Polyethylene composite fiber as well as preparation method and application thereof

Abstract

The invention discloses a polyethylene composite fiber as well as a preparation method and application thereof. The polyethylene composite fiber comprises ultra-high molecular weight polyethylene fiber and biological ceramic, and can be used for surgical suture and repair products. The surgical suture and repair product is mainly used for bone suture and repair, promotes bone growth and repair at a wound, and is beneficial to bone healing. The surgical suture and repair product is high in strength, safe, reliable, good in biocompatibility, beneficial to bone wound healing, not prone to adhesion to bone tissue and easy to detach.

Description

Technical Field

[0001] The present invention relates to the field of medical materials. Specifically, it relates to a bone suture and repair material. More precisely, it relates to a polyethylene composite fiber with ultra-high molecular weight polyethylene fiber as the matrix and bioceramics as the bioactive material, and a preparation method thereof, which is used for surgical suture and repair products. Background Art

[0002] With the improvement of people's living standards, medical conditions are constantly improving. Alleviating patients' pain and improving their recovery level are the common goals of medical workers. The use of repair materials is an indispensable part of the treatment process and is also one of the important factors directly affecting the recovery level of patients. Ultra-high molecular weight polyethylene resin is a linear polymer containing only C and H elements, with a molecular weight higher than one million. The ultra-high molecular weight polyethylene fiber prepared therefrom not only has the characteristics of high strength, high modulus, bending resistance, and friction resistance, but also has good biocompatibility, low cytotoxicity, acid-base-salt corrosion resistance, and long service life. It is a kind of material that can be applied to in-vivo implants, especially as surgical sutures and artificial joints. Bioceramics are currently known as an animal bone repair material that can promote bone growth at the wound site and is beneficial to bone healing.

[0003] The invention patent CN111386133A applied by DSM company in China for the method of preparing osteoconductive fiber products and medical implants containing such osteoconductive fiber products discloses a medical implant, mainly by coating bioactive ceramic particles, such as calcium phosphate, bioactive glass, etc., on non-biodegradable polyester fiber polyethylene terephthalate (PET) products to enhance bone growth. The technical solution adopted in this patent is to coat the surface of polyethylene terephthalate (PET) fibers with polymers and bioactive ceramic particles, so that the fiber surface contains bioactive ceramic particles, which is beneficial to the healing of bone wounds. Although this method enables the fiber to meet the invention purpose, the post-treatment process of the fiber will cause certain damage to the mechanical properties of the fiber. At the same time, in order for the ceramic particles to adhere to the fiber, other chemical reagents or components need to be introduced during the preparation process, increasing the preparation cost and external emissions.

[0004] In summary, in the currently disclosed technical solutions, most are to endow the fiber surface with bioactive substances for in-vivo implantation, which is beneficial to the healing of bone wounds. However, the active substances inside the fiber are wrapped by the fiber and cannot be released, so they cannot be efficiently utilized, and there are disadvantages such as relatively high safety risks when used in the body. Summary of the Invention

[0005] To solve the problems existing in the above prior art, the present invention provides a polyethylene composite fiber, comprising ultra-high molecular weight polyethylene fiber and bioceramics, which can be used for biological surgical suture and repair products. The product has characteristics such as simple composition, no solvent residue, light weight, high strength, high biological activity and good biocompatibility.

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

[0007] Among them, the interior and surface of the polyethylene composite fiber have a network pore structure. Preferably, the pore diameter is 0.01 - 50 μm, and the porosity is 10 - 40%; more preferably, the pore diameter is 0.1 - 10 μm, and the porosity is 20 - 40%.

[0008] The breaking strength of the polyethylene composite fiber is ≥ 40 cN / dtex, and the initial modulus is ≥ 1700 cN / dtex.

[0009] Part of the bioceramics is uniformly distributed inside the fiber and part is embedded on the surface of the fiber.

[0010] The bioceramics are selected from at least one of calcium phosphate and bioactive glass.

[0011] The bioceramics are one or a mixture of spheres and sphere-like bodies.

[0012] The particle size of the bioceramics is 20 - 20000 nm.

[0013] The bioceramics account for 2 - 15 wt% of the ultra-high molecular weight polyethylene fiber, preferably 5 - 10 wt%.

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

[0015] Another object of the present invention is to provide a preparation method of 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) Extrude the spinning solution to form a filament fluid;

[0018] 3) The filament fluid is solidified and formed into a dry filament;

[0019] 4) The dry filament is thermally stretched to obtain ultra-high molecular weight polyethylene fiber;

[0020] 5) Treat the ultra-high molecular weight polyethylene fiber, where the treatment includes at least one of twisting, weaving, extrusion, and thermoplastics.

[0021] Among them, the bioceramics added in step 1) are selected from at least one of calcium phosphate, bioglass, etc.

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

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

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

[0025] The bioceramics are one or a mixture of spheres and spheroids with a diameter of 20-20000 nm.

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

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

[0028] The ultra-high molecular weight polyethylene resin in step 1) of the present 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 exceeding 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 decalin, xylene, kerosene, vegetable oil, white oil, liquid paraffin, etc.

[0033] Preferably, the organic solvent is decalin.

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

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

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

[0037] Preferably, for the dissolution described in the present invention, twin-screw extruder dissolution is adopted.

[0038] For the twin-screw extruder, the dissolution temperature is 140 to 210 °C.

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

[0040] For the twin-screw extruder described, the dissolution speed is 80 to 200 rpm.

[0041] Preferably, the rotation speed of the twin-screw extruder is 110 to 140 rpm.

[0042] In step 2) of the present invention, the spinning solution is extruded from the spinneret holes through metering to form spinning filaments. Before metering, the spinning solution is preferably subjected to a pressure stabilization treatment.

[0043] The pressure stabilization treatment is preferably carried out by at least one of a booster pump, a transfer pump, a metering pump, etc.

[0044] After the spinning filaments are subjected to the pressure stabilization treatment, the pressure in the material pipeline is 2 to 6 MPa.

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

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

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

[0048] For the spinning filaments formed by extrusion from the spinneret holes, the extrusion speed of the spinning solution from the spinneret holes is not less than 1 m / min but not more than 20 m / min.

[0049] The filament fluid obtained by extruding the spinning solution through the spinneret holes is stretched by at least 4 times.

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

[0051] More preferably, the filament fluid obtained by extruding the spinning solution through the spinneret holes 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 refers to the process of solidifying and forming after the spinning solution is extruded from the spinneret holes to form independent spinning fine streams.

[0054] The spinning fine streams are independent fluids. Only after solidification can they be shaped into independent filaments. Otherwise, they are prone to sticking together and it is difficult to separate the formed filament bundles.

[0055] The solidification can be carried out by at least one of gas-phase solidification and gas-liquid phase combined solidification.

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

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

[0058] After the spinning fine streams are solidified, they respectively undergo a water bath drawing of 2-8 m and a gas chamber blowing with a wind speed of 0.3 m / s-8 m / s.

[0059] After the solidification and through the water bath drawing process, at least part of the maltose on its surface and inside can be removed, forming a network pore effect. In order to control the removal speed of maltose, the water bath temperature is 60-90 °C and the drawing ratio is 1.1-2. Preferably, the water bath temperature is 60-70 °C and the drawing ratio is 1.1-1.6.

[0060] In the spinning solution, maltose forms a fluid melt under high-temperature conditions and can be dispersed in the solution of ultra-high molecular weight polyethylene in decalin to obtain a uniform spinning system of ultra-high molecular weight polyethylene-maltose-decalin. As the spinning fluid is extruded and formed, maltose is uniformly distributed inside and on the surface of the fiber. After the water bath drawing, maltose is washed off, forming a uniform network pore effect on the surface and inside of the fiber.

[0061] The wind speed of the gas chamber is 0.6 m / s-2 m / s and the wind temperature is 60-90 °C.

[0062] When the solvent is a volatile organic solvent, gas-phase solidification is preferably used.

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

[0064] The extractant is mainly low-boiling organic solvents such as dichloromethane and chloroform.

[0065] The dry filament mainly refers to the filament obtained by removing the spinning solvent while the spinning fine streams are solidified.

[0066] The dry-state filament mainly refers to the raw filament after the solvent is removed, with a solvent residue of 0 ppm, that is, there is no solvent residue.

[0067] The solvent residue is measured by drying and weighing at a high temperature of 150 °C, and the mass change value of the fiber before and after drying is measured to determine the solvent residue.

[0068] The thermal stretching described in step 4) is mainly a process in which the dry-state raw filament deforms under the action of a drawing tension when heated.

[0069] For the described thermal stretching, the heating temperature of the dry-state filament bundle is 110-160 °C.

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

[0071] In the process of deformation under the action of the tension, the dry-state filament mainly elongates under force.

[0072] In the deformation process, the dry-state filament undergoes a deformation of 4-25 times.

[0073] Preferably, the dry-state filament undergoes a deformation of 6-18 times.

[0074] The dry-state filament undergoes at least 2-stage and at most 5-stage thermal stretching.

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

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

[0077] After the dry-state filament undergoes the above thermal stretching, ultra-high molecular weight polyethylene fibers are obtained.

[0078] The breaking strength of the polyethylene composite fiber is ≥40 cN / dtex, and the initial modulus is ≥1700 cN / dtex.

[0079] The mechanical properties of the polyethylene composite fiber are tested by the tensile property test method for high-strength chemical fiber filaments in GB / T 19975-2005.

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

[0081] During the hot stretching process of the ultra-high molecular weight polyethylene fiber, the bioceramics slip under the action of the drawing stress and slide in the direction with less resistance. Since the fiber is subjected to a longitudinal force, the spherical particles inside the fiber will slip transversely to the fiber, that is, to the surface. By regulating parameters such as the drawing tension, drawing temperature, and the network holes formed inside the fiber by removing maltose, the spherical bioceramic particles inside the fiber are controlled to slip to the fiber surface, aggregate or embed on the fiber surface.

[0082] The control of the tension is one of the important factors for regulating the embedding of bioceramics on the fiber surface.

[0083] The interaction between the ultra-high molecular weight polyethylene material and the bioceramics mainly exists in the space between the polyethylene macromolecular chains. When the polyethylene bioceramic fiber acts in the living body, the tissue fluid in the living body penetrates into the fiber interior through the network holes, generates a force after contacting the bioceramics on the fiber surface, and the bioceramics use the force of the network holes and the tissue fluid to slip to the fiber surface, detach from the fiber surface, and aggregate at the bone tissue wound to promote bone growth and repair.

[0084] The network channels inside the fiber make the displacement of the bioceramics inside the fiber relatively easy. At the same time, the network channels can induce the tissue fluid in the living body to diffuse into the channels and induce and capture the active bioceramics inside the fiber.

[0085] In addition, there is no adhesion between the surface of the polyethylene fiber and the bone tissue, and no inflammatory reaction occurs at the wound under the action of the suture.

[0086] This method has a simple process and low cost. The obtained product has characteristics such as simple composition, no solvent residue, stable performance, light weight, high strength, high biological activity, and good biocompatibility, and can meet medical conditions.

[0087] The ultra-high molecular weight polyethylene fiber is processed through at least one of the processes of twisting, weaving, extrusion, thermoplastics, etc. 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 surgical suture and repair products.

[0089] The polyethylene composite fiber of the present invention has the characteristics of high strength, safety and reliability, good biocompatibility, being beneficial to bone wound healing, non-adhesion, and easy removal.

[0090] The surgical suture and repair products of the present invention are mainly used for orthopedic surgical sutures, fixing fibers at bone fracture sites, artificial joints, etc. in animals. They have good biocompatibility in animals. When contacting with the tissue fluid in animals, the bioceramics in the fibers are released outward from the fiber carriers under the action of the tissue fluid, combine with bones, and promote bone growth and bone healing.

[0091] The present invention has the following advantages:

[0092] This technical solution improves the existing spinning process of ultra-high molecular weight polyethylene fibers, adds bioceramics online, regulates the drawing temperature and drawing ratio, and develops a process for preparing polyethylene composite fibers;

[0093] At the same time, the ultra-high molecular weight polyethylene fibers developed by this technical solution contain bioceramics, have application value in the fields of surgical sutures and bone repair, improve the added value of products, and also significantly improve the existing medical level and improve the comfort of patients;

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

[0095] In short, the preparation method of the polyethylene composite fiber provided by the present invention has low cost, is safe and environmentally friendly, and is suitable for modern industrial production; the obtained fibers have excellent mechanical properties, low cytotoxicity, good biocompatibility and other characteristics, meeting the requirements of medical conditions. Specific Embodiments

[0096] The present invention will be specifically described below in conjunction with specific embodiments. It is necessary to point out here that the following embodiments are only for further illustration of the present invention and cannot be construed as limiting the protection scope of the present invention. Some non-essential improvements and adjustments made by those skilled in the art to the present invention based on the content of the present invention still fall within the protection scope of the present invention.

[0097] The raw materials used in the examples and comparative examples, if not specifically defined, are those disclosed in the prior art, for example, they can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0098] Pore size test method for composite fibers: Conduct surface morphology scanning through a scanning electron microscope (SEM) to measure the diameter of fiber holes.

[0099] Porosity test method for composite fibers: Measure the pore size and the number of pores per unit area, and calculate the percentage of the total area of the pores in the unit area.

[0100] Example 1

[0101] Ultra-high molecular weight polyethylene resin with a viscosity-average molecular weight of 4 million is dispersed in decalin (the mass percentage of ultra-high molecular weight polyethylene is 9%). After swelling by stirring at 90 °C for 4 h, maltose (the added mass is 6% of the ultra-high molecular weight polyethylene resin) and calcium phosphate with a diameter of 20 nm (the added mass is 10% of the ultra-high molecular weight polyethylene resin) are respectively added. After uniform dispersion, it is mixed and dissolved by a twin-screw extruder, transported by a booster pump and metered by a metering pump, and then extruded through a spinneret hole with a diameter of 0.4 mm at a speed of 1 m / min to obtain a spinning filament. The spinning filament enters a hot air duct to remove the solvent (the duct air is nitrogen at 60 °C), and then successively passes through a water bath with a length of 2 m, a temperature of 90 °C, a draw ratio of 1.1 times and an air chamber with a wind speed of 2 m / min and a wind temperature of 90 °C to obtain a dry filament. The dry filament successively undergoes a primary draw at 110 °C with a draw ratio of 2 times; a secondary draw at 145 °C with a draw ratio of 5 times; a tertiary draw at 149 °C with a draw ratio of 1.2 times, and finally ultra-high molecular weight polyethylene calcium phosphate salt fiber is obtained. The fiber has a breaking strength of 40 cN / dtex and an initial modulus of 1700 cN / dtex. After detection, the fiber has network pores inside and on the surface, with a pore diameter of 0.01 μm and a porosity of 40%. The calcium phosphate particles in the fiber are 9%. This fiber is used for bone sutures after being twisted.

[0102] Example 2

[0103] Ultra-high molecular weight polyethylene resin with a viscosity-average molecular weight of 5.8 million is dispersed in decalin (the mass percentage of ultra-high molecular weight polyethylene is 7%). After swelling by stirring at 98 °C for 2 h, maltose (the added mass is 1% of the ultra-high molecular weight polyethylene resin) and calcium phosphate with a diameter of 20000 nm (the added mass is 3% of the ultra-high molecular weight polyethylene resin) are respectively added. After uniform dispersion, it is mixed and dissolved by a twin-screw extruder, transported by a booster pump and metered by a metering pump, and then extruded through a spinneret hole with a diameter of 1 mm at a speed of 1 m / min to obtain a spinning filament. The spinning filament enters a hot air duct to remove the solvent (the duct air is nitrogen at 90 °C), and then successively passes through a water bath with a length of 8 m, a temperature of 60 °C, a draw ratio of 2 times and an air chamber with a wind speed of 0.3 m / min and a wind temperature of 60 °C to obtain a dry filament. The dry filament successively undergoes a primary draw at 135 °C with a draw ratio of 5.5 times; a secondary draw at 147 °C with a draw ratio of 2.8 times; a tertiary draw at 150 °C with a draw ratio of 1.1 times, and finally ultra-high molecular weight polyethylene calcium phosphate salt fiber is obtained. The fiber has a breaking strength of 40 cN / dtex and an initial modulus of 1700 cN / dtex. After detection, the fiber has network pores inside and on the surface, with a pore diameter of 50 μm and a porosity of 20%. The calcium phosphate particles in the fiber are 2.9%. This fiber is used for artificial joints after being braided.

[0104] Example 3

[0105] Ultra-high molecular weight polyethylene resin with a viscosity-average molecular weight of 8 million is dispersed in decalin (the mass percentage of ultra-high molecular weight polyethylene is 3%). After swelling by stirring at 100 °C for 3 h, maltose (the added mass is 3% of the ultra-high molecular weight polyethylene resin) and calcium phosphate with a diameter of 100 nm (the added mass is 10% of the ultra-high molecular weight polyethylene resin) are added respectively. After uniform dispersion, it is mixed and dissolved by a twin-screw extruder, transported by a booster pump, metered by a metering pump, and then extruded through a spinneret hole with a diameter of 0.7 mm at a speed of 20 m / min to obtain a spinning filament. The spinning filament enters a hot air duct to remove the solvent (the duct air is 80 °C nitrogen), and then successively passes through a 4 m long, 70 °C, 1.3-fold water bath drawing and an air chamber with a wind speed of 1 m / min and a wind temperature of 70 °C to obtain a dry filament. The dry filament successively undergoes a first-stage drawing at 142 °C with a 4-fold ratio; a second-stage drawing at 147 °C with a 1.6-fold ratio; a third-stage drawing at 144 °C with a 1.5-fold ratio; a fourth-stage drawing at 149 °C with a 1.05-fold ratio; a fifth-stage drawing at 149 °C with a 1.02-fold ratio, and finally ultra-high molecular weight polyethylene calcium phosphate fiber is obtained. The fiber has a breaking strength of 46 cN / dtex and an initial modulus of 2100 cN / dtex. After detection, the fiber has network pores inside and on the surface, with a pore diameter of 0.1 μm and a porosity of 30%. The calcium phosphate particles in the fiber are 8.0%. This fiber is used for artificial joints after hot extrusion treatment.

[0106] Example 4

[0107] Ultra-high molecular weight polyethylene resin with a viscosity-average molecular weight of 5 million is dispersed in decalin (the mass percentage of ultra-high molecular weight polyethylene is 7%). Maltose (the added mass is 6% of the ultra-high molecular weight polyethylene resin) is added. After swelling by stirring at 95 °C for 2 h, bioactive glass with a diameter of 1000 nm (the added mass is 8% of the ultra-high molecular weight polyethylene resin) is added. After uniform dispersion, it is mixed and dissolved by a twin-screw extruder, transported by a booster pump, metered by a metering pump, and then extruded through a spinneret hole with a diameter of 1 mm at a speed of 10 m / min to obtain a spinning filament. The spinning filament enters a hot air duct to remove the solvent (the duct air is 90 °C nitrogen), and then successively passes through a 4 m long, 70 °C, 1.4-fold water bath drawing and an air chamber with a wind speed of 1 m / min and a wind temperature of 70 °C to obtain a dry filament. The dry filament successively undergoes a first-stage drawing at 140 °C with a 6-fold ratio; a second-stage drawing at 147 °C with a 1.2-fold ratio; a third-stage drawing at 144 °C with a 1.08-fold ratio, and finally ultra-high molecular weight polyethylene bioactive glass fiber is obtained. The fiber has a breaking strength of 42 cN / dtex and an initial modulus of 1800 cN / dtex. After detection, the fiber has network pores inside and on the surface, with a pore diameter of 10 μm and a porosity of 40%. The bioactive glass in the fiber is 6.0%. After twisting and then knitting treatment, it is used for orthopedic surgical sutures.

[0108] Example 5

[0109] Ultra-high molecular weight polyethylene resin with a viscosity-average molecular weight of 5 million is dispersed in white oil (the mass percentage of ultra-high molecular weight polyethylene is 7%), maltose is added (the added mass is 3% of the ultra-high molecular weight polyethylene resin), after swelling by stirring at 95°C for 2 h, bioactive glass with a diameter of 1000 nm is added (the added mass is 8% of the ultra-high molecular weight polyethylene resin), after uniform dispersion, it is mixed and dissolved by a twin-screw extruder, transported by a booster pump and metered by a metering pump, and then extruded through a spinneret hole with a diameter of 1 mm at a speed of 5 m / min to obtain a spinning filament. The spinning filament enters a chloroform extraction tank to remove the white oil solvent, is dried in a 50°C gas-phase hot box, and then successively passes through a 2 m long, 90°C, 1.5-fold water bath drawing and an air chamber with a wind speed of 0.6 m / min and a wind temperature of 90°C to obtain a dry filament. The dry filament successively undergoes a first-stage drawing at 140°C and 6 times; a second-stage drawing at 147°C and 1.2 times; a third-stage drawing at 144°C and 1.08 times, and finally ultra-high molecular weight polyethylene bioactive glass fiber is obtained. The fiber has a breaking strength of 41 cN / dtex and an initial modulus of 1750 cN / dtex. After testing, the fiber has network pores inside and on the surface, with a pore diameter of 10 μm and a porosity of 20%, and the bioactive glass in the fiber is 6.0%. After twisting and then knitting treatment, it is used for orthopedic surgical sutures.

[0110] Example 6

[0111] Ultra-high molecular weight polyethylene resin with a viscosity-average molecular weight of 5 million is dispersed in xylene (the mass percentage of ultra-high molecular weight polyethylene is 7%), maltose is added (the added mass is 3% of the ultra-high molecular weight polyethylene resin), after swelling by stirring at 95°C for 2 h, bioactive glass with a diameter of 500 nm is added (the added mass is 8% of the ultra-high molecular weight polyethylene resin), after uniform dispersion, it is mixed and dissolved by a twin-screw extruder, transported by a booster pump and metered by a metering pump, and then extruded through a spinneret hole with a diameter of 1 mm at a speed of 5 m / min to obtain a spinning filament. The spinning filament enters a water tank for solidification, is dried in a 50°C gas-phase hot box, and then successively passes through a 2 m long, 90°C, 1.2-fold water bath drawing and an air chamber with a wind speed of 0.6 m / min and a wind temperature of 90°C to obtain a dry filament. The dry filament successively undergoes a first-stage drawing at 140°C and 6 times; a second-stage drawing at 147°C and 1.2 times; a third-stage drawing at 144°C and 1.08 times, and finally ultra-high molecular weight polyethylene bioactive glass fiber is obtained. The fiber has a breaking strength of 42 cN / dtex and an initial modulus of 1800 cN / dtex. After testing, the fiber has network pores inside and on the surface, with a pore diameter of 2 μm and a porosity of 20%, and the bioactive glass in the fiber is 6.0%. After twisting and then knitting treatment, it is used for orthopedic surgical sutures.

[0112] Example 7

[0113] Ultra-high molecular weight polyethylene resin with a viscosity-average molecular weight of 5 million is dispersed in liquid paraffin (the mass percentage of ultra-high molecular weight polyethylene is 7%), maltose is added (the added mass is 3% of the ultra-high molecular weight polyethylene resin), after swelling by stirring at 95 °C for 2 h, bioactive glass with a diameter of 500 nm is added (the added mass is 8% of the ultra-high molecular weight polyethylene resin), after being dispersed evenly, it is mixed and dissolved by a twin-screw extruder, transported by a booster pump and metered by a metering pump, and then extruded through a spinneret hole with a diameter of 1 mm at a speed of 5 m / min to obtain a spinning filament. The spinning filament enters a chloroform extraction tank to remove liquid paraffin, passes through a gas-phase hot box at 50 °C, and then successively passes through a 2 m long, 90 °C, 1.2-fold water bath drawing and an air chamber with a wind speed of 0.6 m / min and a wind temperature of 90 °C, and is dried to obtain a dry filament. The dry filament successively undergoes a primary drawing at 140 °C with a 5.0-fold ratio; a secondary drawing at 147 °C with a 1.8-fold ratio; a tertiary drawing at 149 °C with a 1.1-fold ratio, and finally ultra-high molecular weight polyethylene bioactive glass fiber is obtained. The fiber has a breaking strength of 41 cN / dtex and an initial modulus of 1750 cN / dtex. After testing, the fiber has network pores inside and on the surface, with a pore diameter of 2 μm and a porosity of 20%, and the bioactive glass in the fiber is 6.1%. After being woven, it is used for orthopedic surgical sutures.

[0114] Example 8

[0115] Ultra-high molecular weight polyethylene resin with a viscosity-average molecular weight of 5 million is dispersed in mineral oil (the mass percentage of ultra-high molecular weight polyethylene is 7%), maltose is added (the added mass is 3% of the ultra-high molecular weight polyethylene resin), after swelling by stirring at 95 °C for 2 h, bioactive glass with a diameter of 500 nm is added (the added mass is 8% of the ultra-high molecular weight polyethylene resin), after being dispersed evenly, it is mixed and dissolved by a twin-screw extruder, transported by a booster pump and metered by a metering pump, and then extruded through a spinneret hole with a diameter of 1 mm at a speed of 5 m / min to obtain a spinning filament. The spinning filament enters a chloroform extraction tank to remove white oil solvent, passes through a gas-phase hot box at 50 °C, and then successively passes through a 2 m long, 90 °C, 1.2-fold water bath drawing and an air chamber with a wind speed of 0.6 m / min and a wind temperature of 90 °C, and is dried to obtain a dry filament. The dry filament successively undergoes a primary drawing at 140 °C with a 5.0-fold ratio; a secondary drawing at 147 °C with a 1.8-fold ratio; a tertiary drawing at 149 °C with a 1.1-fold ratio, and finally ultra-high molecular weight polyethylene bioactive glass fiber is obtained. After testing, the fiber has a breaking strength of 41 cN / dtex and an initial modulus of 1700 cN / dtex. After testing, the fiber has network pores inside and on the surface, with a pore diameter of 2 μm and a porosity of 25%, and the bioactive glass in the fiber is 6.1%. After being twisted, it is used for orthopedic surgical sutures. After being twisted, it is used for orthopedic surgical sutures.

[0116] Example 9

[0117] Ultra-high molecular weight polyethylene resin with a viscosity-average molecular weight of 5 million is dispersed in white oil (the mass percentage of ultra-high molecular weight polyethylene is 7%). Maltose is added (the added mass is 2% of the ultra-high molecular weight polyethylene resin). After swelling by stirring at 95 °C for 2 h, calcium phosphate spheres with a diameter of 20 nm are added (the added mass is 15% of the ultra-high molecular weight polyethylene resin). After uniform dispersion, it is mixed and dissolved by a twin-screw extruder, transported by a booster pump and metered by a metering pump, and then extruded through a spinneret hole with a diameter of 1 mm at a speed of 5 m / min to obtain a spinning filament. The spinning filament enters a chloroform extraction tank to remove the white oil solvent, passes through a 50 °C gas-phase hot box, and then successively passes through a 2 m long, 90 °C, 1.2-fold water bath drawing and an air chamber with a wind speed of 0.6 m / min and a wind temperature of 90 °C, and is dried to obtain a dry filament. The dry filament is successively subjected to a primary drawing at 140 °C and 5.5 times; a secondary drawing at 147 °C and 1.8 times; a tertiary drawing at 144 °C and 1.1 times, and finally ultra-high molecular weight polyethylene calcium phosphate fiber is obtained. The fiber has a breaking strength of 40 cN / dtex and an initial modulus of 1700 cN / dtex. After detection, the fiber has network pores inside and on the surface, with a pore diameter of 0.01 μm and a porosity of 25%. The calcium phosphate content in the fiber is 12%, and it is used for orthopedic surgical sutures after braiding treatment.

[0118] Example 10

[0119] Ultra-high molecular weight polyethylene resin with a viscosity-average molecular weight of 5 million is dispersed in white oil (the mass percentage of ultra-high molecular weight polyethylene is 7%). Maltose is added (the added mass is 4% of the ultra-high molecular weight polyethylene resin). After swelling by stirring at 95 °C for 2 h, calcium phosphate spheres with a diameter of 20000 nm are added (the added mass is 5% of the ultra-high molecular weight polyethylene resin). After uniform dispersion, it is mixed and dissolved by a twin-screw extruder, transported by a booster pump and metered by a metering pump, and then extruded through a spinneret hole with a diameter of 1 mm at a speed of 5 m / min to obtain a spinning filament. The spinning filament enters a chloroform extraction tank to remove the white oil solvent, passes through a 50 °C gas-phase hot box, and then successively passes through a 2 m long, 90 °C, 1.2-fold water bath drawing and an air chamber with a wind speed of 0.6 m / min and a wind temperature of 90 °C, and is dried to obtain a dry filament. The dry filament is successively subjected to a primary drawing at 140 °C and 5.5 times; a secondary drawing at 147 °C and 1.8 times; a tertiary drawing at 144 °C and 1.1 times, and finally ultra-high molecular weight polyethylene calcium phosphate fiber is obtained. The fiber has a breaking strength of 40 cN / dtex and an initial modulus of 1700 cN / dtex. After detection, the fiber has network pores inside and on the surface, with a pore diameter of 50 μm and a porosity of 10%. The calcium phosphate content in the fiber is 4.9%, and it is used for orthopedic repair materials after braiding treatment.

[0120] Example 11

[0121] Ultra-high molecular weight polyethylene resin with a viscosity-average molecular weight of 6 million is dispersed in decalin (the mass percentage of ultra-high molecular weight polyethylene is 9%), maltose is added (the added mass is 6% of the ultra-high molecular weight polyethylene resin), after swelling by stirring at 97 °C for 2 h, calcium phosphate spheres with a diameter of 100 nm are added (the added mass is 6% of the ultra-high molecular weight polyethylene resin), after uniform dispersion, it is mixed and dissolved through a static mixer, transported by a booster pump and metered by a metering pump, and then extruded through a spinneret hole with a diameter of 0.8 mm at a speed of 3 m / min to obtain a spinning filament. The spinning filament enters a hot air duct to remove the solvent (the duct air is 80 °C nitrogen), and then successively passes through a 2 m long, 90 °C, 1.2-fold water bath drawing and an air chamber with a wind speed of 0.6 m / min and a wind temperature of 90 °C to obtain a dry filament. The dry filament successively undergoes a primary drawing at 149 °C and 10 times; a secondary drawing at 147 °C and 2.5 times, and finally ultra-high molecular weight polyethylene calcium phosphate salt fiber is obtained. The fiber has a breaking strength of 41 cN / dtex and an initial modulus of 1900 cN / dtex. After testing, the fiber has network holes inside and on the surface, with a pore diameter of 0.1 μm and a porosity of 10%, and the calcium phosphate content in the fiber is 5.5%. This fiber is used for artificial joints after thermoplastic treatment.

[0122] Example 12

[0123] Ultra-high molecular weight polyethylene resin with a viscosity-average molecular weight of 6 million is dispersed in decalin (the mass percentage of ultra-high molecular weight polyethylene is 8%), maltose is added (the added mass is 6% of the ultra-high molecular weight polyethylene resin), after swelling, bioactive glass spheres with a diameter of 100 nm are added (the added mass is 10% of the ultra-high molecular weight polyethylene resin), after uniform dispersion, it is mixed and dissolved through a dynamic mixer, transported by a booster pump and metered by a metering pump, and then extruded through a spinneret hole with a diameter of 0.8 mm at a speed of 3 m / min to obtain a spinning filament. The spinning filament enters a hot air duct to remove the solvent (the duct air is 80 °C nitrogen), and then successively passes through a 2 m long, 90 °C, 1.2-fold water bath drawing and an air chamber with a wind speed of 0.6 m / min and a wind temperature of 90 °C to obtain a dry filament. The dry filament successively undergoes a primary drawing at 149 °C and 10 times; a secondary drawing at 147 °C and 2.5 times, and finally ultra-high molecular weight polyethylene bioactive glass fiber is obtained. The fiber has a breaking strength of 41 cN / dtex and an initial modulus of 1900 cN / dtex. After testing, the fiber has network holes inside and on the surface, with a pore diameter of 0.1 μm and a porosity of 10%, and the bioactive glass content in the fiber is 7.5%. This fiber is used for artificial joints after thermoplastic treatment.

[0124] Example 13

[0125] Ultra-high molecular weight polyethylene resin with a viscosity-average molecular weight of 6 million is dispersed in decalin (the mass percentage of ultra-high molecular weight polyethylene is 7%), maltose is added (the added mass is 6% of the ultra-high molecular weight polyethylene resin), after swelling, bioactive glass spheres with a diameter of 100 nm are added (the added mass is 10% of the ultra-high molecular weight polyethylene resin), and after being dispersed evenly in the reaction kettle, the temperature is raised to 180 °C for dissolution. It is transported by a transfer pump and metered by a metering pump, and then extruded through a spinneret hole with a diameter of 0.8 mm at a speed of 4 m / min to obtain a spinning filament. The spinning filament enters a hot air duct to remove the solvent (the duct air is 90 °C nitrogen), and then successively passes through a 2 m long, 90 °C, 1.2-fold water bath drawing and an air chamber with a wind speed of 0.6 m / min and a wind temperature of 90 °C to obtain a dry filament. The dry filament successively undergoes a primary drawing at 149 °C with a 10-fold ratio; a secondary drawing at 149 °C with a 2.0-fold ratio, and finally ultra-high molecular weight polyethylene bioactive glass fiber is obtained. The fiber has a breaking strength of 40 cN / dtex and an initial modulus of 1800 cN / dtex. After testing, the fiber has network pores inside and on the surface, with a pore diameter of 0.1 μm, a porosity of 10%, and a bioactive glass content of 7.5% in the fiber. This fiber is used for artificial joints after thermoplastic treatment.

[0126] Example 14

[0127] Ultra-high molecular weight polyethylene resin with a viscosity-average molecular weight of 6 million is dispersed in decalin (the mass percentage of ultra-high molecular weight polyethylene is 7%), maltose is added (the added mass is 6% of the ultra-high molecular weight polyethylene resin), after swelling, bioactive glass spheres with a diameter of 100 nm are added (the added mass is 6% of the ultra-high molecular weight polyethylene resin), and after being dispersed evenly in the reaction kettle, the temperature is raised to 190 °C for dissolution. It is transported by a transfer pump and metered by a metering pump, and then extruded through a spinneret hole with a diameter of 0.8 mm at a speed of 4 m / min to obtain a spinning filament. The spinning filament enters a hot air duct to remove the solvent (the duct air is 90 °C air), and then successively passes through a 2 m long, 90 °C, 1.2-fold water bath drawing and an air chamber with a wind speed of 0.6 m / min and a wind temperature of 90 °C to obtain a dry filament. The dry filament successively undergoes a primary drawing at 149 °C with a 10.00-fold ratio; a secondary drawing at 147 °C with a 1.40-fold ratio; a tertiary drawing at 147 °C with a 1.20-fold ratio, and finally ultra-high molecular weight polyethylene bioactive glass fiber is obtained. The fiber has a breaking strength of 43 cN / dtex and an initial modulus of 1900 cN / dtex. After testing, the fiber has network pores inside and on the surface, with a pore diameter of 0.1 μm, a porosity of 20%, and a bioactive glass content of 5.5% in the fiber. This fiber is used for surgical sutures after braiding treatment.

[0128] Comparative Example 1

[0129] According to the operation process described in Example 4, without adding maltose and keeping other operation steps unchanged, the fiber breaking strength is 20 cN / dtex and the initial modulus is 700 cN / dtex. After detection, there are no network holes inside and on the surface of the fiber, the bio-glass in the fiber is 7.0%, and the mechanical properties of the fiber are low, unable to meet the mechanical property requirements for in-vivo implantation.

[0130] Comparative Example 2

[0131] According to the operation process described in Example 4, without adding maltose and bio-glass and keeping other operation steps unchanged, the fiber breaking strength is 45 cN / dtex and the initial modulus is 2000 cN / dtex. After detection, there are no network holes inside and on the surface of the fiber, and the fiber does not contain bioceramics.

[0132] Contrast Agent 3

[0133] According to the operation process described in Example 4, replace maltose with sodium chloride particles with a mass of 6% of ultra-high molecular weight polyethylene resin and a diameter of 1 μm, and keep other operation steps unchanged. The fiber breaking strength is 18 cN / dtex and the initial modulus is 650 cN / dtex. After detection, there are discontinuous holes inside the fiber with a pore diameter of 1 μm and a porosity of 10%, and the bio-glass in the fiber is 7%. The mechanical properties of the fiber are low, unable to meet the mechanical property requirements for in-vivo implantation.

[0134] Experimental Example

[0135] The UHMWPE fiber samples obtained from Example 4, Comparative Example 1, and Comparative Example 2 were respectively tested for the saline adsorption capacity. In order to more intuitively observe the ability of the three different fiber samples to adsorb tissue fluid, CuSO 4 ·5H 2 O was added to the physiological saline to prepare sky-blue physiological saline. Different UHMWPE fiber samples with a length of 20 cm obtained from Example 4, Comparative Example 1, and Comparative Example 2 were respectively placed in the beaker along the inner wall of the beaker, that is, one end of the fiber was at the bottom of the beaker and the other end was outside the beaker mouth. Sky-blue physiological saline with a height of 1 cm was added to the beaker, and the migration speed of the sky-blue physiological saline inside the fiber was observed. The results were as follows: The simulated physiological saline rose fastest in the fiber of Example 4, followed by the fiber obtained from Comparative Example 1, and finally the fiber obtained from Comparative Example 2 was basically not stained. It shows that the network holes and bio-glass inside the fiber in Example 4 are helpful for adsorbing physiological saline.

Claims

1. A polyethylene composite fiber, comprising ultra-high molecular weight polyethylene fiber and bioceramics.

2. The polyethylene composite fiber according to claim 1, characterized in that: The polyethylene composite fiber has a network pore structure inside and on the surface, preferably, the pore size is 0.01-50 μm, the porosity is 10-40%, more preferably, the pore size is 0.1-10 μm, the porosity is 20-40%; and / or, The breaking strength of the polyethylene composite fiber is ≥40 cN / dtex, and the initial modulus is ≥1700 cN / dtex.

3. 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 spheroid; and / or, The particle size of the bioceramic is 20 to 20000 nm; and / or, The bioceramic accounts for 2-15 wt %, preferably 5-10 wt % of the ultra-high molecular weight polyethylene fiber.

4. The method for preparing the polyethylene composite fiber according to any one of claims 1 to 3, comprising: 1) dissolving an 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) The filament fluid is solidified to obtain dry filaments; 4) The dry filaments are subjected to heat stretching to obtain ultra-high molecular weight polyethylene fibers; 5) processing the ultra-high molecular weight polyethylene fiber, wherein the processing comprises at least one of twisting, weaving, extrusion, and thermoplasticization.

5. The preparation method according to claim 4, characterized in that In step 1): The spinning solution contains maltose, preferably, the maltose accounts for 1-6% of the mass of the ultra-high molecular weight polyethylene resin, more preferably 2-6%; and / or, The organic solvent is selected from at least one of decalin, xylene, kerosene, vegetable oil, white oil, and liquid paraffin; and / or, The concentration of the ultra-high molecular weight polyethylene resin in the spinning solution is 3 to 17 wt%, preferably 7 to 12 wt%; and / or, The viscosity average molecular weight of the ultra-high molecular weight polyethylene resin is not less than 4 million, preferably not less than 5 million, more preferably not less than 5.8 million, but not more than 8 million; and / or, The bioceramic accounts for 2-15% of the mass of the ultra-high molecular weight polyethylene resin, preferably 5-10%.

6. The preparation method according to claim 4, characterized in that In step 2): The diameter of the extruded spinneret hole is 0.1 to 2 mm, preferably 0.4 to 1.0 mm; and / or, The extrusion speed is not less than 1m / min but not more than 20m / min; and / or, The filamentary fluid is stretched at least 4 times, preferably at least 12 times.

7. The preparation method according to claim 4, characterized in that In step 3): The curing is performed by gas phase curing and / or gas-liquid phase combined curing; and / or, Preferably, the conditions for gas phase curing include a gas phase temperature of 30 to 90° C.; and / or, Preferably, the conditions for gas-liquid phase combination solidification include a gas phase temperature of 20 to 80° C. and a liquid phase temperature of 20 to 60° C.; and / or, After the curing, the product is stretched in a water bath for 2 to 8 m and purged in an air chamber with a wind speed of 0.3 to 8 m / s.

8. The preparation method according to claim 7, characterized in that: The temperature of the water bath stretching is 60-90°C, and the stretching ratio is 1.1-2 times; preferably, the temperature of the water bath stretching is 60-70°C, and the stretching ratio is 1.1-1.6; and / or, The wind speed is 0.6-2 m / s, and the wind temperature is 60-90°C.

9. The preparation method according to claim 4, characterized in that In step 4): The heating temperature of the dry filaments in the heat stretching is 110-160° C., preferably 135-149° C.; and / or, The dry silk is stretched to a deformation of 4 to 25 times when heated, preferably 6 to 18 times; Preferably, the dry filament undergoes at least 2 levels of heat stretching and at most 5 levels of heat stretching; more preferably, the conditions for the first-level stretching include a temperature of 128-138°C and a stretching deformation of 2.5-6.0 times, the conditions for the second-level stretching include a temperature of 138-145°C and a stretching deformation of 1.2-2.0 times, the conditions for the third-level stretching include a temperature of 140-145°C and a stretching deformation of 1.1-1.2 times, the conditions for the fourth-level stretching include a temperature of 140-147°C and a stretching deformation of 1.01-1.1 times, and the conditions for the fifth-level stretching include a temperature of 110-160°C and a stretching deformation of 0.8-1.1 times.

10. The polyethylene composite fiber according to any one of claims 1 to 3 or the polyethylene composite fiber obtained by the preparation method according to any one of claims 4 to 9 is used for surgical suture and repair products.