Artificial blood vessel material, preparation method thereof and developing artificial blood vessel product

Abstract

The invention relates to the technical field of biomedical polymer preparation, in particular to the technical field of manufacturing of high-value medical instruments suitable for implantation, intervention and the like, and particularly relates to an artificial blood vessel material, a preparation method thereof and a developing artificial blood vessel product. The material provided by the invention is obtained from fluorine-containing polyarylether or is obtained from fluorine-containing polyarylether and a developing agent; the fluorine-containing polyarylether is prepared from a bisphenol monomer and a fluorine-containing monomer; the bisphenol monomer is selected from one or more of biphenol, hydroquinone, bisphenol A, bisphenol AF and bisphenol S; the fluorine-containing monomer is selected from one or more of hexafluorobenzene, decafluorobiphenyl and decafluorobiphenyl ketone. The advantages of polyarylether and fluorine-containing polymer are combined, amorphous fluorine-containing polyarylether easy to process is synthesized, and the developable artificial blood vessel material with the mechanical property meeting the requirements of human blood vessels, high bursting pressure and high suture traction strength is obtained by combining electrostatic spinning, developing technology and solvent steam welding.

Description

Technical Field

[0001] The present invention relates to the technical field of biomedical polymer preparation, and in particular to the technical field of high-value medical device manufacturing such as implantation and intervention, and specifically to artificial blood vessel materials and preparation methods thereof, and developed artificial blood vessel products. Background Art

[0002] When blood vessels cannot supply blood normally due to aging, arteriosclerosis, embolism or damage, it is necessary to use autologous or artificial blood vessels for replacement, bypass or intervention and other surgical procedures for treatment. Research on artificial blood vessels can be divided into synthetic polymer materials, natural polymer materials and decellularized blood vessels according to the type of materials. Synthetic polymer materials have good mechanical strength and can be scaled; natural polymer materials have excellent biocompatibility, but their mechanical strength is low, and complex designs are required to achieve a balance of various properties; decellularized blood vessels have low immunogenicity, but are inconvenient to prepare and store, and have high overall costs.

[0003] At present, commercial artificial blood vessels are mainly large-caliber, among which expanded polytetrafluoroethylene (ePTFE), polyethylene terephthalate (PET) and polyurethane (PU) occupy the vast majority of the market share. All three are synthetic polymer materials, and the first two are the most common.

[0004] However, the above-mentioned commercial artificial blood vessels have the following disadvantages: PET's solvent resistance makes it difficult to achieve solution processing, and the finished product is a fiber woven structure. The fibers are too large, which can easily cause blood leakage; the raw material of ePTFE is polytetrafluoroethylene (PTFE), which is insoluble and infusible, and requires delicate and complex expanded processing for molding, which makes processing difficult.

[0005] In addition, as an implant, an artificial blood vessel should also have suitable mechanical properties, sufficient bursting pressure and suture pulling strength. The mechanical properties of artificial blood vessels should not be too low or too high. If they are too low, they are prone to rupture, and if they are too high, it is not conducive to the exchange of substances in the body. The bursting pressure of artificial blood vessels should be higher than the physiological pressure, that is, 140 mmHg, and the suture pulling strength should also be high enough to have sufficient mechanical properties to ensure that the natural blood vessels sutured to the transplant site are not easy to burst. The suitability of the mechanical properties of existing artificial blood vessels is limited, and the bursting pressure and suture pulling strength also need to be improved.

[0006] In addition, the development function is also an important function for artificial blood vessels. The development function allows doctors to more easily identify the location of blood vessels, size changes, internal proliferation of blood vessels, torsion, patency of blood vessels, etc. However, the existing commercial artificial blood vessel materials (ePTFE, PET) have a single processing method, and it is difficult to add the development function.

[0007] Therefore, it is of great significance to design and develop a developable artificial vascular material that is easy to process, has mechanical properties that meet the requirements of human blood vessels, has high bursting pressure, and has high suture pulling strength. Summary of the invention

[0008] In view of this, the technical problem to be solved by the present invention is to provide an artificial blood vessel material, a preparation method thereof and a developed artificial blood vessel product. The artificial blood vessel material provided by the present invention not only has high bursting pressure and suture pulling strength, but also has mechanical properties that meet the requirements of human blood vessels.

[0009] The present invention provides an artificial blood vessel material, wherein the artificial blood vessel material is obtained from fluorine-containing polyarylether; or, the artificial blood vessel material is obtained from fluorine-containing polyarylether and a developer;

[0010] The fluorine-containing polyarylether is obtained from bisphenol monomers and fluorine-containing monomers;

[0011] The bisphenol monomer is selected from one or more of biphenol, hydroquinone, bisphenol A, bisphenol AF and bisphenol S;

[0012] The fluorine-containing monomer is selected from one or more of hexafluorobenzene, decafluorobiphenyl and decafluorobiphenyl ketone.

[0013] The fluorinated polyarylether of the present invention combines the advantages of polyarylether and fluorinated polymer, has the characteristics of being amorphous and easy to process, and can be made into an artificial blood vessel material with excellent mechanical properties and meeting the mechanical properties of human blood vessels. The fluorinated polyarylether prepared by the present invention has excellent solubility and environmental stability in a variety of solvents, is not only convenient for storage and transportation, but also has a wide range of preparation conditions in the electrospinning process.

[0014] The fluorinated polyarylether of the present invention is a soluble fluorinated polyarylether, which is obtained from a bisphenol monomer and a fluorinated monomer; specifically, the fluorinated polyarylether of the present invention is obtained from a bisphenol monomer and a fluorinated monomer in a molar ratio of 1: (1-1.04), preferably from a bisphenol monomer and a fluorinated monomer in a molar ratio of 1: 1.02. The bisphenol monomer of the present invention is selected from one or more of biphenol, hydroquinone, bisphenol A, bisphenol AF and bisphenol S; the fluorinated monomer is selected from one or more of hexafluorobenzene, decafluorobiphenyl and decafluorobiphenyl ketone. In some embodiments of the present invention, the fluorinated polyarylether is obtained from a bisphenol monomer and a fluorinated monomer, the bisphenol monomer is bisphenol AF or bisphenol A, and the fluorinated monomer is hexafluorobenzene or decafluorobiphenyl. In two embodiments of the present invention, the fluorinated polyarylether is obtained from bisphenol AF and decafluorobiphenyl. In the other two embodiments of the present invention, the fluorinated polyarylether is obtained from bisphenol A and decafluorobiphenyl. The number average molecular weight of the fluorinated polyarylether of the present invention is 40000 Da to 70000 Da, preferably 54000 Da to 60000 Da.

[0015] The fluorinated polyarylether of the present invention can also be combined with a developing technology, that is, it can be made into a developable artificial blood vessel material with excellent mechanical properties and mechanical properties that meet the requirements of human blood vessels together with a developer. In certain embodiments of the present invention, the artificial blood vessel material is obtained from the fluorinated polyarylether and a developer with a mass fraction of 15 wt% to 40 wt%. The developer of the present invention is selected from one or more of barium sulfate, tungsten powder, bismuth oxide, bismuth subcarbonate and bismuth oxychloride.

[0016] The fluorinated polyarylether of the present invention is prepared by the following steps:

[0017] S1) heating the bisphenol monomer, the alkaline catalyst and the water-carrying agent in a solvent under reflux in a protective gas atmosphere;

[0018] S2) reacting the material obtained in step S1) with a fluorine-containing monomer to obtain a fluorine-containing polyarylether.

[0019] The present invention first heats bisphenol monomers, alkaline catalysts and water-carrying agents in a solvent under a protective gas atmosphere to reflux and carry water to completely remove the water generated during the deprotonation process. The bisphenol monomers of the present invention are the same as those described above and will not be described in detail; the protective gas is selected from one or more of nitrogen, helium, neon or argon; the alkaline catalyst is selected from any one of potassium carbonate, cesium carbonate, cesium fluoride, sodium carbonate, sodium fluoride and sodium bicarbonate; the water-carrying agent is selected from one or more of benzene, toluene, xylene and cyclohexane; the solvent is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N,-methylpyrrolidone, dimethyl sulfoxide, cyclopentane sulfone and diphenyl sulfone. The molar ratio of the alkaline catalyst to the bisphenol monomer of the present invention is 1.15~1.40. The heating reflux temperature of the present invention is 140°C to 185°C, preferably 170°C to 175°C, and the heating reflux time is 1.5 h to 4 h, preferably 2.5 h to 3 h.

[0020] After heating and refluxing, the obtained material is reacted with a fluorine-containing monomer to obtain a fluorine-containing polyarylether. Specifically, after heating and refluxing, the temperature of the reaction system is lowered to room temperature, and then a fluorine-containing monomer is added to the reaction system, and the temperature is raised to react. After the reaction is completed, the mixture is poured into deionized water to obtain a strip-shaped white polymer, and the polymer is crushed into fine particles, and then fully washed with distilled water and ethanol in turn, and vacuum dried to obtain a fluorine-containing polyarylether polymer. The fluorine-containing monomers described in the present invention are the same as those described above and will not be repeated. The reaction described in the present invention is an aromatic nucleophilic substitution, the reaction temperature is 80°C~100°C, and the reaction time is 10 h~30 h. In the system of the reaction described in the present invention, the monomer mass concentration is 15 wt%~25 wt%, and the solid content is 15 wt%~30 wt%.

[0021] The present invention provides a method for preparing an artificial blood vessel material as described in any of the above technical solutions, comprising the following steps: sequentially subjecting a fluorinated polyarylether solution to electrospinning and solvent vapor welding to obtain the artificial blood vessel material; or sequentially subjecting a solution of a fluorinated polyarylether and a developer to electrospinning and solvent vapor welding to obtain the artificial blood vessel material. The process of sequentially subjecting a fluorinated polyarylether solution to electrospinning and solvent vapor welding is as follows: Figure 1 As shown, Figure 1 This is a schematic diagram of the process of sequentially electrospinning and solvent vapor welding a fluorinated polyarylether solution according to the present invention.

[0022] If the present invention is to prepare a non-developable artificial blood vessel material, the fluorinated polyarylether solution is subjected to electrostatic spinning and solvent vapor welding in sequence; the fluorinated polyarylether solution is obtained by mixing the fluorinated polyarylether and a solvent and ultrasonically, and the solution concentration is 40 wt% to 55 wt%. If the present invention is to prepare a developable artificial blood vessel material, the solution of the fluorinated polyarylether and a developer is subjected to electrostatic spinning and solvent vapor welding in sequence; the solution of the fluorinated polyarylether and a developer is obtained by mixing the fluorinated polyarylether, a developer and a solvent and ultrasonically, and the solution concentration is 40 to 55 wt%. The solvent of the present invention is selected from one or more of acetone, dichloromethane, chloroform, N,N-dimethylformamide and N,N-dimethylacetamide, preferably a mixed solution of acetone and N,N-dimethylformamide, and more preferably a mixed solution of acetone and N,N-dimethylformamide in a mass ratio of 1:(3 to 4). The mixing time of the present invention is 0.5 h to 1 h; the ultrasonic process is carried out at 150 W and 40 kHz for 0.5 to 1 h.

[0023] The present invention uses a fluorinated polyarylether solution or a solution of fluorinated polyarylether and a developer as a spinning solution for electrospinning. Specifically, the spinning solution is transferred to an electrospinning syringe, and spinning is performed on an electrospinning device, and the product is collected to obtain a fluorinated polyarylether porous fiber tube.

[0024] In the electrospinning of the present invention, the distance between the spinning needle and the metal collecting drum is 9 cm~18 cm, the spinning voltage is 10 kV~25 kV, the temperature in the spinning machine is 18°C~60°C, the humidity is 20%~60%, and the liquid feeding rate is 0.8 mL / h~1.5 mL / h. Preferably, in the electrospinning, the spinning needle specification is 21G. In certain embodiments of the present invention, the fiber diameter in the obtained fluorinated polyarylether porous fiber tube is 0.4 μm~1.5 μm, and the porosity is 60%~85%.

[0025] After electrospinning, the present invention performs solvent vapor welding on the fluorinated polyarylether porous fiber tube obtained by electrospinning to obtain an artificial blood vessel material; specifically, the fluorinated polyarylether porous fiber tube obtained by electrospinning is placed in a low-boiling point organic solvent for solvent vapor welding to obtain an artificial blood vessel material. The artificial blood vessel material is also called a fiber adhesion-enhanced tube, and if combined with a developing technology, it is called a fiber adhesion-enhanced developing tube. If the fiber adhesion-enhanced tube is cut longitudinally, it is called a fiber adhesion-enhanced film, and if combined with a developing technology, it is called a fiber adhesion-enhanced developing film.

[0026] The volume of the solvent used in the solvent vapor welding of the present invention is 20 μL~40 μL, the ambient temperature of the solvent vapor welding is 25°C, and the humidity is 20%~60%. The time of the solvent vapor welding of the present invention is 0.5 h~2 h. The concentration of the solvent used in the solvent vapor welding of the present invention is: every 30 μL~40 μL of solvent released in a 20 mL volume closed container corresponds to 5 cm 2 ~10 cm 2 Electrospinning original tube. In certain embodiments of the present invention, the fluorinated polyarylether porous fiber tube obtained by electrospinning is cut into a 5 cm long tube, fixed in the center of a 20 mL reagent bottle, a low boiling point organic solvent is added to the reagent bottle, the bottle cap is sealed, solvent vapor welding is performed, and the product is desolventized to obtain an artificial blood vessel material; during the desolventization process, the product is soaked in anhydrous ethanol for 10 min to 15 min, and then vacuum dried at 80°C for 4 h. The solvent used in the solvent vapor welding of the present invention is one or more of petroleum ether, dichloromethane, ethyl acetate, acetone and tetrahydrofuran. One of the functions of the solvent vapor welding of the present invention is to improve the mechanical strength of the porous fiber tube, improve the structural strength of the fiber mesh without substantially changing the pore size and microscopic morphology, and obtain an artificial blood vessel material that is more suitable for actual application scenarios and meets the mechanical strength of natural blood vessels.

[0027] In certain embodiments of the present invention, the present invention sequentially electrospins and solvent vapor welds a solution of fluorinated polyarylether and a developer to obtain the artificial vascular material; the fiber diameter of the obtained artificial vascular material is 0.35 μm~1.4 μm, the porosity is 55%~80%; the tensile strength is 2 MPa~8 MPa; and the elongation at break is 20%~40%.

[0028] The present invention also provides an artificial blood vessel product, which is processed from the artificial blood vessel material described in any of the above technical solutions or the artificial blood vessel material obtained by the preparation method described in any of the above technical solutions.

[0029] The present invention provides an artificial blood vessel material, a preparation method thereof, and an artificial blood vessel product. The artificial blood vessel material provided by the present invention is obtained from a fluorinated polyarylether or from a fluorinated polyarylether and a developer; the fluorinated polyarylether is obtained from a bisphenol monomer and a fluorinated monomer; the bisphenol monomer is selected from one or more of bisphenol A, bisphenol AF, and bisphenol S; the fluorinated monomer is selected from one or more of hexafluorobenzene, decafluorobiphenyl, and decafluorobiphenyl ketone. The present invention combines the advantages of polyarylether and fluorinated polymer to synthesize an amorphous and easy-to-process fluorinated polyarylether, so that it can combine electrospinning technology, developing technology, and solvent vapor welding to obtain a developable artificial blood vessel material with mechanical properties that meet the requirements of human blood vessels, high bursting pressure, and high suture pulling strength. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is a schematic diagram of the process of sequentially performing electrostatic spinning and solvent vapor welding on a fluorinated polyarylether solution according to the present invention;

[0031] Figure 2 This is a real photo of the fiber adhesion enhanced developing tube obtained in Example 1 of the present invention;

[0032] Figure 3 This is a SEM image of the fiber adhesion enhanced developing film obtained in Example 1 of the present invention;

[0033] Figure 4 This is a SEM image of the fluorine-containing polyarylether membrane material film obtained in Comparative Example 1 of the present invention;

[0034] Figure 5 This is a SEM image of the porous fiber membrane obtained in Comparative Example 2 of the present invention;

[0035] Figure 6 CT image of the fiber adhesion enhanced developing film obtained in Example 1 of the present invention;

[0036] Figure 7 CT image of the fiber adhesion enhanced membrane obtained in Example 4 of the present invention;

[0037] Figure 8 This is a fluorescent staining photograph of the fiber adhesion enhanced developing film obtained in Example 1 of the present invention;

[0038] Fig. 9 This is a SEM image of the growth state of mouse fibroblast L929 cells on the fiber adhesion enhanced developing film obtained in Example 1 of the present invention. DETAILED DESCRIPTION

[0039] The present invention discloses an artificial blood vessel material, a preparation method thereof, and an artificial blood vessel product. A person skilled in the art can refer to the content of this article and appropriately improve the process parameters to achieve the above. It should be particularly noted that all similar substitutions and modifications are obvious to a person skilled in the art and are considered to be included in the present invention. The method and application of the present invention have been described through preferred embodiments, and relevant personnel can obviously modify or appropriately change and combine the method and application of this article without departing from the content, spirit and scope of the present invention to implement and apply the technology of the present invention.

[0040] The present invention relates to the following testing method:

[0041] (1) Tensile properties test: The tensile properties test shall be carried out in accordance with GB / T 1040.1-2006 “Determination of tensile properties of plastics Part 1: General principles”.

[0042] (2) Test for reducing substance content of water-soluble substances: According to GB / T 14233.1-2022 "Test methods for medical infusion, transfusion and injection equipment Part 1: Chemical analysis methods", the extraction ratio is 0.2 g / mL, the extraction temperature is 37°C, and the extraction time is 72 h. The indirect titration method is used to test the reducing substance content of the water-soluble substances of the developing composite material.

[0043] (3) Cytotoxicity test: Cytotoxicity test of the developing composite material shall be conducted in accordance with GB / T 16886.5-2017 “Biological evaluation of medical devices Part 5: In vitro cytotoxicity test”.

[0044] (4) Hydrophilicity test: The water contact angle test of the membrane material is carried out in accordance with GB / T 30693-2014 "Measurement of the contact angle of plastic film with water".

[0045] (5) Burst pressure test: The water contact angle test of the membrane material is carried out according to the standard YY / T 0500-2021 "Cardiovascular Implants, Vascular Prostheses, Tubular Vascular Grafts and Vascular Patches".

[0046] (6) Suture pull strength: The membrane material suture pull strength test is carried out according to standard YY / T 0500-2021.

[0047] The present invention will be further described below in conjunction with embodiments:

[0048] Example 1

[0049] 50.434 g of bisphenol AF, 24.878 g of anhydrous potassium carbonate, 575.469 g of N,N-dimethylacetamide, and 191.823 g of toluene were placed in a 1000 mL three-necked flask equipped with a mechanical stirrer and a water separator. The atmosphere in the flask was replaced with argon and stirred at room temperature for 30 min. The oil bath was heated to 175°C and refluxed with water for 3 h. During this period, water continued to reflux into the water separator. This was the deprotonation process. After the process was completed, all the remaining toluene was evaporated, and the oil bath was cooled to room temperature. Then 51.119 g of decafluorobiphenyl was added, the oil bath was heated to 80°C, mechanically stirred at 250 r / min, and the reaction continued for 24 h. This was an aromatic nucleophilic substitution process. After the reaction was completed, the solution was poured into warm water to precipitate a strip-like crude product, which was purified 5 times in ethanol and ultrapure water and dried to obtain a white fluorinated polyarylether powder (number average molecular weight of 56,000 Da) containing 14 fluorine atoms in the structural unit.

[0050] Weigh 1.8 g of the obtained fluorinated polyarylether powder, 0.4 g of barium sulfate developer, and a mixed solvent of acetone and N,N-dimethylformamide in a mass ratio of 1:3. After mixing, ultrasonicate for 1 h at 140 W and 40 kHz. Pour the solution into a syringe and prepare a porous fiber developer tube through an electrospinning machine (model: Yunfan Technology YFSP-T). In the electrospinning process, a 21G metal needle was used, the electrospinning spacing was 9 cm, the spinning voltage was 20 KV, the temperature in the spinning machine was 30 ° C, the humidity was 30%, and the liquid feeding rate was 1.0 mL / h. After all the solution was exhausted, a fluorinated polyarylether porous fiber developer tube with a thickness of 0.2 mm was obtained.

[0051] The fluorinated polyarylether porous fiber developing tube was cut into a tube with a radius of 0.6 cm and a length of 5 cm, fixed in the center of a 20 mL reagent bottle, and dichloromethane was added to the reagent bottle, which was quickly covered with a cap and sealed. Solvent vapor welding was performed for 0.5 h, and the product was soaked in anhydrous ethanol for 10 min and then vacuum dried at 80 °C for 4 h to obtain a fiber adhesion-enhanced developing tube with a thickness of about 0.19 mm, such as Figure 2 As shown, Figure 2 This is a real picture of the fiber adhesion enhanced developing tube obtained in Example 1 of the present invention. At this time, the fiber adhesion enhanced developing film is obtained by cutting it longitudinally.

[0052] Example 2

[0053] 34.244 g bisphenol A, 24.878 g anhydrous potassium carbonate, 483.720 g N,N-dimethylacetamide, and 161.240 g cyclohexane were placed in a 1000 mL three-necked flask equipped with a mechanical stirrer and a water separator. The atmosphere in the flask was replaced with argon and stirred at room temperature for 30 min. The oil bath was heated to 175°C and refluxed with water for 3 h. During this period, water continued to reflux into the water separator. This was the deprotonation process. After the process was completed, all the remaining cyclohexane was evaporated, and the oil bath was cooled to room temperature. Then 51.119 g decafluorobiphenyl was added, the oil bath was heated to 80°C, mechanical stirring was 250 r / min, and the reaction was continued for 24 h. This was an aromatic nucleophilic substitution process. After the reaction was completed, the solution was poured into warm water to precipitate a strip-like crude product, which was purified 5 times in ethanol and ultrapure water and dried to obtain a white fluorinated polyarylether powder (number average molecular weight of 54,000 Da) containing 10 fluorine atoms in the structural unit.

[0054] The preparation process of the porous fiber developing film and the fiber adhesion enhanced developing film is the same as that of Example 1.

[0055] Example 3

[0056] 34.244g bisphenol A, 24.878g anhydrous potassium carbonate, 355.357g N,N-dimethylacetamide, 118.452g cyclohexane were placed in a 1000mL three-necked flask equipped with a mechanical stirrer and a water separator, and the atmosphere in the flask was replaced with argon and stirred at room temperature for 30 min. The oil bath was heated to 175℃, and refluxed with water for 3 h, during which water continued to reflux into the water separator. This was the deprotonation process. After the process was completed, all the remaining cyclohexane was evaporated, and the oil bath was cooled to room temperature. Then 28.466g hexafluorobenzene was added, the oil bath was heated to 80℃, and the mechanical stirring was 250 r / min. The reaction continued for 24 h. This was an aromatic nucleophilic substitution process. After the reaction was completed, the solution was poured into warm water to precipitate a strip-like crude product, which was purified 5 times in ethanol and ultrapure water and dried to obtain a white fluorinated polyarylether powder (number average molecular weight of 57,000 Da) containing 4 fluorine atoms in the structural unit.

[0057] The preparation process of the porous fiber developing tube and the fiber adhesion enhanced developing tube is the same as that of Example 1. The fiber adhesion enhanced developing tube is cut longitudinally to obtain a fiber adhesion enhanced developing film.

[0058] Example 4

[0059] The process of preparing fluorinated polyarylether powder is the same as that in Example 1.

[0060] Weigh 1.8 g of the obtained fluorinated polyarylether powder and a mixed solvent of acetone and N,N-dimethylformamide in a mass ratio of 1:3, mix them, ultrasonicate them at 140 W and 40 kHz for 1 h, pour the solution into a syringe, and prepare a porous fiber membrane through an electrospinning machine (model: Yunfan Technology YFSP-T). In the electrospinning process, a 21G metal needle is used, the electrospinning spacing is 9 cm, the spinning voltage is 20 KV, the temperature in the spinning machine is 30 ° C, the humidity is 30%, and the liquid feeding rate is 1.0 mL / h. After all the solution is exhausted, a fluorinated polyarylether porous fiber tube with a thickness of 0.2 mm is obtained. At this time, it is cut longitudinally to obtain a fluorinated polyarylether porous fiber membrane.

[0061] The fluorinated polyarylether porous fiber tube was cut into a tube with a radius of 0.6 cm and a length of 5 cm, fixed in the center of a 20 mL reagent bottle, and dichloromethane was added to the reagent bottle, which was quickly sealed with a bottle cap, and solvent vapor welding was performed for 0.5 h. The product was soaked in anhydrous ethanol for 10 min and then vacuum dried at 80 °C for 4 h to obtain a fiber adhesion-reinforced tube with a thickness of about 0.19 mm. The fiber adhesion-reinforced membrane was obtained by cutting it longitudinally.

[0062] Comparative Example 1

[0063] The process of preparing fluorinated polyarylether powder is the same as that in Example 1.

[0064] Dissolve 1.5 g of fluorinated polyarylether powder in 12 mL of cyclopentanone and stir under sealed magnetic stirring to fully dissolve to obtain a clear casting solution. Pour the casting solution onto a cleaned, dried and leveled glass plate (10×10 cm 2 ), and after it is leveled, it is dried at a gradient temperature (40°C, 60°C, 80°C, 100°C, 120°C) to obtain a fluorinated polyarylether casting film with a thickness of about 130 μm.

[0065] Comparative Example 2

[0066] The process of preparing fluorinated polyarylether powder is the same as that in Example 2.

[0067] Weigh 1.8 g of the obtained fluorinated polyarylether powder and a mixed solvent of acetone and N,N-dimethylformamide in a mass ratio of 1:3, mix them, and ultrasonicate them for 1 h at 140 W and 40 kHz to obtain a spinning solution. Pour the solution into a syringe and pass it through an electrospinning machine (model: Yunfan Technology YFSP-T) to prepare a porous fiber developing membrane. In the electrospinning process, a 21G metal needle was used, the electrospinning spacing was 9 cm, the spinning voltage was 20 KV, the temperature in the spinning machine was 30 °C, the humidity was 30%, and the liquid feeding rate was 1.0 mL / h. After all the solution was exhausted, a fluorinated polyarylether porous fiber tube with a thickness of 0.2 mm was obtained. At this time, it was cut longitudinally to obtain a fluorinated polyarylether porous fiber membrane.

[0068] The fiber adhesion enhanced developing film obtained in Example 1, the fluorinated polyarylether cast film obtained in Comparative Example 1, and the porous fiber membrane obtained in Comparative Example 2 were photographed by scanning electron microscope. Figure 3~Figure 5 As shown, Figure 3 This is a SEM image of the fiber adhesion enhanced developing film obtained in Example 1 of the present invention. Figure 4 This is a SEM image of the fluorinated polyarylether membrane material film obtained in Comparative Example 1 of the present invention. Figure 5 This is a SEM image of the porous fiber membrane obtained in Comparative Example 2 of the present invention.

[0069] The fiber adhesion enhanced developing films obtained in Example 1 and Example 4 were respectively photographed by computer tomography (CT). The results are as follows: Figure 6~Figure 7 As shown, Figure 6 This is a CT image of the fiber adhesion enhanced developing film obtained in Example 1 of the present invention, Figure 7 This is a CT image of the fiber adhesion enhanced membrane obtained in Example 4 of the present invention. Figure 6 and Figure 7 It can be seen that the fiber adhesion enhanced developing film obtained by combining the developing technology has a developing function.

[0070] The fiber adhesion enhanced developing film obtained in Example 1 was fluorescently stained and photographed. The results are as follows: Figure 8 As shown, Figure 8 This is a fluorescent staining photograph of the fiber adhesion enhanced developing film obtained in Example 1 of the present invention.

[0071] The fiber adhesion enhanced developing film obtained in Example 1 was used to grow L929 cells and photographed under a scanning electron microscope. The results are as follows: Fig. 9 As shown, Fig. 9 This is a SEM image of the growth state of mouse fibroblast L929 cells on the fiber adhesion enhanced developing film obtained in Example 1 of the present invention.

[0072] The film mechanical properties of the fiber adhesion enhanced developing films obtained in Examples 1 to 3, the fiber adhesion enhanced film obtained in Example 4, the fluorinated polyarylether film material film obtained in Comparative Example 1, and the fluorinated polyarylether porous fiber film obtained in Comparative Example 2 were tested, and the results are shown in Table 1:

[0073] Table 1

[0074]

[0075] The fiber adhesion enhanced developing films obtained in Examples 1 to 3, the fiber adhesion enhanced film obtained in Example 4, the fluorinated polyarylether membrane material film obtained in Comparative Example 1, and the fluorinated polyarylether porous fiber membrane obtained in Comparative Example 2 were tested for reducing substances of film water extracts, and the results are shown in Table 2:

[0076] Table 2

[0077]

[0078] The fiber adhesion enhanced developing films obtained in Examples 1 to 3, the fiber adhesion enhanced film obtained in Example 4, the fluorinated polyarylether membrane material film obtained in Comparative Example 1, and the fluorinated polyarylether porous fiber membrane obtained in Comparative Example 2 were tested for film cytotoxicity. A cell survival rate of ≥70% was considered to be low cytotoxic. The results are shown in Table 3:

[0079] Table 3

[0080]

[0081] The fiber adhesion enhanced developing films obtained in Examples 1 to 3, the fiber adhesion enhanced film obtained in Example 4, the fluorinated polyarylether membrane material film obtained in Comparative Example 1, and the fluorinated polyarylether porous fiber membrane obtained in Comparative Example 2 were tested for film hydrophilicity, and the results are shown in Table 4:

[0082] Table 4

[0083]

[0084] The fiber adhesion enhanced developing films obtained in Examples 1 to 3, the fiber adhesion enhanced film obtained in Example 4, the fluorinated polyarylether membrane material film obtained in Comparative Example 1, and the fluorinated polyarylether porous fiber membrane obtained in Comparative Example 2 were respectively subjected to bursting pressure tests, and the results are shown in Table 5:

[0085] Table 5

[0086]

[0087] The fiber adhesion enhanced developing films obtained in Examples 1 to 3, the fiber adhesion enhanced film obtained in Example 4, the fluorinated polyarylether membrane material film obtained in Comparative Example 1, and the fluorinated polyarylether porous fiber membrane obtained in Comparative Example 2 were tested for suture pulling strength, and the results are shown in Table 6:

[0088] Table 6

[0089]

[0090] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. An artificial blood vessel material, characterized in that: The artificial blood vessel material is obtained from fluorinated polyarylether; or, the artificial blood vessel material is obtained from fluorinated polyarylether and a developer; The fluorine-containing polyarylether is obtained from bisphenol monomers and fluorine-containing monomers; The bisphenol monomer is selected from one or more of biphenol, hydroquinone, bisphenol A, bisphenol AF and bisphenol S; The fluorine-containing monomer is selected from one or more of hexafluorobenzene, decafluorobiphenyl and decafluorobiphenyl ketone.

2. The artificial blood vessel material according to claim 1, characterized in that: The fluorinated polyarylether is obtained from a bisphenol monomer and a fluorinated monomer in a molar ratio of 1:(1-1.04).

3. The artificial blood vessel material according to claim 1, characterized in that: The number average molecular weight of the fluorinated polyarylether is 40000 Da to 70000 Da.

4. The artificial blood vessel material according to claim 1, characterized in that: The artificial blood vessel material is obtained from fluorine-containing polyarylether and a developer with a mass fraction of 15 wt% to 40 wt%.

5. The artificial blood vessel material according to claim 1, characterized in that: The developer is selected from one or more of barium sulfate, tungsten powder, bismuth oxide, bismuth subcarbonate and bismuth oxychloride.

6. The method for preparing an artificial blood vessel material according to any one of claims 1 to 5, characterized in that: The following steps are involved: The artificial blood vessel material is obtained by sequentially subjecting a fluorinated polyarylether solution to electrospinning and solvent vapor welding; or, sequentially subjecting a fluorinated polyarylether and developer solution to electrospinning and solvent vapor welding.

7. The method for preparing an artificial blood vessel material according to claim 6, characterized in that: The fluorinated polyarylether is prepared by the following steps: S1) heating the bisphenol monomer, the alkaline catalyst and the water-carrying agent in a solvent under reflux in a protective gas atmosphere; S2) reacting the material obtained in step S1) with a fluorine-containing monomer to obtain a fluorine-containing polyarylether.

8. The method for preparing an artificial blood vessel material according to claim 6, characterized in that: The solvent used in the solvent vapor welding is one or more of petroleum ether, dichloromethane, ethyl acetate, acetone and tetrahydrofuran.

9. The method for preparing an artificial blood vessel material according to claim 6, characterized in that: The solvent vapor welding time is 0.5 h~2 h.

10. An artificial vascular product, characterized in that: The artificial blood vessel material is obtained from the artificial blood vessel material described in any one of claims 1 to 6 or the artificial blood vessel material obtained by the preparation method described in any one of claims 7 to 9.

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