CN117736566B

CN117736566B - Carbon fiber reinforced polyaryletherketone medical composite material and preparation method and application thereof

Info

Publication number: CN117736566B
Application number: CN202410182240.1A
Authority: CN
Inventors: 李晓萌; 李春明; 欧阳兆飞; 王耀; 殷敬华
Original assignee: Shanghai Perli Medical Materials Co ltd
Current assignee: Shanghai Perli Medical Materials Co ltd
Priority date: 2024-02-19
Filing date: 2024-02-19
Publication date: 2024-05-10
Anticipated expiration: 2044-02-19
Also published as: CN117736566A

Abstract

The invention provides a carbon fiber reinforced polyaryletherketone medical composite material, and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing carbon fiber, polyaryletherketone, acrylate-terminated polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer, an active functional group-terminated multi-arm polyethylene glycol derivative and water for reaction to obtain a hydrogel composite system; and carrying out hot press molding, banburying, drying and melt extrusion on the hydrogel composite system to obtain the granules of the carbon fiber reinforced polyaryletherketone medical composite material. According to the invention, the acrylate-terminated PEG-PPG-PEG triblock copolymer is adopted, so that the interfacial compatibility of the polyaryletherketone and the carbon fiber can be promoted, and the fusion of the polyaryletherketone and the carbon fiber is promoted through the formed three-dimensional reticular hydrogel structure, so that the polyaryletherketone is not easy to fall off in the preparation process, and meanwhile, the production efficiency is high; ensure that the reactant is green, environment-friendly and excellent in biocompatibility.

Description

Carbon fiber reinforced polyaryletherketone medical composite material and preparation method and application thereof

Technical Field

The invention belongs to the technical field of medical composite materials, and particularly relates to a carbon fiber reinforced polyaryletherketone medical composite material, and a preparation method and application thereof.

Background

The carbon fiber is of a six-membered ring stable structure, has few surface active groups, has fast crystallinity, high melt viscosity and high processing temperature, has poor wettability, is difficult to completely infiltrate carbon fiber tows, cannot exert the excellent performance of the carbon fiber as a reinforcement, and causes weak interface interaction, so that the carbon fiber and the carbon fiber cannot be well combined together in the processing and forming process of an actual composite material, and a large number of tiny cavities appear in the processed and formed material to influence the mechanical property of the processed and formed material. Therefore, the preparation of the carbon fiber reinforced polyaryletherketone with high biosafety and excellent mechanical property is the key point of research. The polyaryletherketone is used as a special polymer material and comprises polyether-ether-ketone, polyether-ether-ketone or polyether-ketone-ether-ketone, and the like. The preparation methods of carbon fiber reinforced polyaryletherketone raw materials reported in most of the prior patents (CN 113248863A, CN114133697A, CN111533931A and CN 111423695A) are suitable for manufacturing industrial-grade raw materials because of excessive additives and most industrial additives.

CN111410759a relates to a Carbon Fiber (CF)/Polyetheretherketone (PEEK) composite material with excellent high-temperature mechanical properties and a preparation method thereof, the preparation method comprises the following steps: (1) decomposing the original sizing agent on the surface of the CF at high temperature; (2) In a saturated steam environment, carrying out microwave radiation and ultraviolet radiation on CF simultaneously, and marking a product as modified CF; (3) Immersing the modified CF into polyamide acid/N-methyl-2-pyrrolidone/carbon nano tube suspension, taking out, drying, and performing two-stage heat treatment to obtain the sized modified carbon fiber CF. The polyamide acid contained in the CF/PEEK composite material is converted into polyimide in the later period, has potential cytotoxicity side effects, and is not suitable for applying biological materials for in vivo interventional implantation.

CN113501982a provides a preparation method of a carbon fiber reinforced PEEK composite material, which comprises the following steps: s1) oxidizing the carbon fiber without the sizing agent on the surface by a hot air method to obtain surface oxidized carbon fiber; s2) carrying out acyl chlorination reaction on the surface oxidized carbon fiber and thionyl chloride, and drying to obtain acyl chlorinated carbon fiber; s3) blending the acyl chloride carbon fiber and PEEK, and obtaining the carbon fiber reinforced PEEK composite material through a hot pressing method. The invention has no acid treatment step in the complete preparation process, improves the possibility of industrial production, and can obtain the carbon fiber reinforced PEEK composite material without pretreatment of PEEK, thereby improving the production efficiency. The prepared composite material has the characteristics of no acid treatment, good interface compatibility, good mechanical property, good biocompatibility and the like. However, the method carries out chemical modification on CF to form surface defects, so that the damage to the strength of the monofilaments is large, and the damage degree is difficult to control; in addition, hazardous chemicals such as thionyl chloride and the like are used, and the waste liquid is difficult to treat.

In view of the above, in order to improve wettability between the polyaryletherketone and the carbon fiber, obtaining the carbon fiber reinforced polyaryletherketone medical composite material meeting the requirements of high biosafety and excellent mechanical properties is still a technical difficulty of the industry.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a carbon fiber reinforced polyaryletherketone medical composite material, and a preparation method and application thereof.

In order to avoid the problem of poor interfacial compatibility of the polyaryletherketone and the carbon fiber, a polyethylene glycol-polypropylene glycol-polyethylene glycol (PEG-PPG-PEG) triblock amphiphilic copolymer is adopted as a high molecular nonionic surfactant, and the interfacial compatibility of the polyaryletherketone and the carbon fiber is promoted by adjusting the hydrophilicity and hydrophobicity of the PEG-PPG-PEG. The hydrophilic-hydrophobic nature of PEG-PPG-PEG depends on the ratio of hydrophilic segment (ethylene glycol)/hydrophobic segment (propylene glycol), the higher the ethylene glycol content, the better the oil-in-water stabilizer performance.

Therefore, the PEG-PPG-PEG triblock copolymer is used as a bridge, and the polyaryletherketone powder and the carbon fiber can be uniformly compounded; to further immobilize and fuse the two, this can be achieved by forming hydrogels with three-dimensional network structure. Preparation of hydrogels this can be achieved by modifying the carbon-carbon double bonds at the end groups of the PEG-PPG-PEG triblock copolymer: the hydrogel is obtained by Michael addition reaction of a carbon-carbon double bond and amino or sulfhydryl groups of a multi-arm polyethylene glycol derivative. The amphiphilic polymer of the PEG-PPG-PEG capped by the carbon-carbon double bond comprises PEG-PPG-PEG capped by acrylic ester and PEG-PPG-PEG capped by vinyl sulfone. In view of the complex preparation process and high manufacturing cost of the vinyl sulfone end capped PEG-PPG-PEG, the invention selects the acrylic ester end capped PEG-PPG-PEG amphiphilic polymer. The adopted amphiphilic polymer of the PEG-PPG-PEG with the end capped by the acrylic ester has the advantages that the PEG chain segment structure is hydrophilic, the PPG chain segment structure is hydrophobic, and the hydrophilic and hydrophobic properties of the PEG-PPG-PEG with the end capped by the acrylic ester can be adjusted by adjusting the proportion of the hydrophilic and hydrophobic structures of the PEG-PPG-PEG, so that the interfacial compatibility of the polyaryletherketone and the carbon fiber is promoted.

According to the invention, the PEG-PPG-PEG triblock copolymer modified by acrylic ester is used as an emulsifier, and the Michael addition reaction of the carbon-carbon double bond functional group of the PEG-PPG-PEG triblock copolymer and the amino and/or mercapto active functional group of the polyethylene glycol derivative is carried out to form a three-dimensional reticular hydrogel structure, so that the interfacial fusion of the carbon fiber and the polyaryletherketone is further enhanced.

According to the invention, the acrylate-terminated PEG-PPG-PEG triblock copolymer is adopted, so that the interfacial compatibility of the polyaryletherketone and the carbon fiber can be promoted, and the fusion of the polyaryletherketone and the carbon fiber is promoted through the formed three-dimensional reticular hydrogel structure, so that the polyaryletherketone is not easy to fall off in the preparation process, and meanwhile, the production efficiency is high; the preparation method adopts polyethylene glycol derivatives with excellent biocompatibility and no participation of organic solvents, ensures that reactants are green, environment-friendly and excellent in biocompatibility, and the prepared carbon fiber reinforced polyaryletherketone medical composite material is suitable for being applied to polyaryletherketone biomedical materials.

To achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the invention provides a preparation method of a carbon fiber reinforced polyaryletherketone medical composite material, which comprises the following steps:

mixing carbon fiber, polyaryletherketone, acrylate-terminated polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer, an active functional group-terminated multi-arm polyethylene glycol derivative and water for reaction to obtain a hydrogel composite system;

And carrying out hot press molding, banburying, drying and melt extrusion on the hydrogel composite system to obtain the carbon fiber reinforced polyaryletherketone medical composite material.

The PEG-PPG-PEG triblock copolymer capped by acrylic ester is used as a nonionic surfactant and is used as a bridge for connecting carbon fibers and the interface action of the polyaryletherketone, so that the wettability of the carbon fibers and the polyaryletherketone resin is enhanced, and the polyaryletherketone resin is promoted to be fused with the carbon fibers more uniformly; meanwhile, the three-dimensional network structure hydrogel formed by the PEG-PPG-PEG capped by the acrylic resin and the multi-arm polyethylene glycol derivative capped by the active functional group further enhances the fusion property of the carbon fiber and the polyaryletherketone, so that the subsequent hot press molding is convenient to carry out; the tensile strength of the prepared section can reach more than 198.2MPa, and the osteoblast culture research proves that the carbon fiber reinforced polyaryletherketone medical composite material has no cell toxic or side effect and has great application value in the polyaryletherketone medical material.

The mass ratio of the carbon fiber, the polyaryletherketone, the acrylic ester end capped polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer and the active functional group end capped multi-arm polyethylene glycol derivative is (0.03-30): 1: (0.02-50): (0.02-50), which may be 0.03：1：0.02：0.02、0.3：1：0.2：0.2、3：1：2：2、1：1：2：2、1：1：1：2、3：1：1.5：1.5、4：1：1.5：1.5、5：1：1.5：1.5、3：1：2：2、4：1：2：2、5：1：2：2、3：1：3：3、4：1：3：3、5：1：3：3、30：1：25：50、20：1：50：25, and specific point values between the above point values, is limited in space and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values included in the range.

The carbon fibers are discontinuous carbon fibers.

The carbon fibers may have a length of 10-1000 μm, for example, 10 um, 100 μm, 200 μm, 300 μm, 500 μm, 800 μm, 1000 μm, and specific point values between the above point values, are limited in space and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the range.

The original sizing agent on the surface of the commercial carbon fiber is decomposed at high temperature to obtain the carbon fiber; wherein pyrolysis refers to sintering at 300-420 deg.C for 5-180min.

The polyaryletherketone comprises any one or a combination of at least two of polyether-ether-ketone, polyether-ketone, polyether-ether-ketone or polyether-ketone-ether-ketone.

The particle size of the polyaryletherketone is 2-100 um, for example, 2 um, 5 um, 10 um, 50 um, 80 um, 90 um, 100 um, and specific point values among the above point values, are limited in space and for simplicity, the present invention is not exhaustive of the specific point values included in the range.

The acrylate-terminated polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer has a structure shown in a formula 1:

Where x is 1-100, y is 1-100, and z is 1-100, e.g., x, y, z may each independently be 1,2, 5, 10, 15, 20, 30, 50, 80, 90, 100, and specific point values between the above point values, are for brevity and for brevity, the invention is not intended to be exhaustive of the specific point values encompassed by the described ranges.

The adopted acrylic ester end capped polyethylene glycol-polypropylene glycol-polyethylene glycol (PEG-PPG-PEG) is an amphiphilic polymer, the PEG block structure is hydrophilic, the PPG block structure is hydrophobic, and the hydrophilic and hydrophobic properties of the PEG-PPG-PEG end capped by carbon-carbon double bonds can be adjusted by adjusting the proportion of the hydrophilic and hydrophobic structures of the PEG-PPG-PEG, so that the interfacial compatibility of the polyaryletherketone and the carbon fibers is promoted.

The preparation method of the acrylate-terminated polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer comprises the following steps:

Mixing hydroxyl-terminated polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer, carbonate and acryloyl chloride, and reacting to obtain the acrylate-terminated polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer.

The hydroxyl-terminated polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer has a structure shown in a formula 2:

The carbonate comprises potassium carbonate and/or sodium carbonate.

The hydroxyl-terminated polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer is mixed with carbonate, dissolved in a solvent, and then the acryloyl chloride is dropwise added into an ice-water bath for reaction.

The mass ratio of the hydroxyl-terminated polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer to the carbonate is (0.05-20): 1, for example, may be 0.05: 1. 0.1: 1. 0.5: 1. 1: 1. 2: 1. 5: 1. 8: 1. 10: 1. 15: 1. 18: 1. 20:1, and specific point values between the above point values, are limited in space and for the sake of brevity, the present invention is not intended to exhaustively list the specific point values encompassed by the described range.

The molar ratio of the hydroxyl-terminated polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer to the acryloyl chloride is (0.05-20): 1, for example, may be 0.05: 1. 0.1: 1. 0.5: 1. 1: 1. 2: 1. 5: 1. 8: 1. 10: 1. 15: 1. 18: 1. 20:1, and specific point values between the above point values, are limited in space and for the sake of brevity, the present invention is not intended to exhaustively list the specific point values encompassed by the described range.

Preferably, the temperature of the reaction is 50-70 ℃, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, and specific values between the above values, are not exhaustive of the specific values included in the range for reasons of space and for reasons of simplicity.

Preferably, the reaction is carried out for a period of 3 to 5 days, for example, 3 days, 4 days, 5 days, and specific values between the above values, although for reasons of length and for reasons of simplicity, the invention is not intended to be exhaustive of the specific values included in the range.

Filtering, extracting, drying and distilling the reaction product to obtain the acrylic ester end capped polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer.

The reactive functional group-terminated multi-arm polyethylene glycol derivative includes an amino-terminated multi-arm polyethylene glycol derivative and/or a mercapto-terminated multi-arm polyethylene glycol derivative.

The multi-arm polyethylene glycol derivative with the end capped by the active functional group comprises any one or a combination of at least two of amino-end capped three-arm polyethylene glycol derivative, amino-end capped four-arm polyethylene glycol derivative, amino-end capped six-arm polyethylene glycol derivative, amino-end capped eight-arm polyethylene glycol derivative, mercapto-end capped three-arm polyethylene glycol derivative, mercapto-end capped four-arm polyethylene glycol derivative, mercapto-end capped six-arm polyethylene glycol derivative or mercapto-end capped eight-arm polyethylene glycol derivative.

The reactive functional group-terminated multi-arm polyethylene glycol derivative comprises a structure shown in any one of formulas 3-6:

where n is 1-100, and may be, for example, 1, 2, 5, 10, 15, 20, 30, 50, 80, 90, 100, and specific point values between the above point values, the present invention is not intended to be exhaustive of the specific point values included in the range for reasons of space and for reasons of brevity.

The adopted acrylic ester end capped PEG-PPG-PEG can be prepared by medical grade PEG-PPG-PEG block copolymer, and the multi-arm polyethylene glycol derivative with the end capped active functional group can also be prepared by medical grade multi-arm polyethylene glycol modification; the acrylate-capped PEG-PPG-PEG and the reactive functional group-capped multi-arm polyethylene glycol derivative have no toxic and side effects, so that the PEG derivative is widely reported to be applicable to in vivo through FDA authentication. Therefore, the hydrogel reaction system has no participation of organic solvents and no pollution to the environment, and the carbon fiber reinforced polyaryletherketone medical composite material has no toxic and side effects of cells and is suitable for biomedical materials.

Preferably, the number average molecular weight of the reactive functional group-terminated multi-arm polyethylene glycol derivative is 200-50000, for example, 200, 500, 1000, 2000, 3000, 5000, 8000, 10000, 50000, and specific point values among the above point values, are limited in space and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the range.

And after the carbon fiber is decomposed at high temperature, mixing the carbon fiber with the polyaryletherketone, adding the mixture into an aqueous solution of an acrylic ester end-capped PEG-PPG-PEG triblock copolymer to form a suspension, adding a multi-arm polyethylene glycol derivative with an end capped by an active functional group into the suspension, stirring and standing the mixture to obtain a hydrogel composite system, and carrying out hot press molding, banburying, drying and melt extrusion on the hydrogel composite system to obtain the carbon fiber reinforced polyaryletherketone medical composite material.

The purpose of the pyrolysis is to remove the sizing agent from the surface of the carbon fiber.

The pyrolysis time is 5-180 min, for example, 5min, 10 min, 25 min, 100 min, 150 min, 180 min, and specific point values between the above point values, which are limited in space and for brevity, the present invention is not exhaustive.

The pyrolysis temperature may be 300-420 c, such as 300 c, 350 c, 380 c, 420 c, and specific values between the above values, although for brevity and for simplicity the present invention is not intended to be exhaustive of the specific values included in the ranges.

The carbon fiber and the polyaryletherketone powder are further fused through the three-dimensional reticular hydrogel structure. The three-dimensional reticular hydrogel structure is formed by Michael addition reaction of carbon-carbon double bonds of PEG-PPG-PEG capped by acrylic ester and sulfhydryl and/or amino groups of multi-arm polyethylene glycol derivatives capped by active functional groups.

The stirring and mixing speed is 10-300 r/min, for example, 20 r/min, 50r/min, 100 r/min, 150 r/min, 200 r/min, 250r/min, 300 r/min, and specific point values among the above point values, which are limited in space and for brevity, the present invention is not exhaustive.

The stirring and mixing time is 5-60 min, for example, 5min, 8 min, 10min, 20 min, 30 min, 40 min, 50 min, 60 min, and specific point values among the above point values, are limited in space and for brevity, the present invention is not exhaustive of the specific point values included in the range.

The hot press forming pressure is 1-10 MPa, for example, 1 MPa, 1.5 MPa, 2 MPa, 2.5 MPa, 3 MPa, 5 MPa, and 10MPa, and specific point values between the above point values, which are limited in space and for brevity, the present invention is not intended to be exhaustive.

The hot press forming temperature is 300-450 ℃, such as 300 ℃, 350 ℃, 380 ℃, 400 ℃, 420 ℃, 450 ℃, and specific point values among the above point values, and the present invention is not exhaustive of the specific point values included in the range for the sake of brevity and conciseness.

The hot press molding time is 1-180 min, for example, 1 min, 5min, 8 min, 10 min, 20min, 30min, 40 min, 50 min, 60 min, 100 min, 180 min, and specific point values among the above point values, are limited in length and for brevity, the invention is not intended to be exhaustive of the specific point values included in the range.

The banburying temperature is 300-450 ℃, such as 300 ℃, 350 ℃, 400 ℃, 450 ℃, and specific point values among the point values, which are limited in space and are not exhaustive in the invention for the sake of simplicity.

The time for the banburying is 1-180 min, for example, 1 min, 2 min, 5min, 8 min, 10min, 20 min, 30 min, 50min, 60 min, 80min, 100min, 150min, 180min, and specific point values among the above point values are limited in space and for brevity, the present invention is not exhaustive of the specific point values included in the range.

The drying time is 2-12 h, for example, may be 2h, 3 h, 5h, 8h, 10 h, 12 h, and specific point values between the above point values, and is limited in space and for brevity, the present invention is not exhaustive of the specific point values included in the range.

The drying temperature is 100-200deg.C, such as 100deg.C, 110deg.C, 150deg.C, 180deg.C, 200deg.C, and the specific values between the above values, which are limited in space and for the sake of brevity, the present invention is not exhaustive.

The melt extrusion is performed in a twin screw extruder.

The screw speed of the twin screw extruder may be 20-400 rpm, for example, 20 rpm, 50 rpm, 80 rpm, 100 rpm, 150 rpm, 200 rpm, 300 rpm, 350 rpm, 400 rpm, and specific point values between the above point values, are limited in space and for brevity, the present invention is not exhaustive of the specific point values included in the range.

The twin screw extruder may have a zone temperature of 200-360 c, such as 200 c, 210 c, 250 c, 280 c, 300 c, 350 c, 360 c, and specific values between the above values, although the invention is not intended to be exhaustive of the specific values included in the ranges given herein for the sake of brevity and conciseness.

The two-zone temperature of the twin-screw extruder may be 330-390 c, for example 330 c, 350 c, 380 c, 390 c, and specific values between the above values, although the present invention is not intended to be exhaustive of the specific values included in the ranges given herein for the sake of brevity and conciseness.

The three-zone temperature, four-zone temperature, five-zone temperature of the twin-screw extruder are each independently 320-415 ℃, such as 320 ℃, 340 ℃, 360 ℃, 380 ℃, 400 ℃, 415 ℃, and specific point values between the above-mentioned point values, are limited in space and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the ranges.

The six-zone temperature, seven-zone temperature, eight-zone temperature, nine-zone temperature of the twin-screw extruder are each independently 350-420 ℃, such as 350 ℃, 380 ℃, 400 ℃, 420 ℃, and specific point values between the above-mentioned point values, which are limited in space and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the ranges.

The die operating temperature of the twin screw extruder may be 350-430 c, such as 350 c, 380 c, 400 c, 420 c, 430 c, and specific values between the above values, although the present invention is not intended to be exhaustive of the specific values included in the ranges given herein for the sake of brevity and conciseness.

The twin screw extruder may have a constant temperature of 20-30 min, for example 20 min, 22 min, 24 min, 26 min, 28 min, 30 min, and specific values between the above values, and the present invention is not intended to be exhaustive of the specific values included in the range for reasons of space and brevity.

The preparation method specifically comprises the following steps:

(1) Mixing carbon fiber with polyaryletherketone to obtain mixed powder;

The length of the carbon fiber is 10-1000 mu m; the polyaryletherketone comprises any one or a combination of at least two of polyether-ether-ketone, polyether-ketone, polyether-ether-ketone or polyether-ketone-ether-ketone;

(2) Mixing the mixed powder obtained in the step (1), the acrylate-terminated polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer and the multi-arm polyethylene glycol derivative terminated by the active functional group to obtain a hydrogel composite system;

(3) Carrying out hot press molding on the hydrogel composite system obtained in the step (2) to obtain a composite material of carbon fiber and polyaryletherketone;

The pressure of the hot press molding is 1-10 MPa; the temperature of the hot press molding is 300-450 ℃; the hot press molding time is 1-180 min;

(4) Carrying out banburying, drying and melt extrusion on the carbon fiber and polyaryletherketone composite material obtained in the step (3) to obtain the carbon fiber reinforced polyaryletherketone medical composite material;

The banburying temperature is 300-450 ℃; the banburying time is 1-180 min; the drying time is 2-12 h; the drying temperature is 100-200 ℃.

The preparation method comprises the steps of mixing carbon fibers with polyaryletherketone, adding the mixture into an aqueous solution of an acrylic ester-terminated PEG-PPG-PEG triblock copolymer to form a suspension, adding a multi-arm polyethylene glycol derivative with an active functional group terminated into the suspension, stirring, mixing and standing to obtain a hydrogel composite system, and carrying out hot press molding, banburying, drying and melt extrusion on the hydrogel composite system to obtain granules of the carbon fiber-reinforced polyaryletherketone medical composite material.

In a second aspect, the invention provides a carbon fiber reinforced polyaryletherketone medical composite material, which is prepared by the preparation method in the first aspect.

In a third aspect, the present invention provides the use of a carbon fiber reinforced polyaryletherketone medical composite as described in the second aspect in a medical device;

Preferably, the application comprises application in 3D printing medical materials, artificial prostheses, medical catheters, oral implants, maxillofacial bones, heart valves, infusion ports, cardiac pacemaker housings, medical sighting rods, medical sighting frames, human bone locking systems, medical wrenches, medical connectors, medical locating frames, surgical head and retraction systems, medical handles, medical puncture needles, medical connectors, medical sutures, artificial bones, artificial joints, femoral condyles, bone nails, screws, anchors, rivets, intramedullary needles, bone plates, tibial trays, skull repair systems, or spinal interbody fusion devices.

Compared with the prior art, the invention has the following beneficial effects:

The invention provides a preparation method of a carbon fiber reinforced polyaryletherketone medical composite material, which is characterized in that acrylic ester-terminated PEG-PPG-PEG is used as an amphiphilic surfactant and is used as a bridge for connecting carbon fibers and polyether-ether-ketone, so that infiltration and fusion of the polyether-ether-ketone and the carbon fibers are promoted; further fusing and fixing the carbon fiber and the polyaryletherketone through a three-dimensional reticular hydrogel formed by PEG-PPG-PEG so as to further enhance the interfacial force between the carbon fiber and the polyaryletherketone; the hydrogel is produced by Michael addition reaction of carbon-carbon double bond of PEG-PPG-PEG capped by acrylic ester and amino and/or mercapto of multi-arm polyethylene glycol derivative capped by active functional group, the preparation method has high production efficiency, is suitable for mass continuous production of composite materials, and the PEG derivative adopted has no toxic and side effects, and the carbon fiber reinforced polyaryletherketone medical composite material has high application value in the biomedical field, and has tensile strength reaching 189.9-198.2MPa.

Drawings

Fig. 1 is a schematic diagram of a three-dimensional network hydrogel structure formed on carbon fibers in the preparation process of the carbon fiber reinforced polyaryletherketone medical composite material provided in embodiment 1 of the present invention.

Detailed Description

The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.

The experimental materials used in the examples and comparative examples of the present invention are as follows:

1. carbon fiber, east ZOLTEK ™ PX35, japan, fiber diameter 7.2 μm, average fiber length: 100. μm.

2. Polyaryletherketone material: in the embodiment, polyether ether ketone (PEEK) is selected for a test, wherein PEEK is purchased from Jilin, and is ground into 330UPF,950 meshes, and the particle size of powder is 18um;

3. hydroxy-terminated PEG-PPG-PEG triblock copolymer:

Purchased from Sigma-Aldrich company, trade name 1: pluronic is L-31, and the number average molecular weight Mn= -1, 100; brand 2: pluronic F-108, number average molecular weight mn= -14, 600;

4. The active functional group end capped multi-arm polyethylene glycol derivative is prepared from amino end capped four-arm polyethylene glycol as raw material: molecular weight 2K, 4 arm-PEG-NH ₂, purchased from Sigma-Aldrich;

5. The active functional group end-capped multi-arm polyethylene glycol derivative is prepared from the following raw materials: molecular weight 10K, 4 arm-PEG-SH, (pentaerythritol core, core structure pentaerythritol), purchased from Sigma-Aldrich;

6. Acrylate-terminated polyethylene glycol: acrylate-PEG-acrylate, molecular weight mn= -700, purchased from Sigma-Aldrich.

Preparation example 1

The preparation example provides an acrylic ester end capped PEG-PPG-PEG triblock copolymer and a preparation method thereof, wherein the preparation method comprises the following steps:

Pluronic L-31 with OH end groups, and potassium carbonate were vacuum dried in a vacuum oven at 110deg.C for 4 hours to remove moisture. Then, pluronic L-31 (number average molecular weight Mn= -1, 100,5 g) and potassium carbonate (3 g) were added to a 50mL three-necked flask under a nitrogen protection system, and mixed in a dichloromethane solvent. Acryloyl chloride (1 mL) was added dropwise in an ice-water bath. The mixture was stirred under nitrogen at 60 ℃ for 4 days. The solution was filtered and then poured into ice-cold petroleum ether (cooled by ice water). The solution was stirred for 10 minutes and then isolated to give the crude product. The crude product was dissolved in 50mL of dichloromethane, then extracted 3 times with saturated NaCl solution, the organic layer was collected, dried over magnesium sulfate overnight, then filtered to remove the magnesium sulfate, then the solvent was removed by distillation under reduced pressure to give an acrylate-terminated PEG-PPG-PEG triblock copolymer, whose chemical structure was characterized by 1H-NMR nuclear magnetism (Bruker, model AVANCE III) with a nuclear magnetic pattern (¹H-NMR,400 MHz, CDCl₃) of: acrylate-capped PEG-PPG-PEG with ¹H-NMR（CDCl₃) demonstrated the following:

(a: =C-H trans 5.78ppm ; b: CH=C 6.03 ppm; c: =C-H cis 6.35 pm; d: (C=O)OCH₂ 4.25ppm; e: OCH₂CH₂O 3.59ppm; f: O-CH(CH₃)-CH₂- 3.47ppm; g: O-CH(CH₃)-CH₂- 3.33ppm; h: O-CH(CH₃)-CH₂- 1.07 ppm).

Preparation example 2

Pluronic F-108 with OH end groups, and potassium carbonate were vacuum dried in a vacuum oven at 110deg.C for 4 hours to remove moisture. Then, pluronic F-108 (number average molecular weight Mn= -14,600, 5 g) and potassium carbonate (3 g) were added to a 50mL three-necked flask under a nitrogen protection system, and mixed in a dichloromethane solvent. Acryloyl chloride (1 mL) was added dropwise in an ice-water bath. The mixture was stirred under nitrogen at 60 ℃ for 4 days. The solution was filtered and then poured into ice-cold petroleum ether (cooled by ice water). The solution was stirred for 10 minutes and then isolated to give the crude product. The crude product was dissolved in 50mL of dichloromethane, then extracted 3 times with saturated NaCl solution, the organic layer was collected, dried over magnesium sulfate overnight, then filtered to remove the magnesium sulfate, then the solvent was removed by distillation under reduced pressure to give an acrylate-terminated PEG-PPG-PEG triblock copolymer, whose nuclear magnetic pattern (¹H-NMR,400 MHz, CDCl₃) was characterized by ¹ H-NMR nuclear magnetism (Bruker, model AVANCE III): acrylate-capped PEG-PPG-PEG with ¹H NMR（CDCl₃) demonstrated the following:

(a: =C-H trans 5.78ppm ; b: CH=C 6.03 ppm; c: =C-H cis 6.35 ppm; d: (C=O)OCH₂ 4.25ppm; e: OCH₂CH₂O 3.59ppm; f: O-CH(CH₃)-CH₂- 3.47ppm; g: O-CH(CH₃)-CH₂- 3.33ppm; h: O-CH(CH₃)-CH₂- 1.07 ppm).

Example 1

The embodiment provides a carbon fiber reinforced polyaryletherketone medical composite material and a preparation method thereof, wherein the polyaryletherketone adopted in the embodiment is polyetheretherketone, namely PEEK powder.

The preparation method comprises the following steps:

1. Uniformly mixing carbon fiber and PEEK powder;

First, the original sizing agent on the surface of the carbon fiber is decomposed at high temperature; wherein pyrolysis refers to sintering at 350deg.C for 60min.

Secondly, mixing the carbon fiber and PEEK powder according to a certain proportion (mass ratio of 80:20), and uniformly mixing under a high-speed stirrer.

The mixing operation conditions of the high-speed mixer are as follows: weighing PEEK resin and carbon fiber according to parts by weight, and then carrying out high-speed mixing to uniformly mix, wherein the rotating speed of a mixer is 100r/min, and the mixing time is 60 min;

2. Preparing a hydrogel composite system of carbon fibers and PEEK powder;

(1) The well-mixed carbon fiber and PEEK powder were added in 500 g to 500mL of an aqueous solution (mass fraction of block copolymer: 50%) of an acrylate-terminated PEG-PPG-PEG triblock copolymer (preparation example 1) and stirred well to form a suspension.

(2) Adding an amino-terminated multi-arm polyethylene glycol derivative (4-arm-PEG-NH ₂) into the acrylate-terminated PEG-PPG-PEG aqueous solution mixed system, wherein the mass ratio of the multi-arm polyethylene glycol derivative to the acrylate-terminated PEG-PPG-PEG is 1:1, uniformly stirring, and standing to obtain the hydrogel composite system.

3. Preliminarily preparing granules of the carbon fiber-PEEK composite material;

Firstly, carrying out hot press molding on a hydrogel composite system of PEEK powder and carbon fibers to obtain a polyether-ether-ketone-carbon fiber composite material solid with a certain thickness;

The hot press forming operation specifically comprises the following steps: the method comprises the steps of firstly filling a hydrogel composite system of a carbon fiber/polyether-ether-ketone composite material into a die of the vacuum hot press, wherein the die is 10cm x 2cm in size, placing the die into the vacuum hot press, setting and executing a forming program, namely heating, pressurizing, saturating and cooling, driving a lower pressing plate to move upwards, and starting vacuumizing in a non-compacting state, so that the absolute vacuum degree in the press is below 10 KPa; heating from room temperature to 380 ℃ at a rate of 5 ℃/min, and exhausting for 10 times, each time lasting for 10s; pressurizing to 10MPa, and preserving heat for 60min under the pressure; and then cooling to 25 ℃ at a cooling rate of 5 ℃/min, deflating to balance the internal and external air pressure of the press, taking out the die, and demoulding to obtain the solid of the carbon fiber reinforced polyether-ether-ketone-based composite material. Cutting PEEK-carbon fiber composite solid by a cutter (SMD-50, sanchu plastic machinery Co., dongguan Co., ltd.) to obtain irregularly-shaped granules;

4. banburying of the carbon fiber-PEEK composite material;

because the carbon fiber-PEEK composite solid in the step 3 is cut into granules, residual polyethylene glycol derivatives exist in the granules, and the internal mixing is needed in an internal mixer to further remove the residual polyethylene glycol derivatives and further purify, more importantly, the carbon fiber and PEEK powder can be further mixed uniformly through internal mixing, so that the interfacial fusion between the carbon fiber and PEEK powder is enhanced.

Putting the obtained PEEK-carbon fiber composite material granules into an internal mixer for banburying processing to obtain PEEK master batches filled with carbon fibers again; the specific process is as follows: firstly, when an internal mixer (brand: POTOP Guangzhou common, guangzhou common experimental analysis instrument Co., ltd.) is kept at 380 ℃, starting equipment, wherein the idling time of the equipment is not less than 2 minutes, and observing whether the equipment runs normally in an idle state; and then, putting the particles of the PEEK-carbon fiber composite material into an internal mixer for banburying, wherein the total amount of the raw materials is 500g, the mixing time is 60 minutes, and cutting the PEEK/carbon fiber composite material solid obtained after banburying by a cutter (SMD-50, sanchuang plastic machinery Co., dongguan Co., ltd.) to obtain irregularly-shaped particles.

5. Preparing granules of a carbon fiber reinforced polyaryletherketone medical composite material;

First, the irregularly shaped pellets of carbon fiber-reinforced PEEK obtained after the banburying in step 4 above were dried at a temperature of 200 ℃ for 10 hours. Secondly, adding 2 kg PEEK powder into a double-screw extruder through a main feeding port, adding dried irregular-shaped particles (1 kg, carbon fiber mass fraction is 80%) of the carbon fiber reinforced PEEK manufactured in the step 4 into the double-screw extruder from a side feeding port, heating, melting, plasticizing, kneading, extruding, cooling and granulating the particles through the double-screw extruder (brand: THERMATIC series, purchased from Davis Standard mechanical Co., ltd.) to obtain carbon fiber reinforced PEEK particles with a certain size, wherein the mass fraction of the carbon fiber is about 25%.

The specific parameters are as follows: the screw speed of the twin-screw extruder was 60rpm; preheating an extruder: checking the rotation perfect condition of each part of the double-screw extruder, starting a temperature control switch and adjusting a temperature control meter to a target working temperature, wherein the target working temperature of each region of the double-screw extruder is as follows: the working temperature of a first area is 250 ℃; the working temperature of the second area is 330 ℃; the working temperatures of the third region, the fourth region and the fifth region are 320 ℃; the working temperatures of the six zone, the seven zone, the eight zone and the nine zone are 380 ℃; the working temperature of the die head is 350 ℃, and the die head is kept at the constant temperature for 20 minutes after the working temperature of each zone is increased to the target working temperature.

6. Manufacturing a PEEK/carbon fiber profile;

The granules of the carbon fiber reinforced polyaryletherketone medical composite material which is melt extruded by the steps are used for manufacturing profiles.

Placing the sample of the medical composite material of the carbon fiber reinforced polyaryletherketone with the carbon fiber content of 25% and manufactured in the step 5 into a mould, paving the sample to the thickness of 2mm, drying the sample at 180 ℃ for 2h, placing the sample into a vacuum press with the set temperature of 410 ℃, closing the mould, adjusting the pressure to be 2 MPa, controlling the pressing time to be 20 min, taking the mould out, placing the mould into a press with the set temperature of 150 ℃ for cooling for 1h, taking the material, cooling the material to the room temperature, and enabling the sample bar size to be 12mm multiplied by 4mm multiplied by 2mm.

In the preparation process of the carbon fiber reinforced polyaryletherketone medical composite material, a schematic diagram of a three-dimensional reticular hydrogel structure formed on carbon fibers is shown in figure 1.

Example 2

The embodiment provides a carbon fiber reinforced polyaryletherketone medical composite material and a preparation method thereof, wherein the polyaryletherketone adopted in the embodiment is polyetheretherketone, namely PEEK powder. The preparation method comprises the following steps:

1. Uniformly mixing carbon fiber and PEEK powder;

2. Preparing a hydrogel composite system of carbon fibers and PEEK powder;

(1) The well-mixed carbon fiber and PEEK powder were added in 500 g to 500mL of an aqueous solution (mass fraction of block copolymer: 50%) of an acrylate-terminated PEG-PPG-PEG triblock copolymer (preparation 2) and stirred well to form a suspension.

4. banburying of the carbon fiber-PEEK composite material;

6. Manufacturing a PEEK/carbon fiber profile;

Example 3

1. Uniformly mixing carbon fiber and PEEK powder;

2. Preparing a hydrogel composite system of carbon fibers and PEEK powder;

(2) Adding a multi-arm polyethylene glycol derivative (4-arm-PEG-SH) containing a sulfhydryl end-capped PEG-PPG-PEG into the acrylate end-capped PEG-PPG-PEG aqueous solution mixed system, wherein the mass ratio of the multi-arm polyethylene glycol derivative to the acrylate end-capped PEG-PPG-PEG is 1:1, uniformly stirring, and standing to obtain the hydrogel composite system.

4. banburying of the carbon fiber-PEEK composite material;

First, the irregularly shaped pellets of carbon fiber-reinforced PEEK obtained after the banburying in step 4 above were dried at a temperature of 200 ℃ for 10 hours. Secondly, adding 2 kg PEEK powder into a double-screw extruder through a main feeding port, adding dried irregular-shaped granules (1 kg, carbon fiber mass fraction is 80%) of the carbon fiber reinforced PEEK manufactured in the step 4 into the double-screw extruder from a side feeding port, heating, melting, plasticizing, kneading, extruding, cooling and granulating the granules through the double-screw extruder (brand: THERMATIC series, purchased from Davis Standard mechanical Co., ltd.) to obtain the carbon fiber reinforced polyaryletherketone medical composite material with a certain size, wherein the mass fraction of the carbon fiber is about 25%.

6. Manufacturing a PEEK/carbon fiber profile;

Comparative example 1

1. Uniformly mixing carbon fiber and PEEK powder;

2. Preparing a hydrogel composite system of carbon fibers and PEEK powder;

(1) The well-mixed carbon fiber and PEEK powder were added to 500mL of an acrylate-terminated polyethylene glycol (PEG), i.e., an aqueous solution of acrylate-PEG-acrylate (mass fraction of acrylate-PEG-acrylate: 50%), in 500 g total, and stirred well to form a suspension.

(2) Adding an amino-terminated multi-arm polyethylene glycol derivative (4-arm-PEG-NH ₂) into the acrylic ester-terminated PEG aqueous solution mixed system, wherein the mass ratio of the multi-arm polyethylene glycol derivative to the acrylic ester-terminated PEG is 1:1, uniformly stirring, and standing to obtain the hydrogel composite system.

4. banburying of the carbon fiber-PEEK composite material;

6. Manufacturing a PEEK/carbon fiber profile;

Comparative example 2

1. Uniformly mixing carbon fiber and PEEK powder;

2. preliminarily preparing granules of the carbon fiber-PEEK composite material;

firstly, performing hot press molding on a mixture of PEEK powder and carbon fibers to obtain a polyether-ether-ketone-carbon fiber composite material solid with a certain thickness;

The hot press forming operation specifically comprises the following steps: the method comprises the steps of firstly filling a composite system of carbon fiber/polyether-ether-ketone composite materials into a die of the vacuum hot press, wherein the die is 10cm x 2cm in size, placing the die into the vacuum hot press, setting and executing a forming program, namely heating, pressurizing, saturating and cooling, driving a lower pressing plate to move upwards, and starting vacuumizing in a non-compacting state, so that the absolute vacuum degree in the press is below 10 KPa; heating from room temperature to 380 ℃ at a rate of 5 ℃/min, and exhausting for 10 times, each time lasting for 10s; pressurizing to 10MPa, and preserving heat for 60min under the pressure; and then cooling to 25 ℃ at a cooling rate of 5 ℃/min, deflating to balance the internal and external air pressure of the press, taking out the die, and demoulding to obtain the solid of the carbon fiber reinforced polyether-ether-ketone-based composite material. Cutting PEEK-carbon fiber composite solid by a cutter (SMD-50, sanchu plastic machinery Co., dongguan Co., ltd.) to obtain irregularly-shaped granules;

3. Banburying of the carbon fiber-PEEK composite material;

Because the carbon fiber-PEEK composite solid in the step 2 is cut into granules, residual polyethylene glycol derivatives exist in the granules, and the internal mixing is needed in an internal mixer to further remove the residual polyethylene glycol derivatives and further purify, more importantly, the carbon fiber and PEEK powder can be further mixed uniformly through internal mixing, so that the interfacial fusion between the carbon fiber and PEEK powder is enhanced.

4. Preparing granules of a carbon fiber reinforced polyaryletherketone medical composite material;

First, the irregularly shaped pellets of carbon fiber-reinforced PEEK obtained after the banburying in step 4 above were dried at a temperature of 200 ℃ for 10 hours.

Secondly, adding 2 kg PEEK powder into a double-screw extruder through a main feeding port, adding dried irregular-shaped granules (1 kg, carbon fiber mass fraction is 80%) of the carbon fiber reinforced PEEK manufactured in the step 4 into the double-screw extruder from a side feeding port, heating, melting, plasticizing, kneading, extruding, cooling and granulating the granules through the double-screw extruder (brand: THERMATIC series, purchased from Davis Standard mechanical Co., ltd.) to obtain the carbon fiber reinforced polyaryletherketone medical composite material with a certain size, wherein the mass fraction of the carbon fiber is about 25%.

5. Manufacturing a PEEK/carbon fiber profile;

Comparative example 3

1. Uniformly mixing carbon fiber and PEEK powder;

2. Preparing a composite system of carbon fiber and PEEK powder;

(1) The carbon fiber and PEEK powder were mixed to 500 g, added to 500mL of an aqueous solution of PEG-PPG-PEG triblock copolymer (mass fraction of block: 50%) and stirred uniformly to form a suspension.

(2) Adding an amino-terminated multi-arm polyethylene glycol derivative (4-arm-PEG-NH ₂) into the PEG-PPG-PEG aqueous solution mixed system, wherein the mass ratio of the multi-arm polyethylene glycol derivative to the PEG-PPG-PEG is 1:1, uniformly stirring, and standing to obtain a composite system. Because the PEG-PPG-PEG triblock copolymer does not have a carbon-carbon double bond, it cannot form a hydrogel with the amino group of 4-arm-PEG-NH ₂. The system is not a composite system of hydrogels.

Firstly, carrying out hot press molding on a PEEK powder and carbon fiber composite system to obtain a PEEK-carbon fiber composite material solid with a certain thickness;

4. banburying of the carbon fiber-PEEK composite material;

6. Manufacturing a PEEK/carbon fiber profile;

Comparative example 4

1. Uniformly mixing carbon fiber and PEEK powder;

The mixing operation conditions of the high-speed mixer are as follows: the PEEK resin and the carbon fiber are weighed according to the parts by weight and then mixed at a high speed to be uniformly mixed, the rotating speed of a mixer is 100r/min, and the mixing time is 60 min.

2. Preparing a composite system of carbon fiber and PEEK powder;

The carbon fiber and PEEK powder which are uniformly mixed are added into 500mL of aqueous solution of the PEG-PPG-PEG triblock copolymer with end capped by acrylic ester (the mass fraction of the PEG-PPG-PEG capped by acrylic ester is 50%), and are uniformly stirred to form suspension, and a composite system is obtained after standing. The system failed to form a hydrogel system because no amino or thiol-terminated cross-linking agent was added.

4. banburying of the carbon fiber-PEEK composite material;

6. Manufacturing a PEEK/carbon fiber profile;

Placing the granules of the medical polyaryletherketone composite material with 25% carbon fiber content and prepared in the step 5 into a mould, paving the granules to a thickness of 2mm, drying the granules at 180 ℃ for 2h, placing the granules into a vacuum press with a set temperature of 410 ℃, closing the mould, adjusting the pressure to be 2 MPa, controlling the pressing time to be 20 min, taking out the mould, placing the mould into a press with a set temperature of 150 ℃ for cooling for 1h, taking out the materials, cooling the materials to room temperature, and keeping the spline size to be 12mm multiplied by 4mm multiplied by 2mm.

Performance test:

1. tensile strength test: testing is carried out on an Shimadzu AGS-X universal testing machine, test samples for testing tensile strength are prepared according to GB/T1040.1-2018 "determination of plastic tensile Property", the loading speed of the test samples is 2 mm/min, 5 samples are tested in each group, and the average value of the results is obtained. The test results are shown in Table 1.

2. Cell study test:

Cell researches on the PEEK profile and osteoblast MC3T3-E1 culture prove that the PEEK profile has no toxic and side effects and can be used for biomedical materials.

The cytotoxicity study specific test procedure is as follows:

Cytotoxicity was determined by a live/dead cell staining assay (LIVE DEAD STAINING) for which polyethylene glycol (PEG) based substrates were washed in 70% ethanol, rinsed with Phosphate Buffered Saline (PBS) and incubated in 8-well polystyrene (TCPs) plates. Subsequently, cells were treated at a density of 5 x10 ⁴ cells/mL and incubated in an incubator for 24 hours at 37 degrees, 5% co ₂ atmosphere and 95% relative humidity. Viability of the cells was assessed by live-dead staining after 24 hours. In detail, cells were seeded with 1000. Mu.L of a solution containing 10. Mu.L of fluorescein diacetate (fluorescein diacetate, 0.5 mg/mg in acetone), 20. Mu.L of propidium iodide (0.5 mg/mL in PBS) and 970. Mu.L of PBS. Metabolically active cells can hydrolyze fluorescein diacetate to green fluorescein with the aid of intracellular esterases. Meanwhile, propidium iodide (propidium iodide) can pass through damaged cytoplasmic membrane and bind to nucleic acid of cell nucleus, so that the cell nucleus generates fluorescent red 101. After removal of the dye solution and subsequent washing with PBS, measurements were made by fluorescence microscopy. For visualization of cells, fluorescein and propidium iodide were excited at 496nm and 561nm, respectively; and detected in release ranges of 504nm-559nm and 569nm-663nm, respectively.

The prepared 1.2mmPEEK section is subjected to osteoblast culture, then subjected to a live/dead cell staining test and then subjected to characterization analysis by a fluorescence microscope. The result of the in vitro MC3T3-E1 osteoblast cell staining (LIVE AND DEAD ASSAY) after 24 hours of culture shows that the cells cultured by the polyether-ether-ketone profile are green under a fluorescence microscope, which indicates that the cells survive and the sample has no toxic and side effects.

TABLE 1

As can be seen from the data in table 1, the tensile strength of examples 1,2 and 3 is between 189.8 and 198.2MPa, and the three are three-dimensional network structures of hydrogels formed by PEG-PPG-PEG capped with acrylic ester and multi-arm polyethylene glycol derivatives capped with amino groups or mercapto groups containing active functional groups are adopted to mix and further fixedly fuse PEEK with carbon fibers, and the advantages of examples 1,2 and 3 are that the PEG-PPG-PEG triblock copolymer is used as a nonionic surfactant, and the hydrophilic and hydrophobic chain segment structure of the PEG-PPG triblock copolymer can be used as a 'bridge' for connecting the interface effect of the carbon fibers and PEEK, so that the wettability of the carbon fibers and PEEK resins is enhanced, and the PEEK resins are promoted to be fused with the carbon fibers more uniformly; meanwhile, the carbon fiber and the PEEK powder are further fused and fixed by the aid of the hydrogel with the three-dimensional network structure formed by the acrylic ester end-capped PEG-PPG-PEG and the multi-arm polyethylene glycol derivative with the end-capped active functional group, the interfacial fusion force of the carbon fiber and the PEEK powder is enhanced, and the tensile strength of the PEEK section bar prepared by the carbon fiber reinforced PEEK granules obtained through melt extrusion of the carbon fiber and the PEEK powder is more than 189.8 MPa.

Example 1 compared to comparative example 1, the substitution of the acrylate-capped PEG-PPG-PEG of example 1 with the acrylate-capped PEG of comparative example 1, which resulted in the PEG of comparative example 1 not having the effect of the amphiphilic nonionic surfactant of the PEG-PPG-PEG triblock copolymer, which did not act well as a "bridge" linking the carbon fiber to the PEEK interface, the carbon fiber was poorly wettable to the PEEK resin, resulting in a PEEK powder that was more difficult to fuse with the carbon fiber, and only the acrylate-capped PEG and 4-arm-PEG-NH ₂ formed a hydrogel to promote fusion of the carbon fiber to the PEEK powder, resulting in a tensile strength of only 138.3MPa.

Example 1 compared to comparative example 3, the acrylate-capped PEG-PPG-PEG of example 1 was replaced with PEG-PPG-PEG of comparative example 3 such that comparative example 3 failed to form a hydrogel to further enhance the fusion of the carbon fiber with the PEEK powder, resulting in both PEEK powder and carbon fiber not being well uniformly dispersed and tightly immobilized through the three-dimensional network structure, resulting in a tensile strength of 130.1Mpa.

Comparative example 2 did not have an amphiphilic surfactant and failed to form a hydrogel, resulting in a profile made from carbon fiber-reinforced PEEK pellets obtained by melt extrusion after mixing both PEEK powder and carbon fibers, having a tensile strength of only 112.8MPa. Comparative example 4 the tensile strength of the fabricated profile was increased to 126.9MPa with the addition of the amphiphilic surfactant acrylate-capped PEG-PPG-PEG.

The applicant states that the invention is described by the above examples as a carbon fiber reinforced polyaryletherketone medical composite material, and the preparation method and application thereof, but the invention is not limited to the above examples, i.e. it does not mean that the invention must be practiced depending on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims

1. A preparation method of a carbon fiber reinforced polyaryletherketone medical composite material, which is characterized by comprising the following steps:

The hydrogel composite system is subjected to hot press molding, banburying, drying and melt extrusion to obtain the carbon fiber reinforced polyaryletherketone medical composite material;

The mass ratio of the carbon fiber, the polyaryletherketone, the acrylic ester end capped polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer and the active functional group end capped multi-arm polyethylene glycol derivative is (0.03-30): 1: (0.02-50): (0.02-50);

2. The method of claim 1, wherein the carbon fibers are discontinuous carbon fibers;

the length of the carbon fiber is 10-1000 mu m;

the polyaryletherketone comprises any one or a combination of at least two of polyether-ether-ketone, polyether-ketone, polyether-ether-ketone or polyether-ketone-ether-ketone;

the particle size of the polyaryletherketone is 2-100 mu m.

3. The method of claim 1, wherein the acrylate-terminated polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer has a structure as shown in formula 1:

wherein x is 1-100, y is 1-100, and z is 1-100.

4. The method of claim 1, wherein the acrylate-terminated polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer is prepared by:

Mixing hydroxyl-terminated polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer, carbonate and acryloyl chloride, and reacting to obtain the acrylate-terminated polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer;

The hydroxyl terminated poly (polyethylene glycol) -polypropylene glycol-polyethylene glycol triblock copolymer has a structure shown in a formula 2:

wherein x is 1-100, y is 1-100, z is 1-100;

The carbonate comprises potassium carbonate and/or sodium carbonate;

mixing the hydroxyl-terminated polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer with carbonate, dissolving in a solvent, and dropwise adding acryloyl chloride in an ice-water bath for reaction;

the mass ratio of the hydroxyl-terminated polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer to the carbonate is (0.05-20): 1, a step of;

The mass ratio of the hydroxyl-terminated polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer to the acrylic chloride is (0.05-20): 1.

5. The method of claim 1, wherein the reactive functional group-terminated multi-arm polyethylene glycol derivative comprises any one or a combination of at least two of an amino-terminated tri-arm polyethylene glycol derivative, an amino-terminated tetra-arm polyethylene glycol derivative, an amino-terminated hexa-arm polyethylene glycol derivative, an amino-terminated octa-arm polyethylene glycol derivative, a mercapto-terminated tri-arm polyethylene glycol derivative, a mercapto-terminated tetra-arm ethylene glycol derivative, a mercapto-terminated hexa-arm polyethylene glycol derivative, or a mercapto-terminated octa-arm polyethylene glycol derivative.

6. The method of claim 1, wherein the reactive functional group-terminated multi-arm polyethylene glycol derivative comprises a structure as shown in formulas 3-6:

Wherein n is 1-100;

The number average molecular weight of the multi-arm polyethylene glycol derivative capped by the active functional group is 200-50000.

7. The preparation method of claim 1, wherein the carbon fiber is mixed with polyaryletherketone after pyrolysis, added into an aqueous solution of an acrylic ester-terminated polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer to form a suspension, an active functional group-terminated multi-arm polyethylene glycol derivative is added into the suspension, stirred, mixed and stood to obtain a hydrogel composite system, and the hydrogel composite system is subjected to hot press molding, banburying, drying and melt extrusion to obtain the carbon fiber-reinforced polyaryletherketone medical composite material;

The pyrolysis time is 5-180 min;

the pyrolysis temperature is 300-420 ℃.

8. The method according to claim 1, wherein the pressure of the hot press molding is 1 to 10 MPa;

The temperature of the hot press molding is 300-450 ℃;

The hot press molding time is 1-180 min;

the banburying temperature is 300-450 ℃;

the banburying time is 1-180 min;

the drying time is 2-12 h;

the drying temperature is 100-200 ℃;

the melt extrusion is performed in a twin screw extruder;

the screw rotating speed of the double-screw extruder is 20-400 rpm;

the temperature of one area of the double-screw extruder is 200-360 ℃;

the temperature of the two areas of the double-screw extruder is 330-390 ℃;

the temperature of the three zones, the temperature of the four zones and the temperature of the five zones of the double-screw extruder are respectively and independently 320-415 ℃;

The six-zone temperature, the seven-zone temperature, the eight-zone temperature and the nine-zone temperature of the double-screw extruder are respectively and independently 350-420 ℃;

the working temperature of the die head of the double-screw extruder is 350-430 ℃.

9. The preparation method according to claim 1, characterized in that it comprises in particular:

(1) Mixing carbon fiber with polyaryletherketone to obtain mixed powder;

10. A carbon fiber reinforced polyaryletherketone medical composite material, wherein the carbon fiber reinforced polyaryletherketone composite material is prepared by the preparation method according to any one of claims 1 to 9.

11. Use of the carbon fiber reinforced polyaryletherketone medical composite material of claim 10 in medical devices;

The applications include applications in 3D printed medical materials, artificial prostheses, medical catheters, oral implants, ports of infusion, cardiac pacemaker housings, medical aiming brackets, body bone locking systems, medical wrenches, medical connectors, medical positioning brackets, surgical head and retraction systems, medical handles, medical needles, medical sutures, femoral condyles, bone nails, screws, anchors, rivets, intramedullary needles, bone plates, tibial trays, cranial repair systems, or spinal interbody fusion devices.

12. The use of claim 11, wherein the prosthesis comprises any one or a combination of at least two of a maxillofacial bone, a heart valve, a prosthetic bone, and a prosthetic joint;

The medical connector includes a medical connector.