Polyethylene composite fiber, and method for preparing and use thereof

Abstract

This invention discloses a polyethylene composite fiber, its preparation method, and its applications. The polyethylene composite fiber comprises ultra-high molecular weight polyethylene fiber and bioceramics, and can be used in surgical suture and repair products. This surgical suture and repair product is mainly used for bone suture and repair, promoting bone growth and repair at the wound site, which is beneficial for bone healing. This surgical suture and repair product has high strength, is safe and reliable, has good biocompatibility, promotes bone wound healing, and is not easily adhered to bone tissue, making it easy to remove.

Description

Technical Field

[0001] This invention relates to the field of medical materials, specifically to a bone suture and repair material, and more precisely, to a polyethylene composite fiber with ultra-high molecular weight polyethylene fiber as the matrix and bioceramic as the bioactive material, and its preparation method, for use in surgical suture and repair products. Background Technology

[0002] With the improvement of people's living standards, medical conditions are also constantly improving. Alleviating patient suffering and improving patient recovery are common goals of medical professionals. The use of repair materials is indispensable in the treatment process and is also one of the important factors directly affecting the patient's recovery level. Ultra-high molecular weight polyethylene resin is a linear polymer containing only C and H elements, with a molecular weight exceeding one million. Ultra-high molecular weight polyethylene fibers prepared from it not only possess high strength, high modulus, bending resistance, and abrasion resistance, but also have good biocompatibility, low cytotoxicity, resistance to acid, alkali, and salt corrosion, and long service life. It is a material that can be used in implants, especially as surgical sutures and artificial joints. Bioceramics are currently known animal bone repair materials that can promote bone growth at the wound site and are beneficial to bone healing.

[0003] DSM's Chinese patent CN111386133A, concerning a method for preparing osteoconductive fiber products and a medical implant containing such products, discloses a medical implant that primarily involves coating non-biodegradable polyethylene terephthalate (PET) fibers with bioactive ceramic particles, such as calcium phosphate or bioglass, to enhance bone growth. The patent's technical solution involves coating the surface of PET fibers with polymers and bioactive ceramic particles, resulting in a surface containing these particles that promotes wound healing. While this method achieves the intended purpose, the post-processing of the fibers can damage their mechanical properties. Furthermore, the process requires the introduction of other chemical reagents or components to ensure the ceramic particles adhere to the fibers, increasing manufacturing costs and emissions.

[0004] In summary, most of the currently disclosed technical solutions involve endowing the surface of fibers with bioactive substances for implantation, which is beneficial for bone wound healing. However, the active substances inside the fibers are encapsulated and cannot be released, hindering efficient utilization. Furthermore, the use of fibers in vivo carries significant safety risks and other disadvantages. Summary of the Invention

[0005] To address the problems existing in the prior art, the present invention provides a polyethylene composite fiber, comprising ultra-high molecular weight polyethylene fiber and bioceramics, which can be used in biological surgical sutures and repair products. This product has the characteristics of simple composition, no solvent residue, light weight, high strength, high bioactivity and good biocompatibility.

[0006] One object of the present invention is to provide a polyethylene composite fiber, comprising ultra-high molecular weight polyethylene fiber and bioceramics.

[0007] The polyethylene composite fiber has a network of pores on its interior and surface. Preferably, the pore size is 0.01–50 μm and the porosity is 10–40%. More preferably, the pore size is 0.1–10 μm and the porosity is 20–40%.

[0008] The polyethylene composite fiber has a breaking strength ≥40cN / dtex and an initial modulus ≥1700cN / dtex.

[0009] The bioceramic components are uniformly distributed inside the fiber and partially embedded on the fiber surface.

[0010] The bioceramic is selected from at least one of calcium phosphate and bioglass.

[0011] The bioceramic is a sphere, a spheroid, or a mixture thereof.

[0012] The bioceramic has a particle size of 20–20,000 nm.

[0013] The bioceramic comprises 2 to 15 wt% of the ultra-high molecular weight polyethylene fiber, preferably 5 to 10 wt%.

[0014] This polyethylene composite fiber is mainly used for bone suturing and repair. The bioceramic powder on the fiber migrates under the action of tissue fluid in the body, is released and seeps into the bone injury site, promotes bone growth at the wound site, and is conducive to bone healing.

[0015] Another object of the present invention is to provide a method for preparing the polyethylene composite fiber, comprising the following steps:

[0016] 1) Dissolve ultra-high molecular weight polyethylene resin in an organic solvent and add bioceramics to prepare a spinning solution;

[0017] 2) The spinning solution is extruded to form a fine filament fluid;

[0018] 3) The filament fluid is solidified and molded to obtain a dry filament;

[0019] 4) The dry filaments are thermally stretched to obtain ultra-high molecular weight polyethylene fibers;

[0020] 5) The ultra-high molecular weight polyethylene fiber is processed, wherein the processing includes at least one of twisting, weaving, extrusion, and thermoplasticizing.

[0021] The bioceramic added in step 1) is selected from at least one of calcium phosphate, bioglass, etc.

[0022] The bioceramic added in step 1) accounts for 2 to 15 wt% of the mass of the ultra-high molecular weight polyethylene resin.

[0023] Preferably, the bioceramic accounts for 5-10 wt% of the mass of the ultra-high molecular weight polyethylene resin.

[0024] More preferably, the bioceramic accounts for 6 to 8 wt% of the mass of the ultra-high molecular weight polyethylene resin.

[0025] The bioceramic is a sphere or a spheroid with a diameter of 20 to 20,000 nm, or a mixture thereof.

[0026] Meanwhile, in order to increase the contact between bioceramic powder and biological tissue fluid and improve the utilization rate of bioceramic powder, maltose is added at any time before, during or after the spinning solution obtained in step 1).

[0027] Preferably, the maltose content is 1-6% of the mass of ultra-high molecular weight polyethylene resin, more preferably 2-6%, for example, it can be 1%, 2%, 3%, 4%, 5%, 6%, etc.

[0028] The ultra-high molecular weight polyethylene resin in step 1) of this invention has a viscosity-average molecular weight of not less than 4 million.

[0029] Preferably, the ultra-high molecular weight polyethylene resin has a viscosity-average molecular weight of not less than 5 million.

[0030] More preferably, the ultra-high molecular weight polyethylene resin has a viscosity-average molecular weight of not less than 5.8 million but not more than 8 million.

[0031] The ash content of the ultra-high molecular weight polyethylene resin is less than 100 ppm.

[0032] The organic solvent in step 1) of the present invention is one or a mixture of more than one of the following: decahydronaphthalene, xylene, kerosene, vegetable oil, white oil, liquid paraffin, etc.

[0033] Preferably, the organic solvent is decahydronaphthalene.

[0034] The decahydronaphthalene can be a cis isomer, a trans isomer, or a mixture of cis-trans isomers.

[0035] The concentration of ultra-high molecular weight polyethylene resin in the spinning solution is 3-17 wt%, preferably 7-12 wt%.

[0036] The ultra-high molecular weight polyethylene resin is dissolved to obtain a spinning solution, mainly through at least one method such as kettle dissolution, single-screw dissolution, twin-screw extruder dissolution, static mixer dissolution, and dynamic mixer dissolution.

[0037] Preferably, the dissolution described in this invention is performed using a twin-screw extruder.

[0038] The twin-screw extruder has a melting temperature of 140–210°C.

[0039] Preferably, the melting temperature of the twin-screw extruder is 140–190°C.

[0040] The twin-screw extruder described above has a melting speed of 80–200 rpm.

[0041] Preferably, the twin-screw extruder rotates at a speed of 110–140 rpm.

[0042] In step 2) of the present invention, the spinning solution is metered and extruded from the spinneret to form a spinning stream. The spinning solution is preferably subjected to pressure stabilization treatment before metering.

[0043] The voltage stabilization process is preferably carried out by at least one method, such as a booster pump, a delivery pump, or a metering pump.

[0044] After pressure stabilization treatment, the pressure inside the material pipeline is 2-6 MPa.

[0045] Preferably, the pressure inside the material pipeline is 3 to 5 MPa.

[0046] The diameter of the spinneret orifice is 0.1 to 2.0 mm.

[0047] Preferably, the diameter of the spinneret orifice is 0.4 to 1.0 mm.

[0048] The spinning stream formed by extruding the spinning solution from the spinneret orifice has a speed of not less than 1 m / min and not more than 20 m / min.

[0049] The spinning solution is extruded through a spinneret to obtain a fine filament fluid, which is then stretched by at least 4 times.

[0050] Preferably, the filament fluid obtained by extruding the spinning solution through the spinneret is stretched by at least 12 times.

[0051] More preferably, the filament fluid obtained by extruding the spinning solution through the spinneret is stretched by at least 13 times and at most 30 times.

[0052] In step 3) of the present invention, the filament fluid is solidified to obtain a dry filament.

[0053] The solidification process refers to the process of solidifying and shaping the spinning solution after it is extruded from the spinneret to form independent fine spinning streams.

[0054] The spun fine streams are independent fluids that can only be shaped and form independent filaments after solidification. Otherwise, they are prone to sticking together and the resulting filament bundles are difficult to separate.

[0055] The curing process can be achieved through at least one of gas-phase curing or gas-liquid phase combined curing.

[0056] Preferably, the conditions for vapor phase solidification include a vapor phase temperature of 30–90°C.

[0057] Preferably, the conditions for gas-liquid phase combined curing include a gas phase temperature of 20–80°C and a liquid phase temperature of 20–60°C.

[0058] After solidification, the spun yarn is subjected to water bath stretching of 2-8m and air chamber purging with wind speed of 0.3m / s-8m / s.

[0059] After curing, a water bath stretching process is performed to remove at least part of the maltose on the surface and inside, forming a network of pores. To control the rate of maltose removal, the water bath temperature is 60–90°C and the stretching ratio is 1.1–2. Preferably, the water bath temperature is 60–70°C and the stretching ratio is 1.1–1.6.

[0060] In the spinning solution, maltose forms a fluid melt under high temperature conditions, which can be dispersed in the ultra-high molecular weight polyethylene (UHMWPE) decahydronaphthalene solution to obtain a uniform UHMWPE-maltose-decahydronaphthalene spinning system. During the extrusion and molding of the spinning fluid, maltose is uniformly distributed inside and on the surface of the fiber. After water bath drawing, the maltose is washed away, forming a uniform network of pores on the fiber surface and inside.

[0061] The air velocity in the air chamber is 0.6 m / s to 2 m / s, and the air temperature is 60 to 90℃.

[0062] When the solvent is a volatile organic solvent, vapor phase curing is preferred.

[0063] When the solvent is a non-volatile oil solvent, gas-liquid phase solidification is preferred, and the liquid phase component is preferably an extractant.

[0064] The extractant is mainly a low-boiling-point organic solvent such as dichloromethane and trichloromethane.

[0065] The dry filaments mentioned above mainly refer to filaments obtained by simultaneously removing the spinning solvent while the spinning fine stream is solidified.

[0066] The dry state filaments mainly refer to the original filaments after solvent removal, with a solvent residue of 0 ppm, meaning no solvent residue.

[0067] Solvent residue was measured by drying the fiber at 150℃ and weighing it. The change in the fiber's mass before and after drying was measured to determine the solvent residue.

[0068] The thermal stretching described in step 4) is mainly the process by which the dry filaments deform under heat and stretching tension.

[0069] The aforementioned hot stretching involves a dry filament bundle being heated at a temperature of 110–160°C.

[0070] Preferably, the heating temperature of the dry filament bundle is 135–149°C.

[0071] The deformation process caused by the tension is mainly due to the dry filaments becoming longer under stress.

[0072] During the deformation process described, the dry filaments underwent a deformation of 4 to 25 times.

[0073] Preferably, the dry filaments undergo a deformation of 6 to 18 times.

[0074] The dry filaments undergo at least two stages of thermal stretching and at most five stages of thermal stretching.

[0075] Preferably, the conditions for first-stage drawing include a temperature of 128–138°C and a tensile deformation of 2.5–6.0 times; the conditions for second-stage drawing include a temperature of 138–145°C and a tensile deformation of 1.2–2.0 times; the conditions for third-stage drawing include a temperature of 140–145°C and a tensile deformation of 1.1–1.2 times; the conditions for fourth-stage drawing include a temperature of 140–147°C and a tensile deformation of 1.01–1.1 times; and the conditions for fifth-stage drawing include a temperature of 110–160°C and a tensile deformation of 0.8–1.1 times.

[0076] More preferably, the conditions for first-stage drawing include a temperature of 130–138°C and a tensile deformation of 3.5–5.5 times; the conditions for second-stage drawing include a temperature of 138–144°C and a tensile deformation of 1.2–1.6 times; the conditions for third-stage drawing include a temperature of 140–145°C and a tensile deformation of 1.1–1.18 times; the conditions for fourth-stage drawing include a temperature of 140–147°C and a tensile deformation of 1.01–1.08 times; and the conditions for fifth-stage drawing include a temperature of 110–147°C and a tensile deformation of 0.8–1.08 times.

[0077] After the dry filaments are subjected to the above-mentioned thermal stretching, ultra-high molecular weight polyethylene fibers are obtained.

[0078] The polyethylene composite fiber has a breaking strength ≥40cN / dtex and an initial modulus ≥1700cN / dtex.

[0079] The mechanical properties of the polyethylene composite fiber were tested according to GB / T 19975-2005, Test Method for Tensile Properties of High-Strength Fiber Filaments.

[0080] The ultra-high molecular weight polyethylene fiber contains bioceramics.

[0081] During the thermal stretching process of ultra-high molecular weight polyethylene (UHMWPE) fibers, bioceramics slip under the action of stretching stress, sliding towards the direction of least resistance. Because the fiber is subjected to longitudinal forces, the spherical particles inside the fiber slide laterally, i.e., onto the surface. By controlling parameters such as stretching tension, stretching temperature, and the network of pores within the fiber formed by maltose removal, the sliding of bioceramic spherical particles from the fiber interior towards the fiber surface can be controlled, allowing them to aggregate or embed on the fiber surface.

[0082] Tension control is one of the key factors in regulating the embedding of bioceramics on the fiber surface.

[0083] The interaction between ultra-high molecular weight polyethylene (UHMWPE) materials and bioceramics mainly occurs in the spaces between the polyethylene macromolecular chains. When polyethylene bioceramic fibers act within a living organism, the tissue fluid within the organism permeates into the fiber interior through the network pores. Upon contact with the bioceramic on the fiber surface, a force is generated. The bioceramic, utilizing the network pores and the force of the tissue fluid, slides towards the fiber surface, detaches from the fiber surface, and accumulates at the bone tissue wound site, promoting bone growth and repair.

[0084] The network of pores inside the fiber makes it relatively easy for bioceramics to move within the fiber. At the same time, the network of pores can induce tissue fluid in the body to diffuse into the pores, inducing and capturing active bioceramics within the fiber.

[0085] In addition, the surface of polyethylene fibers does not adhere to bone tissue, and the wound does not experience an inflammatory response under the action of sutures.

[0086] This method is simple and low-cost, and the resulting product has the characteristics of simple composition, no solvent residue, stable performance, light weight, high strength, high biological activity and good biocompatibility, which can meet the requirements for medical use.

[0087] The ultra-high molecular weight polyethylene fiber is processed through at least one process, such as twisting, weaving, extrusion, and thermoplasticizing, to obtain surgical suture and repair products.

[0088] Another object of the present invention is to provide the polyethylene composite fiber or the polyethylene composite fiber obtained by the preparation method for use in surgical suture and repair products.

[0089] The polyethylene composite fiber described in this invention has the characteristics of high strength, safety and reliability, good biocompatibility, and is conducive to bone wound healing, non-adhesive, and easy to remove.

[0090] The surgical suture and repair products described in this invention are mainly used in animal orthopedic surgery sutures, fixation fibers for bone fractures, artificial joints, etc. They have good biocompatibility in animals. When they come into contact with the tissue fluid in the animal's body, the bioceramic inside the fibers is released from the fiber carrier under the action of the tissue fluid, combines with the bone, and promotes bone growth and bone healing.

[0091] This invention has the following advantages:

[0092] This technical solution improves upon the existing ultra-high molecular weight polyethylene fiber spinning process by adding bioceramics online and controlling the drawing temperature and drawing ratio to develop a process for preparing polyethylene composite fibers.

[0093] Meanwhile, the ultra-high molecular weight polyethylene fiber developed by this technical solution contains bioceramics, which has application value in the fields of surgical sutures and bone repair. While increasing the added value of the product, it also significantly improves the existing medical level and enhances patient comfort.

[0094] In addition, this technical solution is simple to implement, the production process is safe and environmentally friendly, and the product has good biocompatibility.

[0095] In summary, the method for preparing polyethylene composite fibers provided by this invention is low-cost, safe, and environmentally friendly, and suitable for modern industrial production; the resulting fibers have excellent mechanical properties, low cytotoxicity, and good biocompatibility, meeting the requirements for medical use. Detailed Implementation

[0096] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0097] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, such as those that can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0098] Method for testing the pore size of composite fibers: Surface morphology is scanned by scanning electron microscopy (SEM) to measure the diameter of fiber pores.

[0099] Composite fiber porosity testing method: Measure the pore diameter and number of pores per unit area, and calculate the percentage of the total pore area per unit area.

[0100] Example 1

[0101] Ultra-high molecular weight polyethylene (UHMWPE) resin with a viscosity-average molecular weight of 4 million was dispersed in decahydronaphthalene (9% by mass of UHMWPE). After swelling by stirring at 90°C for 4 hours, maltose (6% by mass of UHMWPE resin) and calcium phosphate with a diameter of 20 nm (10% by mass of UHMWPE resin) were added separately. After uniform dispersion, the mixture was mixed and dissolved by a twin-screw extruder, conveyed by a booster pump and metered by a metering pump, and then extruded through a 0.4 mm diameter spinneret at a speed of 1 m / min to obtain a spun yarn. The spun yarn entered a hot air duct to remove the solvent (the duct air was 60°C nitrogen), and then successively passed through a 2 m long, 90°C, 1.1 times water bath for stretching and an air chamber with an air speed of 2 m / min and an air temperature of 90°C to obtain dry yarn. The dry filaments were sequentially subjected to a first-stage draw at 110℃ (2 times the strength), a second-stage draw at 145℃ (5 times the strength), and a third-stage draw at 149℃ (1.2 times the strength), ultimately yielding ultra-high molecular weight polyethylene calcium phosphate fiber. The fiber exhibits a breaking strength of 40 cN / dtex and an initial modulus of 1700 cN / dtex. Testing revealed a network of pores on the fiber's interior and surface, with a pore size of 0.01 μm and a porosity of 40%. The fiber contains 9% calcium phosphate particles. This fiber, after twisting treatment, is used in bone sutures.

[0102] Example 2

[0103] Ultra-high molecular weight polyethylene (UHMWPE) resin with a viscosity-average molecular weight of 5.8 million was dispersed in decahydronaphthalene (7% by mass of UHMWPE). After swelling by stirring at 98°C for 2 hours, maltose (1% by mass of UHMWPE resin) and calcium phosphate with a diameter of 20,000 nm (3% by mass of UHMWPE resin) were added separately. After uniform dispersion, the mixture was mixed and dissolved by a twin-screw extruder, conveyed by a booster pump and metered by a metering pump, and then extruded through a 1 mm diameter spinneret at a speed of 1 m / min to obtain a spun yarn. The spun yarn entered a hot air duct to remove the solvent (the duct air was 90°C nitrogen), and then successively passed through an 8 m long, 60°C, twice-sized water bath for stretching and an air chamber with an air speed of 0.3 m / min and an air temperature of 60°C to obtain dry yarn. The dry filaments were sequentially subjected to a first-stage draw at 135℃ and 5.5 times the strength of the original fibers; a second-stage draw at 147℃ and 2.8 times the strength of the original fibers; and a third-stage draw at 150℃ and 1.1 times the strength of the original fibers, ultimately yielding ultra-high molecular weight polyethylene calcium phosphate fibers. The fibers exhibit a breaking strength of 40 cN / dtex and an initial modulus of 1700 cN / dtex. Testing revealed a network of pores with a pore size of 50 μm and a porosity of 20% on both the internal and surface of the fibers. The fibers contain 2.9% calcium phosphate particles. This fiber, after being woven, is intended for use in artificial joints.

[0104] Example 3

[0105] Ultra-high molecular weight polyethylene (UHMWPE) resin with a viscosity-average molecular weight of 8 million was dispersed in decahydronaphthalene (UHMWPE mass percentage was 3%). After swelling by stirring at 100℃ for 3 hours, maltose (3% by mass of UHMWPE resin) and calcium phosphate with a diameter of 100 nm (10% by mass of UHMWPE resin) were added separately. After uniform dispersion, the mixture was mixed and dissolved by a twin-screw extruder, conveyed by a booster pump and metered by a metering pump, and then extruded through a 0.7 mm diameter spinneret at a speed of 20 m / min to obtain a spun yarn. The spun yarn entered a hot air duct to remove the solvent (the duct air was 80℃ nitrogen), and then successively passed through a 4 m long, 70℃, 1.3 times water bath for stretching and an air chamber with an air speed of 1 m / min and an air temperature of 70℃ to obtain dry yarn. The dry filaments were sequentially drawn at 142℃ (4 times the strength of the first stage), 147℃ (1.6 times the strength of the second stage), 144℃ (1.5 times the strength of the third stage), 149℃ (1.05 times the strength of the fourth stage), and 149℃ (1.02 times the strength of the fifth stage) to obtain ultra-high molecular weight polyethylene calcium phosphate fiber. The fiber has a breaking strength of 46 cN / dtex and an initial modulus of 2100 cN / dtex. Testing revealed a network of pores on the fiber's interior and surface, with a pore size of 0.1 μm and a porosity of 30%. The fiber contains 8.0% calcium phosphate particles. This fiber, after hot extrusion treatment, is used in artificial joints.

[0106] Example 4

[0107] Ultra-high molecular weight polyethylene (UHMWPE) resin with a viscosity-average molecular weight of 5 million was dispersed in decahydronaphthalene (7% by mass of UHMWPE). Maltose (6% by mass of UHMWPE resin) was added, and the mixture was stirred at 95°C for 2 hours to swell. Then, 1000 nm diameter bioglass (8% by mass of UHMWPE resin) was added and dispersed evenly. The mixture was then mixed and dissolved using a twin-screw extruder, conveyed by a booster pump, metered by a metering pump, and extruded through a 1 mm diameter spinneret at a speed of 10 m / min to obtain spun yarns. The spun yarns entered a hot air duct to remove the solvent (the duct air was 90°C nitrogen), and then successively passed through a 4 m long, 70°C, 1.4 times water bath for stretching and an air chamber with an air speed of 1 m / min and an air temperature of 70°C to obtain dry yarns. The dry filaments were sequentially subjected to a first-stage draw at 140℃ (6 times the original strength), a second-stage draw at 147℃ (1.2 times the original strength), and a third-stage draw at 144℃ (1.08 times the original strength), ultimately yielding ultra-high molecular weight polyethylene bioglass fibers. The fibers exhibit a tensile strength of 42 cN / dtex and an initial modulus of 1800 cN / dtex. Testing revealed a network of pores on the fiber's interior and surface, with a pore size of 10 μm and a porosity of 40%. The fibers contain 6.0% bioglass. After twisting and weaving, these fibers are intended for use as orthopedic surgical sutures.

[0108] Example 5

[0109] Ultra-high molecular weight polyethylene (UHMWPE) resin with a viscosity-average molecular weight of 5 million was dispersed in white oil (7% by mass of UHMWPE). Maltose (3% by mass of UHMWPE resin) was added, and the mixture was stirred at 95°C for 2 hours to swell. Then, 1000 nm diameter bioglass (8% by mass of UHMWPE resin) was added and dispersed evenly. The mixture was then mixed and dissolved using a twin-screw extruder, conveyed by a booster pump, metered by a metering pump, and extruded through a 1 mm diameter spinneret at a speed of 5 m / min to obtain spun yarn. The spun yarn entered a chloroform extraction tank to remove the white oil solvent, was dried in a 50°C vapor phase hot box, and then sequentially passed through a 2 m long, 90°C, 1.5 times water bath for stretching and an air chamber with a wind speed of 0.6 m / min and a wind temperature of 90°C to obtain dry yarn. The dry filaments were sequentially subjected to a first-stage draw at 140℃ (6 times the strength of the first stage), a second-stage draw at 147℃ (1.2 times the strength of the second stage), and a third-stage draw at 144℃ (1.08 times the strength of the third stage) to obtain ultra-high molecular weight polyethylene bioglass fibers. The fibers have a breaking strength of 41 cN / dtex and an initial modulus of 1750 cN / dtex. Testing revealed a network of pores on the fiber's interior and surface, with a pore size of 10 μm and a porosity of 20%. The fibers contain 6.0% bioglass. After twisting and weaving, these fibers are intended for use as orthopedic surgical sutures.

[0110] Example 6

[0111] Ultra-high molecular weight polyethylene (UHMWPE) resin with a viscosity-average molecular weight of 5 million was dispersed in xylene (7% by mass of UHMWPE). Maltose (3% by mass of UHMWPE resin) was added, and the mixture was stirred at 95°C for 2 hours to swell. Then, 500 nm diameter bioglass (8% by mass of UHMWPE resin) was added and dispersed evenly. The mixture was then mixed and dissolved using a twin-screw extruder, conveyed by a booster pump, metered by a metering pump, and extruded through a 1 mm diameter spinneret at a speed of 5 m / min to obtain spun yarn. After solidification in a water bath, the spun yarn was dried in a 50°C vapor phase heat chamber, and then sequentially passed through a 2 m long water bath at 90°C and 1.2 times the volume of the resin, and an air chamber with a wind speed of 0.6 m / min and a wind temperature of 90°C to obtain dry yarn. The dry filaments were sequentially subjected to a first-stage draw at 140℃ (6 times the original strength), a second-stage draw at 147℃ (1.2 times the original strength), and a third-stage draw at 144℃ (1.08 times the original strength), ultimately yielding ultra-high molecular weight polyethylene bioglass fibers. The fibers exhibit a tensile strength of 42 cN / dtex and an initial modulus of 1800 cN / dtex. Testing revealed a network of pores with a pore size of 2 μm and a porosity of 20% within the fiber's interior and surface. The fibers contain 6.0% bioglass. After twisting and subsequent weaving, these fibers are intended for use as orthopedic surgical sutures.

[0112] Example 7

[0113] Ultra-high molecular weight polyethylene (UHMWPE) resin with a viscosity-average molecular weight of 5 million was dispersed in liquid paraffin (7% by mass of UHMWPE). Maltose (3% by mass of UHMWPE resin) was added, and the mixture was stirred at 95°C for 2 hours to swell. Then, 500 nm diameter bioglass (8% by mass of UHMWPE resin) was added and dispersed evenly. The mixture was then mixed and dissolved using a twin-screw extruder, conveyed by a booster pump, metered by a metering pump, and extruded through a 1 mm diameter spinneret at a speed of 5 m / min to obtain spun yarn. The spun yarn entered a chloroform extraction tank to remove the liquid paraffin, passed through a 50°C vapor phase heat box, and then sequentially passed through a 2 m long, 90°C, 1.2 times water bath for stretching and an air chamber with a wind speed of 0.6 m / min and a wind temperature of 90°C to dry it to obtain dry yarn. The dry filaments were sequentially subjected to a first-stage draw at 140℃ (5.0 times the original strength), a second-stage draw at 147℃ (1.8 times the original strength), and a third-stage draw at 149℃ (1.1 times the original strength), ultimately yielding ultra-high molecular weight polyethylene bioglass fibers. The fibers exhibit a tensile strength of 41 cN / dtex and an initial modulus of 1750 cN / dtex. Testing revealed a network of pores with a pore size of 2 μm and a porosity of 20% within the fiber's interior and surface. The fibers contain 6.1% bioglass and are then braided for use as orthopedic surgical sutures.

[0114] Example 8

[0115] Ultra-high molecular weight polyethylene (UHMWPE) resin with a viscosity-average molecular weight of 5 million was dispersed in mineral oil (7% by mass of UHMWPE). Maltose (3% by mass of UHMWPE resin) was added, and the mixture was stirred at 95°C for 2 hours to swell. Then, 500 nm diameter bioglass (8% by mass of UHMWPE resin) was added and dispersed evenly. The mixture was then mixed and dissolved using a twin-screw extruder, conveyed by a booster pump, metered by a metering pump, and extruded through a 1 mm diameter spinneret at a speed of 5 m / min to obtain spun yarn. The spun yarn entered a chloroform extraction tank to remove the white oil solvent, passed through a 50°C vapor phase hot box, and then sequentially passed through a 2 m long, 90°C, 1.2 times water bath for stretching and an air chamber with a wind speed of 0.6 m / min and a wind temperature of 90°C to dry it to obtain dry yarn. Dry filaments were sequentially subjected to a first-stage draw at 140℃ (5.0 times the original strength), a second-stage draw at 147℃ (1.8 times the original strength), and a third-stage draw at 149℃ (1.1 times the original strength), ultimately yielding ultra-high molecular weight polyethylene bioglass fibers. Testing revealed a fiber tensile strength of 41 cN / dtex and an initial modulus of 1700 cN / dtex. The fibers exhibited a network of pores with a pore size of 2 μm and a porosity of 25%, both internally and on the surface. The fibers contained 6.1% bioglass. After twisting, these fibers were used as orthopedic surgical sutures.

[0116] Example 9

[0117] Ultra-high molecular weight polyethylene (UHMWPE) resin with a viscosity-average molecular weight of 5 million was dispersed in white oil (7% by mass of UHMWPE). Maltose (2% by mass of UHMWPE resin) was added, and the mixture was stirred at 95°C for 2 hours to swell. Then, calcium phosphate spheres with a diameter of 20 nm (15% by mass of UHMWPE resin) were added and dispersed evenly. The mixture was then mixed and dissolved using a twin-screw extruder, conveyed by a booster pump, metered by a metering pump, and extruded through a 1 mm diameter spinneret at a speed of 5 m / min to obtain a spun yarn. The spun yarn entered a chloroform extraction tank to remove the white oil solvent, passed through a 50°C vapor phase hot box, and then sequentially passed through a 2 m long, 90°C, 1.2 times water bath for stretching and an air chamber with a wind speed of 0.6 m / min and a wind temperature of 90°C to dry it to obtain dry yarn. The dry filaments were sequentially subjected to a first-stage draw at 140℃ and 5.5 times the strength of the fiber; a second-stage draw at 147℃ and 1.8 times the strength of the fiber; and a third-stage draw at 144℃ and 1.1 times the strength of the fiber, ultimately yielding ultra-high molecular weight polyethylene calcium phosphate fiber. The fiber has a breaking strength of 40 cN / dtex and an initial modulus of 1700 cN / dtex. Testing revealed a network of pores on the fiber's interior and surface, with a pore size of 0.01 μm and a porosity of 25%. The fiber contains 12% calcium phosphate and is suitable for weaving into orthopedic surgical sutures.

[0118] Example 10

[0119] Ultra-high molecular weight polyethylene (UHMWPE) resin with a viscosity-average molecular weight of 5 million was dispersed in white oil (7% by mass of UHMWPE). Maltose (4% by mass of UHMWPE resin) was added, and the mixture was stirred at 95°C for 2 hours to swell. Then, calcium phosphate spheres with a diameter of 20,000 nm (5% by mass of UHMWPE resin) were added and dispersed evenly. The mixture was then mixed and dissolved using a twin-screw extruder, conveyed by a booster pump, metered by a metering pump, and extruded through a 1 mm diameter spinneret at a speed of 5 m / min to obtain a spun yarn. The spun yarn entered a chloroform extraction tank to remove the white oil solvent, passed through a 50°C vapor phase hot box, and then sequentially passed through a 2 m long, 90°C, 1.2 times water bath for stretching and an air chamber with an air speed of 0.6 m / min and an air temperature of 90°C to obtain dry yarn. The dry filaments were sequentially subjected to a first-stage draw at 140℃ (5.5 times the original strength), a second-stage draw at 147℃ (1.8 times the original strength), and a third-stage draw at 144℃ (1.1 times the original strength), ultimately yielding ultra-high molecular weight polyethylene calcium phosphate fiber. The fiber exhibits a tensile strength of 40 cN / dtex and an initial modulus of 1700 cN / dtex. Testing revealed a network of pores with a pore size of 50 μm and a porosity of 10% within the fiber's interior and surface. The calcium phosphate content in the fiber is 4.9%. After weaving treatment, it is suitable for use as an orthopedic repair material.

[0120] Example 11

[0121] Ultra-high molecular weight polyethylene (UHMWPE) resin with a viscosity-average molecular weight of 6 million was dispersed in decahydronaphthalene (9% by mass of UHMWPE). Maltose (6% by mass of UHMWPE resin) was added, and the mixture was stirred at 97°C for 2 hours to swell. Then, calcium phosphate spheres with a diameter of 100 nm (6% by mass of UHMWPE resin) were added and dispersed evenly. The mixture was then dissolved and mixed in a static mixer, pumped by a booster pump, metered by a metering pump, and extruded through a 0.8 mm diameter spinneret at a speed of 3 m / min to obtain a spun yarn. The spun yarn entered a hot air duct to remove the solvent (the duct air was 80°C nitrogen), and then passed through a 2 m long, 90°C, 1.2 times water bath for drawing and an air chamber with a wind speed of 0.6 m / min and a wind temperature of 90°C to obtain dry yarn. The dry yarn then passed through a primary drawing at 149°C, 10 times the current size; and a secondary drawing at 147°C, 2.5 times the current size, finally yielding UHMWPE calcium phosphate fibers. The fiber has a tensile strength of 41 cN / dtex and an initial modulus of 1900 cN / dtex. Tests show that the fiber has a network of pores with a diameter of 0.1 μm and a porosity of 10%. The fiber contains 5.5% calcium phosphate. This fiber is thermoplasticized and used in artificial joints.

[0122] Example 12

[0123] Ultra-high molecular weight polyethylene (UHMWPE) resin with a viscosity-average molecular weight of 6 million was dispersed in decahydronaphthalene (8% by mass of UHMWPE). Maltose (6% by mass of UHMWPE resin) was added, and after swelling, 100 nm diameter bio-glass spheres (10% by mass of UHMWPE resin) were added. After uniform dispersion, the mixture was dissolved and mixed in a dynamic mixer, then pumped by a booster pump and metered by a metering pump. The spun fibers were then extruded through a 0.8 mm diameter spinneret at a speed of 3 m / min to obtain spun fines. The spun fines entered a hot air duct to remove the solvent (the duct air was 80 °C nitrogen). They then passed through a 2 m long, 90 °C, 1.2 times water bath for stretching and an air chamber with a wind speed of 0.6 m / min and a wind temperature of 90 °C to obtain dry filaments. The dry filaments were then subjected to a first-stage stretching at 149 °C and 10 times the original strength; and a second-stage stretching at 147 °C and 2.5 times the original strength, finally yielding UHMWPE bio-glass fibers. The fiber has a tensile strength of 41 cN / dtex and an initial modulus of 1900 cN / dtex. Tests show that the fiber has a network of pores with a diameter of 0.1 μm and a porosity of 10%. The fiber contains 7.5% bioglass. This fiber is thermoplasticized for use in artificial joints.

[0124] Example 13

[0125] Ultra-high molecular weight polyethylene (UHMWPE) resin with a viscosity-average molecular weight of 6 million was dispersed in decahydronaphthalene (7% by mass of UHMWPE). Maltose (6% by mass of UHMWPE resin) was added, and after swelling, 100 nm diameter bio-glass spheres (10% by mass of UHMWPE resin) were added. The mixture was then evenly dispersed in a reactor and heated to 180°C to dissolve. The solution was transported by a transfer pump and metered by a metering pump, then extruded through a 0.8 mm diameter spinneret at a speed of 4 m / min to obtain spun fibers. The spun fibers entered a hot air duct to remove the solvent (the duct air was 90°C nitrogen). They then passed sequentially through a 2 m long, 90°C, 1.2 times water bath stretching and an air chamber with a wind speed of 0.6 m / min and an air temperature of 90°C to obtain dry filaments. The dry filaments then passed through a primary stretching at 149°C, 10 times the current strength; and a secondary stretching at 149°C, 2.0 times the current strength, finally yielding UHMWPE bio-glass fibers. The fiber has a tensile strength of 40 cN / dtex and an initial modulus of 1800 cN / dtex. Tests show that the fiber has a network of pores with a diameter of 0.1 μm and a porosity of 10%. The fiber contains 7.5% bioglass. This fiber is thermoplasticized for use in artificial joints.

[0126] Example 14

[0127] Ultra-high molecular weight polyethylene (UHMWPE) resin with a viscosity-average molecular weight of 6 million was dispersed in decahydronaphthalene (7% by mass of UHMWPE). Maltose (6% by mass of UHMWPE resin) was added, and after swelling, 100 nm diameter bio-glass spheres (6% by mass of UHMWPE resin) were added. After uniform dispersion in a reactor, the mixture was heated to 190°C to dissolve. The solution was then transported by a transfer pump and metered by a metering pump, and extruded through a 0.8 mm diameter spinneret at a speed of 4 m / min to obtain a spun filament. The spun filament entered a hot air duct to remove the solvent (the duct air was 90°C), and then sequentially passed through a 2 m long, 90°C, 1.2 times water bath for stretching and an air chamber with a wind speed of 0.6 m / min and an air temperature of 90°C to obtain a dry filament. The dry filaments were sequentially subjected to a first-stage draw at 149℃ (10.00 times the original strength), a second-stage draw at 147℃ (1.40 times the original strength), and a third-stage draw at 147℃ (1.20 times the original strength), ultimately yielding ultra-high molecular weight polyethylene bioglass fibers. The fibers exhibit a tensile strength of 43 cN / dtex and an initial modulus of 1900 cN / dtex. Testing revealed a network of pores on the fiber's interior and surface, with a pore size of 0.1 μm and a porosity of 20%. The bioglass content in the fibers is 5.5%. These fibers, after being braided, are intended for use as surgical sutures.

[0128] Comparative Example 1

[0129] Following the operation process described in Example 4, without adding maltose and with other operation steps unchanged, the fiber breaking strength was 20 cN / dtex, the initial modulus was 700 cN / dtex, and the test showed that there were no network pores inside and on the surface of the fiber, the bioglass content in the fiber was 7.0%, the fiber mechanical properties were low and could not meet the mechanical performance requirements for implantation in vivo.

[0130] Comparative Example 2

[0131] Following the operation process described in Example 4, without adding maltose and bioglass, and with other operation steps unchanged, the fiber breaking strength was 45 cN / dtex, the initial modulus was 2000 cN / dtex, and the fiber was found to have no network pores inside or on the surface, and the fiber did not contain bioceramics.

[0132] Contrast agent 3

[0133] Following the procedure described in Example 4, maltose was replaced with sodium chloride particles with a diameter of 1 μm, which account for 6% of the mass of ultra-high molecular weight polyethylene resin. Other operational steps remained unchanged. The fiber breaking strength was 18 cN / dtex, and the initial modulus was 650 cN / dtex. Testing revealed discontinuous pores within the fiber, with a pore size of 1 μm and a porosity of 10%. The fiber contained 7% bioglass. The fiber's mechanical properties were low and could not meet the mechanical performance requirements for in vivo implantation.

[0134] Experimental Example

[0135] The saline adsorption capacity of the UHMWPE fiber samples obtained from Example 4, Comparative Example 1, and Comparative Example 2 was tested. To more intuitively observe the adsorption capacity of the three different liquid fiber samples for tissue fluid, CuSO4·5H2O was added to the saline to prepare a sky-blue saline solution. A 20cm length of each of the different UHMWPE fiber samples obtained from Example 4, Comparative Example 1, and Comparative Example 2 was placed along the wall of a beaker, with one end of the fiber at the bottom and the other end outside the beaker opening. A 1cm layer of sky-blue saline was added to the beaker, and the migration speed of the saline within the fiber was observed. The results showed that the simulated saline solution rose fastest in the fiber of Example 4, followed by the fiber of Comparative Example 1, and the fiber of Comparative Example 2 was essentially unstained. This indicates that the internal network pores and bioglass of the fiber in Example 4 facilitate the adsorption of saline solution.

Claims

1. A polyethylene composite fiber comprising ultra-high molecular weight polyethylene fiber and bioceramics, wherein the polyethylene composite fiber is prepared by the following steps: 1) dissolving ultra-high molecular weight polyethylene resin in an organic solvent and adding bioceramics to obtain a spinning solution; 2) extruding the spinning solution to form a filament fluid; 3) curing the filament fluid to obtain a dry filament; 4) hot-stretching the dry filament to obtain ultra-high molecular weight polyethylene fiber; 5) treating the ultra-high molecular weight polyethylene fiber, wherein the treatment includes at least one of twisting, weaving, extrusion, and thermoplasticizing, wherein the spinning solution contains maltose.

2. The polyethylene composite fiber according to claim 1, characterized in that: The polyethylene composite fiber has a network of pores on its interior and surface, with a pore size of 0.01~50μm and a porosity of 10~40%; and / or, The polyethylene composite fiber has a breaking strength ≥40cN / dtex and an initial modulus ≥1700cN / dtex.

3. The polyethylene composite fiber according to claim 2, characterized in that: The pore size is 0.1~10μm and the porosity is 20~40%.

4. The polyethylene composite fiber according to claim 1, characterized in that: The bioceramic is selected from at least one of calcium phosphate and bioglass; and / or, The bioceramic is a sphere and / or a spherical-like structure; and / or, The bioceramic has a particle size of 20~20000 nm; and / or, The bioceramic accounts for 2 to 15 wt% of the ultra-high molecular weight polyethylene fiber.

5. The polyethylene composite fiber according to claim 4, characterized in that: The bioceramic accounts for 5-10 wt% of the ultra-high molecular weight polyethylene fiber.

6. A method for preparing polyethylene composite fibers according to any one of claims 1 to 5, comprising: 1) Dissolve ultra-high molecular weight polyethylene resin in an organic solvent and add bioceramics to obtain a spinning solution; 2) The spinning solution is extruded to form a fine filament fluid; 3) The filament fluid is solidified and molded to obtain a dry filament; 4) The dry filaments are thermally stretched to obtain ultra-high molecular weight polyethylene fibers; 5) The ultra-high molecular weight polyethylene fiber is processed, wherein the processing includes at least one of twisting, weaving, extrusion, and thermoplasticizing.

7. The preparation method according to claim 6, characterized in that... In step 1): The spinning solution contains maltose, which accounts for 1-6% of the mass of the ultra-high molecular weight polyethylene resin; and / or, The organic solvent is selected from at least one of decahydronaphthalene, xylene, kerosene, vegetable oil, white oil, and liquid paraffin; and / or, The concentration of ultra-high molecular weight polyethylene resin in the spinning solution is 3~17wt%; and / or, The ultra-high molecular weight polyethylene resin has a viscosity-average molecular weight of not less than 4 million; and / or, The bioceramic accounts for 2-15% of the mass of the ultra-high molecular weight polyethylene resin.

8. The preparation method according to claim 7, characterized in that: The maltose constitutes 2-6% of the mass of the ultra-high molecular weight polyethylene resin; and / or, The concentration of ultra-high molecular weight polyethylene resin in the spinning solution is 7-12 wt%; and / or, The ultra-high molecular weight polyethylene resin has a viscosity-average molecular weight of not less than 5 million; and / or, The bioceramic accounts for 5-10% of the mass of the ultra-high molecular weight polyethylene resin.

9. The preparation method according to claim 8, characterized in that: The viscosity-average molecular weight of the ultra-high molecular weight polyethylene resin is not less than 5.8 million but not more than 8 million.

10. The preparation method according to claim 6, characterized in that... In step 2): The diameter of the extruded spinneret orifice is 0.1~2mm; and / or, The extrusion speed shall not be less than 1 m / min, but not more than 20 m / min; and / or, The filament fluid is stretched by at least 4 times.

11. The preparation method according to claim 10, characterized in that: The diameter of the extruded spinneret orifice is 0.4~1.0 mm; and / or, The filament fluid is stretched by at least 12 times.

12. The preparation method according to claim 6, characterized in that... In step 3): The curing is performed using gas-phase curing and / or a combination of gas-liquid phase curing; and / or, After curing, the solidified material is subjected to water bath stretching of 2-8m and air chamber purging at a wind speed of 0.3-8m / s.

13. The preparation method according to claim 12, characterized in that: Conditions for vapor-phase solidification include a vapor phase temperature of 30–90°C; and / or, The conditions for gas-liquid phase combined curing include a gas phase temperature of 20~80℃ and a liquid phase temperature of 20~60℃.

14. The preparation method according to claim 12, characterized in that: The water bath stretching temperature is 60~90℃, and the stretching ratio is 1.1~2 times; and / or, The wind speed is 0.6~2m / s and the wind temperature is 60~90℃.

15. The preparation method according to claim 14, characterized in that: The water bath stretching temperature is 60~70℃, and the stretching ratio is 1.1~1.

6.

16. The preparation method according to claim 6, characterized in that... In step 4): The heating temperature of the dry filaments during the hot stretching process is 110~160℃; and / or, The dry filament undergoes a thermal stretching deformation of 4 to 25 times.

17. The preparation method according to claim 16, characterized in that: The heating temperature of the dry filaments during the hot stretching process is 135~149℃; and / or, The dry filaments undergo a thermal stretching deformation of 6 to 18 times; The dry filament undergoes at least two stages of hot stretching and at most five stages of hot stretching. The conditions for the first stage of stretching include a temperature of 128~138℃ and a tensile deformation of 2.5~6.0 times; the conditions for the second stage of stretching include a temperature of 138~145℃ and a tensile deformation of 1.2~2.0 times; the conditions for the third stage of stretching include a temperature of 140~145℃ and a tensile deformation of 1.1~1.2 times; the conditions for the fourth stage of stretching include a temperature of 140~147℃ and a tensile deformation of 1.01~1.1 times; and the conditions for the fifth stage of stretching include a temperature of 110~160℃ and a tensile deformation of 0.8~1.1 times.

18. The polyethylene composite fiber according to any one of claims 1 to 5 or the polyethylene composite fiber obtained by the preparation method according to any one of claims 6 to 17 is used in surgical suture and repair products.