Medical-grade PEEK composite material with developing property and preparation method of medical-grade PEEK composite material

Abstract

The invention relates to the technical field of high polymer materials, in particular to a medical-grade PEEK composite material with developability and a preparation method thereof. Raw materials of the PEEK composite material comprise barium sulfate in-situ modified carbon fibers and medical-grade polyether-ether-ketone, and in the raw materials of the barium sulfate in-situ modified carbon fibers, the carbon fibers adopt acidified carbon fiber short fibers. The preparation method of the PEEK composite material provided by the invention is simple, the prepared medical-grade PEEK composite material with the developing property meets the standard of a medical implantation-grade PEEK material, barium sulfate grows on carbon fibers in situ, dispersion of barium sulfate in a PEEK / carbon fiber matrix is facilitated, the agglomeration phenomenon of nano particles is reduced, the developing property of the PEEK composite material is improved, and the development performance of the PEEK composite material is improved. The composite material is stable and uniform in performance, and the mechanical property of the PEEK material is enhanced.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, in particular to a medical-grade PEEK composite material with developing property and a preparation method thereof. BACKGROUND

[0002] Polyether ether ketone (PEEK) is a kind of high polymer material with good biological compatibility, chemical stability and mechanical properties, and also has X-ray permeability. It can be exposed to high temperature steam, gamma rays and ethylene oxide for a long time without changing its original properties. In recent years, medical-grade polyether ether ketone material has been widely used in clinical medical field. In addition, PEEK has no biological toxicity, corrosion resistance, light weight and high strength. Its elastic modulus (3-4 GPa) is close to the elastic modulus of human bone (14 GPa for compact bone and 1 GPa for trabecular bone). Compared with titanium alloy (106-155 GPa) with high elastic modulus, PEEK implant can reduce the occurrence of "stress shielding" phenomenon after operation, so PEEK can be used to replace metal to manufacture human bone. Compared with industrial-grade PEEK, medical-grade PEEK needs to be refined and purified to meet the medical implant-grade polyether ether ketone material standard for human implantation.

[0003] Polyether ether ketone and carbon fiber / polyether ether ketone composite material are both X-ray permeable materials. However, most clinical operations require implants to have certain X-ray blocking properties. Barium sulfate is a common contrast agent, which is a small white particle that does not easily dissolve in acidic or alkaline environment and is harmless to human body, showing a white image under X-ray irradiation. Usually, a certain proportion of barium sulfate is added to the polyether ether ketone resin matrix to make the composite material have X-ray blocking property. Then, the method for preparing PEEK and nano-barium sulfate composite material is by ball milling blending, high-speed stirring or double screw extrusion. Since PEEK has high viscosity and is not soluble in most solvents at room temperature, and nano-particles have relatively large specific surface area, agglomeration phenomenon easily occurs in PEEK matrix, which greatly affects the mechanical properties of PEEK composite material. SUMMARY

[0004] In order to solve the above technical problems, the present application provides a medical-grade PEEK composite material with developing property and a preparation method thereof.

[0005] In the first aspect, the present invention provides a medical-grade PEEK composite material with development properties, wherein the raw materials of the PEEK composite material include carbon fibers modified in situ with barium sulfate and medical-grade polyetheretherketone, and the raw materials of the carbon fibers modified in situ with barium sulfate include acidified carbon fiber staple fibers. The medical-grade PEEK composite material with development properties provided by the present invention ensures that PEEK meets the standards of medical implant-grade polyetheretherketone materials, and that barium sulfate is evenly dispersed in the PEEK matrix, and the performance of the composite material is stable and uniform. Unlike traditional mixing processes, the present invention acidifies the carbon fiber staple fibers to allow barium sulfate to grow in situ on the carbon fibers, which is beneficial to the dispersion of barium sulfate in the PEEK / carbon fiber matrix, reduces the agglomeration of nanoparticles, and improves the development properties of the PEEK composite material. At the same time, the barium sulfate on the carbon fibers acts as a "bonding point" to connect the PEEK matrix and the carbon fibers, thereby enhancing the interfacial bonding and mechanical properties of PEEK and the carbon fibers.

[0006] Preferably, the mass ratio of the carbon fiber modified with barium sulfate in situ to medical-grade polyetheretherketone is 10:90 to 50:50, preferably 15:85 to 30:70, and more preferably 25:75 to 22:78. For example, the mass fraction of the carbon fiber modified with barium sulfate in situ is 15%, 20%, 25%, 30%, etc., and the mass fraction of the medical-grade polyetheretherketone is 70%, 75%, 80%, 85%, etc.

[0007] In the present invention, by optimizing the ratio of carbon fiber in situ modified with barium sulfate and medical-grade polyetheretherketone, the interfacial bonding performance and mechanical properties of the PEEK composite material can be further enhanced.

[0008] Preferably, the raw materials of the carbon fiber modified in situ with barium sulfate include acidified carbon fiber short fibers, barium chloride and sodium sulfate. The barium chloride and sodium sulfate react to form barium sulfate.

[0009] It is further preferred that in the carbon fiber in situ modified with barium sulfate, the mass ratio of the acidified carbon fiber staple fiber and barium sulfate is 1~100:0~50; preferably, the mass ratio of the acidified carbon fiber staple fiber and barium sulfate is 50~90:10~50, and most preferably is 50:12.5. For example, in 125 parts by mass of the carbon fiber in situ modified with barium sulfate, the acidified carbon fiber staple fiber and barium sulfate are 100 parts and 25 parts, respectively.

[0010] Further preferably, the raw materials of the acidified carbon fiber staple fibers include carbon fiber staple fibers and mixed acid solvent in a ratio of 200 g:500-1000 mL, preferably 100 g:300-400 mL.

[0011] More preferably, the mixed acid solvent is concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 5 to 1:1; preferably 2 to 4:1, for example, 2:1, 3:1, 4:1, etc.

[0012] In the present invention, the preparation of acidified carbon fibers through acidification with a mixed acidic solution can effectively change the surface structure of the carbon fibers, thereby increasing the number of oxygen-containing active functional groups on the carbon fibers, enhancing their active sites for complexation reaction with barium chloride, increasing the binding force between barium sulfate and PEEK, and improving the dispersibility of barium sulfate in PEEK. The degree of carbon fiber acidification can be adjusted by adjusting the volume ratio and concentration of the acid solution.

[0013] Further preferably, the average length of the carbon fiber staple is 2~10 mm, and the average diameter is 6~9 μm; preferably, the average length is 4~8 mm, and the average diameter is 6~8 μm, etc.; the concentration of the concentrated sulfuric acid is 85%~99%; the concentration of the concentrated nitric acid is 60%~75%.

[0014] In a second aspect, the present invention provides a method for preparing the above-mentioned medical-grade PEEK composite material with developability, comprising: 1) Barium sulfate is in situ grown on acidified carbon fiber staple fibers to obtain barium sulfate in situ modified carbon fibers.

[0015] 2) The carbon fiber modified with barium sulfate in situ is mixed with medical-grade polyetheretherketone and subjected to twin-screw extrusion granulation to obtain a medical-grade PEEK composite material with developability.

[0016] Preferably, in step 1), the acidified carbon fiber staple fibers are mixed with deionized water, barium chloride and sodium sulfate are added and reacted in situ, and then washed with water and dried to obtain carbon fibers in situ modified with barium sulfate; Further preferably, the method comprises: mixing acidified carbon fiber staple fibers, barium chloride and deionized water to carry out a complexation reaction, then adding a coupling agent and sodium sulfate, heating and continuing to stir, washing and drying.

[0017] In the present invention, under the conditions of preferred raw materials, mixing order, temperature and reaction time, barium chloride and sodium sulfate react better with the surface of the acidified carbon fiber, thereby improving the modification effect and better ensuring uniformity and stability.

[0018] Further preferably, the temperature of the complexation reaction is 20-40 ° C, and the reaction is carried out for 3-8 hours under stirring conditions; for example, the temperature is 20, 23, 25, 27, 28, 29, 30, 31, 32, 33, 35, 36, 37, 39, 40 ° C, etc., and the time is 3, 4, 5, 6, 7, 8 hours, etc.

[0019] Preferably, the coupling agent is selected from one or two of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, cetyltrimethylammonium sulfate and cetyltrimethylacetoxyethylammonium chloride.

[0020] Preferably, the heating temperature is 35-50°C, for example, 39, 40, 42, 42, 44°C, etc.; the stirring time is 6-10 h, for example, 7, 8, 9 h, etc.

[0021] Preferably, the ratio of the deionized water to the acidified carbon fiber staple is 800 mL:50-100 g.

[0022] Preferably, step 1) further comprises: mixing carbon fiber staple fibers with a mixed acid solvent, heating and stirring, washing with ice water after the reaction, and drying to obtain acidified carbon fiber staple fibers. Preferably, the reaction temperature is 50-70°C, the stirring time is 1-4 hours, and the drying is performed at 90-115°C, preferably 100°C, for 2-5 hours.

[0023] Preferably, in step 2), the carbon fiber modified with barium sulfate in situ and medical-grade polyetheretherketone are mixed and dried, and then subjected to twin-screw extrusion granulation; the drying temperature is 110-130° C., and the drying time is 1-5 h.

[0024] Preferably, in step 2), the conditions for the twin-screw extrusion granulation include: introducing the carbon fiber in situ modified with barium sulfate from the first exhaust port of the twin-screw extruder, adding medical-grade polyetheretherketone from the feed port of the twin-screw extruder, the processing temperature is 280~380℃, the extrusion granulation, the temperature of the feeding section is 280~330℃, the temperature of the processing section is 320~360℃, the temperature of the head die is 350~380℃, and the screw speed is 75~85 r / min.

[0025] The beneficial effects of the present invention are at least as follows: PEEK / carbon fiber composite materials are usually prepared by physically blending the two or extruding them in a twin-screw extruder. The present invention first prepares acidified carbon fibers, adds a coupling agent, barium chloride and sodium sulfate, and then in situ grows barium sulfate nanoparticles on the carbon fiber staple fibers, thereby increasing the spatial steric resistance potential energy between the particles and effectively reducing the agglomeration of the nanoparticles added to the PEEK / carbon fiber matrix. The present invention solves the problem of X-ray transparency of PEEK / carbon fiber composite materials by adding barium sulfate nanoparticles, achieves the development effect for clinical use, and broadens the application range of PEEK / carbon fiber composite materials. The present invention regulates the concentration of barium chloride and sodium sulfate in the system and controls the cooling temperature to allow the barium sulfate particles to grow in situ. In the barium sulfate / carbon fiber / polyetheretherketone composite material of the present invention, the barium sulfate grown in situ on the carbon fiber staple fibers serves as the bonding point between the PEEK resin and the carbon fiber, thereby improving the interfacial strength between the fiber and the resin and enhancing the mechanical properties of the composite material. DETAILED DESCRIPTION

[0026] To make the objectives, technical solutions, and advantages of the present invention more clear, the technical solutions of the present invention are described clearly and completely below. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0027] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to form one or more new numerical ranges, and these numerical ranges should be considered to be specifically disclosed in the present invention.

[0028] Where specific techniques or conditions are not specified in the examples of the present invention, the techniques or conditions described in the literature in the field or in the product specifications were followed. All devices, instruments, reagents, etc. used, where the manufacturer is not specified, are conventional products available through regular channels. All experimental reagents and raw materials involved are commercially available, and all reagents are analytically pure.

[0029] In the following examples of the present invention, the polyetheretherketone powder used is a coarse powder of Zhongyan medical grade polyetheretherketone; in the examples of the present invention, the concentration of concentrated sulfuric acid is 98.3%, and the concentration of concentrated nitric acid is 68%.

[0030] Example 1 The present embodiment provides a medical-grade PEEK composite material with a developing function, and the raw materials of the PEEK composite material include carbon fibers modified in situ by barium sulfate and medical-grade polyetheretherketone. The mass ratio of the carbon fibers modified in situ by barium sulfate and medical-grade polyetheretherketone is 20:80; the raw materials of the carbon fibers modified in situ by barium sulfate include acidified carbon fiber staple fibers, barium chloride and sodium sulfate; the mass ratio of acidified carbon fiber staple fibers, barium chloride and sodium sulfate is 75:23.95:14.5. The raw materials of the acidified carbon fiber staple fibers include carbon fiber staple fibers and a mixed acid solvent in a ratio of 200g:600 mL, and the mixed acid solvent is concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1. The average length of the carbon fiber staple fibers is 6 mm and the average diameter is 7 μm.

[0031] This embodiment also provides a method for preparing the above-mentioned medical-grade PEEK composite material with development function: S1: Preparation of acidified carbon fiber; 200 g of carbon fiber staple (length 6 mm, diameter 7 μm) was placed in 600 mL of a mixed acid solvent prepared with concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1. The reaction temperature was 60 °C and stirred at constant temperature for 3 h. After the reaction was completed, ice water was added for washing and the mixture was dried in an oven at 100 °C for 4 h to obtain acidified carbon fiber staple.

[0032] S2: Preparation of carbon fibers modified in situ with barium sulfate: 23.95 g of barium chloride and 75 g of acidified carbon fiber staple fibers were added to 800 mL of deionized water. The mixture was heated to 30°C and stirred for 6 h for a complexation reaction. After the reaction, 0.3 g of hexadecyltrimethylammonium bromide as a coupling agent and 14.50 g of sodium sulfate were added. The mixture was heated to 40°C and stirred for another 8 h. The mixture was washed with deionized water and dried to obtain 100 g of carbon fibers modified in situ with barium sulfate.

[0033] S3: Preparation of PEEK / carbon fiber / barium sulfate ternary composite material; the mass fraction of carbon fiber modified by barium sulfate in situ was 20%, and the mass fraction of polyetheretherketone powder was 80% (5:15:80; the mass fraction of barium sulfate was 5%, and the mass fraction of carbon fiber was 15%). The in situ modified carbon fiber and polyetheretherketone were heated at 120 o C oven and dried for 3 h. The carbon fiber modified with barium sulfate in situ was introduced from the first exhaust port of the twin-screw extruder, and polyetheretherketone was added from the feed port of the twin-screw extruder. The processing temperature was 280°C to 380°C. The extruder was extruded and pelletized. The temperatures of the feeding section, processing section, and die were 325°C, 345°C, 365°C, 380°C, and 370°C, respectively. The screw speed was 80 r / min. After extrusion, a PEEK / carbon fiber / barium sulfate ternary composite material was obtained.

[0034] Example 2 The present embodiment provides a medical-grade PEEK composite material with a developing function, and the raw materials of the PEEK composite material include carbon fibers modified in situ by barium sulfate and medical-grade polyetheretherketone. The mass ratio of the carbon fibers modified in situ by barium sulfate and the medical-grade polyetheretherketone is 25:75; the raw materials of the carbon fibers modified in situ by barium sulfate include acidified carbon fiber staple fibers, barium chloride and sodium sulfate; the mass ratio of the acidified carbon fiber staple fibers, barium chloride and sodium sulfate is 75:47.9:29. The raw materials of the acidified carbon fiber staple fibers include carbon fiber staple fibers and a mixed acid solvent in a ratio of 200 g:800 mL, and the mixed acid solvent is concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1. The average length of the carbon fiber staple fibers is 6 mm and the average diameter is 7 μm.

[0035] This embodiment also provides a method for preparing the above-mentioned medical-grade PEEK composite material with development function: S1: Preparation of acidified carbon fiber; 200 g of carbon fiber staple (length 6 mm, diameter 7 μm) was placed in 800 mL of a mixed acid solvent of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3:1. The reaction temperature was 60 °C and stirred at constant temperature for 3 h. After the reaction was completed, ice water was added for washing and the mixture was dried in an oven at 100 °C for 4 h to obtain acidified carbon fiber staple.

[0036] S2: Preparation of carbon fibers modified with barium sulfate in situ: 47.9 g of barium chloride and 75 g of acidified carbon fiber staple fibers were added to 800 mL of deionized water. The mixture was heated to 30°C and stirred for 6 h for a complexation reaction. After the reaction, 0.3 g of hexadecyltrimethylammonium bromide as a coupling agent and 29 g of sodium sulfate were added. The mixture was heated to 40°C and stirred for another 8 h. The mixture was washed with deionized water and dried to obtain 125 g of carbon fibers modified with barium sulfate in situ.

[0037] S3: Preparation of PEEK / carbon fiber / barium sulfate ternary composite material; The mass fraction of carbon fiber modified with barium sulfate in situ was 25%, and the mass fraction of polyetheretherketone powder was 75%. The in situ modified carbon fiber and polyetheretherketone were dried in a 120 ℃ oven for 3 h. The carbon fiber modified with barium sulfate in situ was introduced from the first exhaust port of the twin-screw extruder, and polyetheretherketone was added from the feed port of the twin-screw extruder. The processing temperature was 280 ℃~380 ℃, and the extrusion pelletization was carried out. The feeding section, processing section, and die temperature were 325 ℃, 345 ℃, 365 ℃, 380 ℃, and 370 ℃, respectively. The screw speed was 80 r / min. After extrusion, the PEEK / carbon fiber / barium sulfate ternary composite material was obtained.

[0038] Example 3 The present embodiment provides a medical-grade PEEK composite material with a developing function. The raw materials of the PEEK composite material include carbon fibers modified in situ by barium sulfate and medical-grade polyetheretherketone. The mass ratio of the carbon fibers modified in situ by barium sulfate and the medical-grade polyetheretherketone is 30:70; the raw materials of the carbon fibers modified in situ by barium sulfate include acidified carbon fiber staple fibers, barium chloride and sodium sulfate; the mass ratio of the acidified carbon fiber staple fibers, barium chloride and sodium sulfate is 75:71.85:43.5. The raw materials of the acidified carbon fiber staple fibers include carbon fiber staple fibers and a mixed acid solvent in a ratio of 200 g:800 mL, and the mixed acid solvent is concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1. The average length of the carbon fiber staple fibers is 6 mm and the average diameter is 7 μm.

[0039] This embodiment also provides a method for preparing the above-mentioned medical-grade PEEK composite material with development function: S1: Preparation of acidified carbon fiber; 200 g of carbon fiber staple (length 6 mm, diameter 7 μm) was placed in 800 mL of a mixed acid solvent of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3:1. The reaction temperature was 60 °C and stirred at constant temperature for 3 h. After the reaction was completed, ice water was added for washing and the mixture was dried in an oven at 100 °C for 4 h to obtain acidified carbon fiber staple.

[0040] S2: Preparation of carbon fibers modified in situ with barium sulfate: 71.85 g of barium chloride and 75 g of acidified carbon fiber staple fibers were added to 800 mL of deionized water. The mixture was heated to 30°C and stirred for 6 h for a complexation reaction. After the reaction, 0.3 g of hexadecyltrimethylammonium bromide as a coupling agent and 43.5 g of sodium sulfate were added. The mixture was heated to 40°C and stirred for another 8 h. The mixture was washed with deionized water and dried to obtain 150 g of carbon fibers modified in situ with barium sulfate.

[0041] S3: Preparation of PEEK / carbon fiber / barium sulfate ternary composite material; The mass fraction of carbon fiber modified with barium sulfate in situ was 30%, and the mass fraction of polyetheretherketone powder was 70%. The in situ modified carbon fiber and polyetheretherketone were dried in a 120 ℃ oven for 3 h. The carbon fiber modified with barium sulfate in situ was introduced from the first exhaust port of the twin-screw extruder, and polyetheretherketone was added from the feed port of the twin-screw extruder. The processing temperature was 280 ℃~380 ℃, and the extrusion pelletization was carried out. The feeding section, processing section, and die temperature were 325 ℃, 345 ℃, 365 ℃, 380 ℃, and 370 ℃, respectively. The screw speed was 80 r / min. After extrusion, the PEEK / carbon fiber / barium sulfate ternary composite material was obtained.

[0042] Example 4 The present embodiment provides a medical-grade PEEK composite material with a developing function. The raw materials of the PEEK composite material include carbon fibers modified in situ by barium sulfate and medical-grade polyetheretherketone. The mass ratio of the carbon fibers modified in situ by barium sulfate and the medical-grade polyetheretherketone is 15:85; the raw materials of the carbon fibers modified in situ by barium sulfate include acidified carbon fiber staple fibers, barium chloride and sodium sulfate; the mass ratio of the acidified carbon fiber staple fibers, barium chloride and sodium sulfate is 50:23.95:14.5. The raw materials of the acidified carbon fiber staple fibers include carbon fiber staple fibers and a mixed acid solvent in a ratio of 200 g:800 mL, and the mixed acid solvent is concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1. The average length of the carbon fiber staple fibers is 6 mm and the average diameter is 7 μm.

[0043] This embodiment also provides a method for preparing the above-mentioned medical-grade PEEK composite material with development function: S1: Preparation of acidified carbon fiber; 200 g of carbon fiber staple (length 6 mm, diameter 7 μm) was placed in 800 mL of a mixed acid solvent of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3:1. The reaction temperature was 60 °C and stirred at constant temperature for 3 h. After the reaction was completed, ice water was added for washing and the mixture was dried in an oven at 100 °C for 4 h to obtain acidified carbon fiber staple.

[0044] S2: Preparation of carbon fibers modified with barium sulfate in situ: 23.95 g of barium chloride and 50 g of acidified carbon fiber staple fibers were added to 800 mL of deionized water. The mixture was heated to 30°C and stirred for 6 h for a complexation reaction. After the reaction, 0.3 g of hexadecyltrimethylammonium bromide as a coupling agent and 14.5 g of sodium sulfate were added. The mixture was heated to 40°C and stirred for another 8 h. The mixture was washed with deionized water and dried to obtain 75 g of carbon fibers modified with barium sulfate in situ.

[0045] S3: Preparation of PEEK / carbon fiber / barium sulfate ternary composite material; The mass fraction of carbon fiber modified with barium sulfate in situ was 15%, and the mass fraction of polyetheretherketone powder was 85%. The in situ modified carbon fiber and polyetheretherketone were dried in a 120 ℃ oven for 3 h. The carbon fiber modified with barium sulfate in situ was introduced from the first exhaust port of the twin-screw extruder, and polyetheretherketone was added from the feed port of the twin-screw extruder. The processing temperature was 280 ℃~380 ℃, and the extrusion pelletization was carried out. The feeding section, processing section, and die temperature were 325 ℃, 345 ℃, 365 ℃, 380 ℃, and 370 ℃, respectively. The screw speed was 80 r / min. After extrusion, the PEEK / carbon fiber / barium sulfate ternary composite material was obtained.

[0046] Example 5 The present embodiment provides a medical-grade PEEK composite material with a developing function. The raw materials of the PEEK composite material include carbon fibers modified in situ by barium sulfate and medical-grade polyetheretherketone. The mass ratio of the carbon fibers modified in situ by barium sulfate and the medical-grade polyetheretherketone is 25:75; the raw materials of the carbon fibers modified in situ by barium sulfate include acidified carbon fiber staple fibers, barium chloride and sodium sulfate; the mass ratio of the acidified carbon fiber staple fibers, barium chloride and sodium sulfate is 100:23.95:14.5. The raw materials of the acidified carbon fiber staple fibers include carbon fiber staple fibers and a mixed acid solvent in a ratio of 200 g:800 mL, and the mixed acid solvent is concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1. The average length of the carbon fiber staple fibers is 6 mm and the average diameter is 7 μm.

[0047] This embodiment also provides a method for preparing the above-mentioned medical-grade PEEK composite material with development function: S1: Preparation of acidified carbon fiber; 200 g of carbon fiber staple (length 6 mm, diameter 7 μm) was placed in 800 mL of a mixed acid solvent of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3:1. The reaction temperature was 60 °C and stirred at constant temperature for 3 h. After the reaction was completed, ice water was added for washing and the mixture was dried in an oven at 100 °C for 4 h to obtain acidified carbon fiber staple.

[0048] S2: Preparation of carbon fibers modified with barium sulfate in situ: 23.95 g of barium chloride and 100 g of acidified carbon fiber staple fibers were added to 800 mL of deionized water. The mixture was heated to 30°C and stirred for 6 h for a complexation reaction. After the reaction, 0.3 g of hexadecyltrimethylammonium bromide as a coupling agent and 14.5 g of sodium sulfate were added. The mixture was heated to 40°C and stirred for another 8 h. The mixture was washed with deionized water and dried to obtain 125 g of carbon fibers modified with barium sulfate in situ.

[0049] S3: Preparation of PEEK / carbon fiber / barium sulfate ternary composite material; The mass fraction of carbon fiber modified with barium sulfate in situ was 25%, and the mass fraction of polyetheretherketone powder was 75%. The in situ modified carbon fiber and polyetheretherketone were dried in a 120 ℃ oven for 3 h. The carbon fiber modified with barium sulfate in situ was introduced from the first exhaust port of the twin-screw extruder, and polyetheretherketone was added from the feed port of the twin-screw extruder. The processing temperature was 280 ℃~380 ℃, and the extrusion pelletization was carried out. The feeding section, processing section, and die temperature were 325 ℃, 345 ℃, 365 ℃, 380 ℃, and 370 ℃, respectively. The screw speed was 80 r / min. After extrusion, the PEEK / carbon fiber / barium sulfate ternary composite material was obtained.

[0050] Example 6 The present embodiment provides a medical-grade PEEK composite material with a developing function. The raw materials of the PEEK composite material include carbon fibers modified in situ by barium sulfate and medical-grade polyetheretherketone. The mass ratio of the carbon fibers modified in situ by barium sulfate and medical-grade polyetheretherketone is 20:80; the raw materials of the carbon fibers modified in situ by barium sulfate include acidified carbon fiber staple fibers, barium chloride and sodium sulfate; the mass ratio of acidified carbon fiber staple fibers, barium chloride and sodium sulfate is 75:23.95:14.5. The raw materials of the acidified carbon fiber staple fibers include carbon fiber staple fibers and a mixed acid solvent in a ratio of 200 g:800 mL, and the mixed acid solvent is concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 1:1. The average length of the carbon fiber staple fibers is 6 mm and the average diameter is 7 μm.

[0051] This embodiment also provides a method for preparing the above-mentioned medical-grade PEEK composite material with development function: S1: Preparation of acidified carbon fiber; 200 g of carbon fiber staple (length 6 mm, diameter 7 μm) was placed in 800 mL of a mixed acid solvent of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 1:1. The reaction temperature was 60 °C and stirred at constant temperature for 4 h. After the reaction was completed, ice water was added for washing and the mixture was dried in an oven at 100 °C for 4 h to obtain acidified carbon fiber staple.

[0052] S2: Preparation of carbon fibers modified with barium sulfate in situ: 23.95 g of barium chloride and 75 g of acidified carbon fiber staple fibers were added to 800 mL of deionized water. The reaction was heated to 30°C and stirred for 6 h to allow for a complexation reaction. After the reaction was complete, 0.3 g of hexadecyltrimethylammonium bromide as a coupling agent and 14.5 g of sodium sulfate were added. The mixture was heated to 40°C and stirred for another 8 h. The mixture was washed with deionized water and dried to obtain 100 g of carbon fibers modified with barium sulfate in situ.

[0053] S3: Preparation of PEEK / carbon fiber / barium sulfate ternary composite material; The mass fraction of carbon fiber modified with barium sulfate in situ was 20%, and the mass fraction of polyetheretherketone powder was 80%. The in situ modified carbon fiber and polyetheretherketone were dried in a 120 ℃ oven for 3 h. The carbon fiber modified with barium sulfate in situ was introduced from the first exhaust port of the twin-screw extruder, and polyetheretherketone was added from the feed port of the twin-screw extruder. The processing temperature was 280 ℃~380 ℃, and the extrusion pelletization was carried out. The feeding section, processing section, and die temperature were 325 ℃, 345 ℃, 365 ℃, 380 ℃, and 370 ℃, respectively. The screw speed was 80 r / min. After extrusion, the PEEK / carbon fiber / barium sulfate ternary composite material was obtained.

[0054] Comparative Example 1 Preparation of PEEK / carbon fiber / barium sulfate ternary composite material; barium sulfate, carbon fiber short fibers (length 6 mm, diameter 7 μm), and polyetheretherketone powder with mass fractions of (5:20:75) were placed in a 120 ℃ oven and dried for 3 h. The barium sulfate and carbon fiber short fibers were mixed in a high-speed mixer for 30 min. The barium sulfate and carbon fiber mixture was introduced from the first exhaust port of the twin-screw extruder, and polyetheretherketone was added from the feeding port of the twin-screw extruder. The processing temperature was 280 ℃~380 ℃, and the extrusion pelletization was carried out. The temperatures of the feeding section, processing section, and die head were 325 ℃, 345 ℃, 365 ℃, 380 ℃, and 370 ℃, respectively. The screw speed was 80 r / min. After extrusion, the PEEK / carbon fiber / barium sulfate ternary composite material was obtained.

[0055] Comparative Example 2 Preparation of PEEK / carbon fiber binary composite materials; carbon fiber short fibers (length 6 mm, diameter 7 μm) and polyetheretherketone powder with a mass fraction of (20:80) were placed in a 120 ℃ oven and dried for 3 h. The carbon fibers were introduced from the first exhaust port of the twin-screw extruder, and polyetheretherketone was added from the feeding port of the twin-screw extruder. The processing temperature was 280 ℃ ~ 380 ℃, and the extrusion pelletizing was carried out. The temperatures of the feeding section, processing section, and die were 325 ℃, 345 ℃, 365 ℃, 380 ℃, and 370 ℃, respectively. The screw speed was 80 r / min, and the PEEK / carbon fiber binary composite materials were obtained after extrusion.

[0056] The composite materials obtained in the above examples and comparative examples were subjected to performance tests. The tensile performance test was conducted in accordance with ISO 527 Plastics — Determination of tensile properties — Part 1: General; the flexural performance test was conducted in accordance with ISO 178 Plastics — Determination of flexural properties; and the impact strength test was conducted in accordance with ISO 180 Plastics — Determination of impact strength.

[0057] Table 1 Mechanical properties of PEEK composites

[0058] The composite material prepared in Example 5 was subjected to a cytotoxicity test using an extract solution (MTT method) in accordance with the national standard GB / T 14233.2-2005 (GB / T 16886.5-2003). Cell morphology was normal, and the cytotoxicity test results are shown in Table 2. This table demonstrates that the composite material prepared by the present invention exhibits excellent biocompatibility, broadening the application of PEEK materials in the medical field.

[0059] Table 2 Cytotoxicity of the composite material in Example 5

[0060] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A medical-grade PEEK composite material with developability, characterized in that: The raw materials of the PEEK composite material include carbon fibers modified in situ by barium sulfate and medical-grade polyetheretherketone. Among the raw materials of the carbon fibers modified in situ by barium sulfate, the carbon fibers are acidified carbon fiber short fibers.

2. The medical-grade PEEK composite material with developability according to claim 1, characterized in that: The mass ratio of the barium sulfate in-situ modified carbon fiber to medical-grade polyetheretherketone is 10:90-50:50, preferably 15:85-30:

70.

3. The medical-grade PEEK composite material with developability according to claim 1 or 2, characterized in that: The raw materials of the carbon fiber modified in situ by barium sulfate include acidified carbon fiber short fibers, barium chloride and sodium sulfate; Preferably, in the carbon fiber in situ modified with barium sulfate, the mass ratio of the acidified carbon fiber staple fiber to the barium sulfate is 1~100:0~50; preferably, the mass ratio of the acidified carbon fiber staple fiber to the barium sulfate is 50~90:10~50.

4. The medical-grade PEEK composite material with developability according to claim 3, characterized in that: The raw materials of the acidified carbon fiber staple fibers include carbon fiber staple fibers and mixed acid solvent in a ratio of 200 g:500-1000 mL, preferably 100 g:300-400 mL; Preferably, the mixed acid solvent is concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 5 to 1:1; the average length of the carbon fiber staple fibers is 2 to 10 mm, and the average diameter is 6 to 9 μm; the concentration of the concentrated sulfuric acid is 85% to 99%; and the concentration of the concentrated nitric acid is 60% to 75%.

5. The method for preparing the medical-grade PEEK composite material with developability according to any one of claims 1 to 4, characterized in that: include: 1) In-situ growth of barium sulfate on acidified carbon fiber staple fibers to obtain barium sulfate in-situ modified carbon fibers; 2) The carbon fiber modified with barium sulfate in situ is mixed with medical-grade polyetheretherketone and subjected to twin-screw extrusion granulation to obtain a medical-grade PEEK composite material with developability.

6. The preparation method according to claim 5, characterized in that In step 1), the acidified carbon fiber staple fibers are mixed with deionized water, barium chloride and sodium sulfate are added and reacted in situ, and then washed with water and dried to obtain carbon fibers in situ modified with barium sulfate; Preferably, the method comprises: mixing acidified carbon fiber staple fibers, barium chloride and deionized water to carry out complexation reaction, then adding a coupling agent and sodium sulfate, heating and continuing stirring, washing and drying.

7. The preparation method according to claim 6, characterized in that The complexation reaction temperature is 20-40°C, and the reaction is carried out for 3-8 hours under stirring conditions; And / or, the coupling agent is selected from one or two of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, cetyltrimethylammonium sulfate and cetyltrimethylacetoxyethylammonium chloride.

8. The preparation method according to any one of claims 5 to 7, characterized in that Step 1) further comprises: mixing carbon fiber staple fibers with a mixed acid solvent, heating and stirring, washing with ice water after the reaction, and drying to obtain acidified carbon fiber staple fibers; Preferably, the reaction temperature is 50-70° C., the stirring time is 1-4 h, and the drying is performed at 90-115° C. for 2-5 h.

9. The preparation method according to any one of claims 5 to 8, characterized in that In step 2), the carbon fiber modified in situ with barium sulfate and medical-grade polyetheretherketone are mixed and dried, and then subjected to twin-screw extrusion granulation; the drying temperature is 110-130° C., and the drying time is 1-5 h.

10. The preparation method according to any one of claims 5 to 9, characterized in that: In step 2), the conditions for the twin-screw extrusion granulation include: introducing the barium sulfate in-situ modified carbon fiber from the first exhaust port of the twin-screw extruder, adding medical-grade polyetheretherketone from the feed port of the twin-screw extruder, the processing temperature is 280~380°C, extrusion and pelletizing, the temperature of the feeding section is 280~330°C, the temperature of the processing section is 320~360°C, the temperature of the head die is 350~380°C, and the screw speed is 75~85 r / min.

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