle.

[0109] (3) Deposition of inorganic functional nanoparticles (NPs): 2 g of hydroxyapatite NPs with an average particle size of 200 nm were dispersed in 100 mL of water under ultrasonic conditions for 10 min. The UHMWPE fiber bundle obtained in step (2) was placed in the particle dispersion at a bath ratio of 1 g:2500 mL and stirred at room temperature for 3 h. The fiber bundle was taken out, washed with water, and dried at 40°C to obtain a UHMWPE fiber bundle with NPs deposited.

[0110] (4) Extraction of silk fibroin: Degummed silk was dissolved in 9.3 M LiBr solution at 60°C with a silk to solution ratio (w:v) of 1 g:50 mL. The solution was centrifuged at 3000 rpm for 10 min and packaged in a dialysis bag with a molecular weight cutoff of 7000 and dialyzed for three days. The water was changed every 5 h and the solution was freeze-dried to obtain silk fibroin.

[0111] (5) Coating of UHMWPE Fibers with Silk Fibroin: The silk fibroin prepared in step (4) was dissolved in hexafluoroisopropanol to prepare a 5 wt% silk fibroin solution. The UHMWPE fiber bundle obtained in step (3) was placed in 100 mL of the silk fibroin solution at a bath ratio of 1 g:2500 mL and soaked for 30 min. The fiber bundle was then placed in anhydrous ethanol at a bath ratio of 1 g:1000 mL for 4 h to obtain a UHMWPE fiber bundle coated with silk fibroin.

[0112] (6) Coating and cross-linking of polylysine (PLL): The UHMWPE fiber bundle obtained in step (5) was placed in 100 mL of a 3 M polylysine (PLL) aqueous solution at a bath ratio of 1 g:2500 mL. 6 g of N-hydroxysuccinimide, 4 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 20 mL of a 1 wt% genipin solution were added per 1 g of the fiber bundle. The mixture was stirred in the dark for 30 min, taken out, and freeze-dried to obtain UHMWPE composite fibers.

[0113] Comparative Example 6 (PLL concentration is too low)

[0114] (1) Ultra-high molecular weight polyethylene (UHMWPE) fiber weaving: A 32-spindle vertical braiding machine was used to add 30 axial yarn fibers along the braiding curling direction. The gear ratio (driving wheel: driven wheel) was set to 30:88, and a three-way braided UHMWPE fiber bundle was obtained at a rotation speed of 40 rpm.

[0115] (2) Phenolamine co-precipitation modification: 0.7 g of tris(hydroxymethyl)aminomethane hydrochloride) was dissolved in 100 mL of deionized water. After thorough stirring, 1 mol / L dilute hydrochloric acid solution was added to adjust the pH to 9. 0.3 g of catechol and 0.3 g of 1,6-hexanediamine were added and stirred until dissolved. The UHMWPE fiber bundle prepared in step (1) was placed in the solution at a bath ratio of 1 g:2500 mL and reacted under shaking conditions for 24 h. The fiber bundle was then removed, washed with water, and dried at 40°C to obtain a phenolamine co-precipitation modified UHMWPE fiber bundle.

[0116] (3) Deposition of inorganic functional nanoparticles (NPs): 2 g of hydroxyapatite NPs with an average particle size of 200 nm were dispersed in 100 mL of water under ultrasonic conditions for 10 min. The UHMWPE fiber bundle obtained in step (2) was placed in the particle dispersion at a bath ratio of 1 g:2500 mL and stirred at room temperature for 3 h. The fiber bundle was taken out, washed with water, and dried at 40°C to obtain a UHMWPE fiber bundle with NPs deposited.

[0117] (4) Extraction of silk fibroin: Degummed silk was dissolved in 9.3 M LiBr solution at 60°C with a silk to solution ratio (w:v) of 1 g:50 mL. The solution was centrifuged at 3000 rpm for 10 min and packaged in a dialysis bag with a molecular weight cutoff of 7000 and dialyzed for three days. The water was changed every 5 h and the solution was freeze-dried to obtain silk fibroin.

[0118] (5) Coating of UHMWPE Fibers with Silk Fibroin: The silk fibroin prepared in step (4) was dissolved in hexafluoroisopropanol to prepare a 5 wt% silk fibroin solution. The UHMWPE fiber bundle obtained in step (3) was placed in 100 mL of the silk fibroin solution at a bath ratio of 1 g:2500 mL and soaked for 30 min. The fiber bundle was then placed in anhydrous ethanol at a bath ratio of 1 g:1000 mL for 4 h to obtain a UHMWPE fiber bundle coated with silk fibroin.

[0119] (6) Coating and cross-linking of polylysine (PLL): The UHMWPE fiber bundle obtained in step (5) was placed in 100 mL of a 0.001 M polylysine (PLL) aqueous solution at a bath ratio of 1 g:2500 mL. 6 g of N-hydroxysuccinimide, 4 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 20 mL of a 1 wt% genipin solution were added per 1 g of the fiber bundle. The mixture was stirred in the dark for 30 min, taken out, and freeze-dried to obtain UHMWPE composite fibers.

[0120] Comparative Example 7 (freeze drying was not performed in step 6)

[0121] (1) Ultra-high molecular weight polyethylene (UHMWPE) fiber weaving: A 32-spindle vertical braiding machine was used to add 30 axial yarn fibers along the braiding curling direction. The gear ratio (driving wheel: driven wheel) was set to 30:88, and a three-way braided UHMWPE fiber bundle was obtained at a rotation speed of 40 rpm.

[0122] (2) Phenolamine co-precipitation modification: 0.7 g of tris(hydroxymethyl)aminomethane hydrochloride) was dissolved in 100 mL of deionized water. After thorough stirring, 1 mol / L dilute hydrochloric acid solution was added to adjust the pH to 9. 0.3 g of catechol and 0.3 g of 1,6-hexanediamine were added and stirred until dissolved. The UHMWPE fiber bundle prepared in step (1) was placed in the solution at a bath ratio of 1 g:2500 mL and reacted under shaking conditions for 24 h. The fiber bundle was then removed, washed with water, and dried at 40°C to obtain a phenolamine co-precipitation modified UHMWPE fiber bundle.

[0123] (3) Deposition of inorganic functional nanoparticles (NPs): 2 g of hydroxyapatite NPs with an average particle size of 200 nm were dispersed in 100 mL of water under ultrasonic conditions for 10 min. The UHMWPE fiber bundle obtained in step (2) was placed in the particle dispersion at a bath ratio of 1 g:2500 mL and stirred at room temperature for 3 h. The fiber bundle was taken out, washed with water, and dried at 40°C to obtain a UHMWPE fiber bundle with NPs deposited.

[0124] (4) Extraction of silk fibroin: Degummed silk was dissolved in 9.3 M LiBr solution at 60°C with a silk to solution ratio (w:v) of 1 g:50 mL. The solution was centrifuged at 3000 rpm for 10 min and packaged in a dialysis bag with a molecular weight cutoff of 7000 and dialyzed for three days. The water was changed every 5 h and the solution was freeze-dried to obtain silk fibroin.

[0125] (5) Coating of UHMWPE Fibers with Silk Fibroin: The silk fibroin prepared in step (4) was dissolved in hexafluoroisopropanol to prepare a 5 wt% silk fibroin solution. The UHMWPE fiber bundle obtained in step (3) was placed in 100 mL of the silk fibroin solution at a bath ratio of 1 g:2500 mL and soaked for 30 min. The fiber bundle was then placed in anhydrous ethanol at a bath ratio of 1 g:1000 mL for 4 h to obtain a UHMWPE fiber bundle coated with silk fibroin.

[0126] (6) Coating and cross-linking of polylysine (PLL): The UHMWPE fiber bundle obtained in step (5) was placed in 100 mL of a 0.05 M polylysine (PLL) aqueous solution at a bath ratio of 1 g:2500 mL. 6 g of N-hydroxysuccinimide, 4 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 20 mL of a 1 wt% genipin solution were added per 1 g of the fiber bundle. The mixture was stirred in the dark for 30 min and then taken out to obtain a UHMWPE composite fiber.

[0127] Performance Testing

[0128] Particle stability: The composite fibers were immersed in a PBS solution at a ratio of 1 g:1000 mL and ultrasonicated for 15 minutes. The nanoparticles were tested for a specific element using an inductively coupled plasma emission spectrometer. The Ca element was measured for hydroxyapatite, and the Si element was measured for bioactive glass. The cumulative drop rate of active particles was calculated and analyzed.

[0129] Ion release: The composite fiber was immersed in a PBS solution at a ratio of 1 g:100 mL. After 72 h, the content of specific elements in the PBS solution was measured using an inductively coupled plasma emission spectrometer.

[0130] Porosity ratio statistics: Image J software was used to calculate the ratio of pores to the image area in the SEM photos of the coating, which reflects the porosity of the coating.

[0131] Mechanical strength test: Clamp both ends of the composite fiber on a universal testing machine, set the tensile rate to 10 mm / min, test 5 groups of samples and calculate the average value. When testing the unwoven fibers of Comparative Example 1, 30 fibers were tested.

[0132] Antibacterial performance test: 0.1g composite fiber was mixed with 5mL of 10 7 The CFU / mL bacterial solution was co-cultured at 37°C and 200 r / min for 4 h. The bacterial solution was diluted and plated. The number of colonies on the nutrient agar plate was counted and the antibacterial rate was calculated.

[0133] The test results are shown in the following table:

[0134]

[0135] From the analysis of the results in the above table, it can be seen that by co-deposition of phenolamines on the three-directional woven fiber bundles, and depositing bioactive NPs on the surface of the composite fiber bundles, using silk fibroin to form a coating, and compounding PLL with antibacterial effect, UHMWPE fiber bundle composite fibers with a porous coating on the surface were successfully prepared (Examples 1-4), which have excellent particle composite stability, mechanical strength, bioactivity and antibacterial properties.

[0136] If the UHMWPE fibers are not triaxially woven (Comparative Example 1), the woven structure cannot be relied upon to evenly distribute the force, and the phenolamine co-deposition modified layer has limited effect on improving the mechanical strength, resulting in poor mechanical strength of the fiber bundle.

[0137] Without phenolamine co-deposition modification (Comparative Example 2), the NPs were unable to stably adhere to the smooth UHMWPE fiber surface, resulting in easy particle detachment and limited release of active ions. Furthermore, without phenolamine co-deposition modification, the mechanical strength of the fiber could not be further improved.

[0138] If NPs deposition is not performed (Comparative Example 3), the composite fiber cannot release active ions, does not have the ability to promote bone regeneration, and cannot stimulate rapid healing of damaged bone sites.

[0139] If the silk fibroin coating is not modified with ethanol (Comparative Example 4), since the silk fibroin coating has a certain water solubility, when treated in the PLL solution, the silk fibroin coating dissolves and the coated NPs fall off more easily, resulting in a very low concentration of active ions released by the fibers, which cannot effectively volatilize the bone regeneration-promoting performance.

[0140] If the PLL concentration is too high (Comparative Example 5) or freeze-drying is not performed in step 6 (Comparative Example 7), the porosity of the silk fibroin / PLL coating is low, resulting in a low concentration of active ions released by the NPs, weakening the bone regeneration effect. If the PLL concentration is too low (Comparative Example 6), the antibacterial effect of the fiber bundle is poor, which may increase the risk of postoperative infection.

[0141] Unless otherwise specified, the raw materials and equipment used in the present invention are commonly used in the art; the methods used in the present invention are conventional methods in the art unless otherwise specified.

[0142] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any way. Any simple modification, change and equivalent transformation made to the above embodiment based on the technical essence of the present invention still fall within the scope of protection of the technical solution of the present invention.

Claims

1. A UHMWPE composite fiber with a functional coating, characterized by: The invention comprises a UHMWPE fiber bundle with a three-way braided structure, and a phenolamine co-deposition modification layer, an inorganic functional nanoparticle deposition layer, and a silk fibroin / polylysine cross-linked porous layer sequentially coated on the surface of the UHMWPE fiber bundle; Inorganic functional nanoparticles have the function of promoting osteoblast differentiation and bone regeneration; After modification with anhydrous ethanol, silk fibroin changes from α-helical conformation to β-sheet conformation; The silk fibroin / polylysine cross-linked porous layer is prepared by placing a silk fibroin-coated UHMWPE fiber bundle in a 0.01-0.1 mol / L polylysine aqueous solution at a bath ratio of 1 g: (2200-2900) mL and adding a cross-linking agent, reacting in a dark place with stirring, taking out, and freeze-drying.

2. The UHMWPE composite fiber according to claim 1, wherein: The inorganic functional nanoparticles are one or more combinations of nanohydroxyapatite and nanobioactive glass.

3. A method for preparing the UHMWPE composite fiber according to claim 1 or 2, characterized in that The following steps are involved: (1) Weaving UHMWPE fibers into three-way woven UHMWPE fiber bundles; (2) Immersing the UHMWPE fiber bundle in a Tris solution containing catechol and 1,6-hexanediamine for oscillation reaction, taking it out, washing it with water, and drying it to obtain a phenolamine co-precipitation modified UHMWPE fiber bundle; (3) Immerse the UHMWPE fiber bundle modified by phenolamine co-deposition in a dispersion containing 1.5-3 g / 100 mL of inorganic functional nanoparticles at a bath ratio of 1 g: (2200-2900) mL and stir, then take out, wash with water, and dry to obtain a UHMWPE fiber bundle with inorganic functional nanoparticles deposited; (4) soaking the UHMWPE fiber bundle with inorganic functional nanoparticles deposited in a silk fibroin solution, taking it out, modifying the fiber bundle in anhydrous ethanol, taking it out, and drying it to obtain a UHMWPE fiber bundle with a silk fibroin coating; (5) The UHMWPE fiber bundle with silk fibroin coating was placed in a polylysine aqueous solution with a concentration of 0.01-0.1 mol / L at a bath ratio of 1 g: (2200-2900) mL, a cross-linking agent was added, the reaction was stirred in the dark, the fiber bundle was taken out, and freeze-dried to obtain a UHMWPE composite fiber with a functional coating.

4. The preparation method according to claim 3, wherein: In step (2), The pH of the Tris solution containing catechol and 1,6-hexanediamine is 8-10; The concentration of the catechol is 0.25-0.35 g / 100 mL, and the concentration of 1,6-hexanediamine is 0.2-0.5 g / 100 mL; The bath ratio of the UHMWPE fiber bundle to the Tris solution containing catechol and 1,6-hexanediamine is 1 g: (2200-2900) mL.

5. The preparation method according to claim 3 or 4, characterized in that: In step (2), The oscillation reaction time is 20-30 hours, and the drying temperature is 30-50°C.

6. The preparation method according to claim 3, wherein: In step (3), The average particle size of the inorganic functional nanoparticles is 50-200 nm; The stirring time is 2-4h and the drying temperature is 30-50℃.

7. The preparation method according to claim 3, wherein: In step (4), The silk fibroin extraction method comprises the following steps: dissolving 1 g of degummed silk in a 9.0-9.3 mol / L LiBr solution at a ratio of 1 g: (40-50) mL at 50-60° C., centrifuging the solution and dialyzing it for 2-4 days, changing the water every 4-6 hours, and freeze-drying the solution to obtain the silk fibroin.

8. The preparation method according to claim 7, wherein: In step (4), The centrifugal speed is 3000-5000 r / min, the centrifugal time is 10-15 min, and the molecular weight cut-off of the dialysis bag used for dialysis is 7000-10000 Mw.

9. The preparation method according to claim 3 or 7, wherein: In step (4), The concentration of the silk fibroin solution is 4-8 wt %, and the solvent is formic acid or hexafluoroisopropanol; The bath ratio of UHMWPE fiber bundles deposited with inorganic functional nanoparticles to silk fibroin solution was 1 g: (2300-2900) mL; Soaking time is 15-30 minutes; The bath ratio of the fiber bundle to anhydrous ethanol is 1 g: (1000-1500) mL, and the modification time in anhydrous ethanol is 4-8 h.

10. The preparation method according to claim 3, wherein: In step (5), The cross-linking agent includes N-hydroxysuccinimide, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and genipin solution; The amount ratio of the UHMWPE fiber bundle with silk fibroin coating, N-hydroxysuccinimide, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and genipin solution is 1 g: (6.0-8.0) g: (4.0-6.0) g: (10-25) mL, wherein the concentration of the genipin solution is 0.8-1.2 wt %; The stirring reaction time is 30-60 minutes.

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