WO2020258945A1 - Medical tube preparation method and medical tube - Google Patents

Medical tube preparation method and medical tube Download PDF

Info

Publication number
WO2020258945A1
WO2020258945A1 PCT/CN2020/080771 CN2020080771W WO2020258945A1 WO 2020258945 A1 WO2020258945 A1 WO 2020258945A1 CN 2020080771 W CN2020080771 W CN 2020080771W WO 2020258945 A1 WO2020258945 A1 WO 2020258945A1
Authority
WO
WIPO (PCT)
Prior art keywords
core wire
preparing
coating agent
medical tube
coating
Prior art date
Application number
PCT/CN2020/080771
Other languages
French (fr)
Chinese (zh)
Inventor
秦明林
李兆敏
刘敏
赵涛
吴海杰
张新华
阙亦云
Original Assignee
脉通医疗科技(嘉兴)有限公司
创脉医疗科技(上海)有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 脉通医疗科技(嘉兴)有限公司, 创脉医疗科技(上海)有限公司 filed Critical 脉通医疗科技(嘉兴)有限公司
Publication of WO2020258945A1 publication Critical patent/WO2020258945A1/en

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04—Macromolecular materials
    • A61L31/048—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04—Macromolecular materials
    • A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/18—Materials at least partially X-ray or laser opaque

Definitions

  • the invention relates to the technical field of medical devices, in particular to a method for preparing a medical tube and a medical tube.
  • Minimally invasive interventional therapy is a technique in which instruments or drugs are inserted into diseased tissues with minimal trauma under the guidance of images to perform physical, mechanical or chemical treatments.
  • medical precision tubing is required for accurate, safe and effective transmission. Therefore, higher requirements are put forward for the comprehensive performance of precision tubing, including good biocompatibility and matching mechanical properties.
  • Polyimide has a rigid structure, closely arranged molecular chains, and strong interaction. When it is applied to medical precision tubing, the medical precision tubing has correspondingly better mechanical strength. However, the blood vessels in the human body are fine and complex. Therefore, medical precision tubing is not only required to have high maneuverability, but also needs good lubricity to reduce the frictional damage to the blood vessels during the introduction into the body and to push drugs or The resistance of the appliance. However, the existing medical precision tubing made of polyimide has a relatively large coefficient of friction, which does not meet the requirements of lubricity. At the same time, there are a large number of polar groups on the surface of the polyimide molecule, which makes it very easy to interact with the surface of the molding substrate in the process of manufacturing the pipe, which is not conducive to the separation of the two.
  • the purpose of the present invention is to provide a method for preparing a medical tube and a medical tube.
  • the surface of the medical tube has a low coefficient of friction and can reduce the friction during the process of introducing the tube into the body.
  • the present invention provides a method for preparing a medical tube, including providing a coating agent and a core wire, the coating agent includes a polyimide precursor solution and a solution dispersed in the polyimide precursor PTFE in body solution;
  • the coating agent further includes a contrast agent dispersed in the polyimide precursor solution.
  • the step of coating the coating agent on the outer surface of the core wire includes:
  • the core wire is immersed in the coating agent so that the coating agent is attached to the outer surface of the core wire.
  • the step of imidization treatment includes:
  • the second temperature is not lower than the first temperature.
  • the first temperature is 80°C to 300°C
  • the second temperature is 300°C to 420°C.
  • the step of providing a coating agent includes:
  • the modified polytetrafluoroethylene is dispersed in the polyimide precursor solution.
  • the step of using a surface modifier to modify the surface of polytetrafluoroethylene includes:
  • the suspension is dried to obtain particulate modified polytetrafluoroethylene.
  • the surface modifier includes at least one of an ionic surfactant, an amphoteric surfactant, and a silicone modifier.
  • the weight of the particulate modified polytetrafluoroethylene is 2%-50% of the total weight of the coating agent.
  • the weight of the surface modifier added to the polar solvent is 0.05%-0.2% of the total weight of the surface modifier and the polar solvent.
  • the polar solvent includes N,N-dimethylacetamide, trifluoroacetic acid, dimethylsulfoxide, acetonitrile, dimethylimide, hexamethylphosphoramide, methanol, ethanol, isopropanol At least one of pyridine, acetone, n-butanol and aniline.
  • the concentration of the polytetrafluoroethylene in the suspension is 5%-25%.
  • the preparation method of the medical tube further includes: preparing the polyimide precursor solution, and the reactant for preparing the polyimide precursor solution includes at least one aromatic dianhydride and at least one Kind of aromatic diamine.
  • the concentration of the polyimide precursor solution is 5%-30%, and the viscosity is 10-100 Pa ⁇ s.
  • the weight of the contrast agent dispersed in the polyimide precursor solution is 0.1% to 5% of the total weight of the coating agent.
  • the core wire is immersed in the coating agent, and after the coating agent is attached to the outer surface of the core wire, the coating agent is applied to the outer surface of the core wire.
  • the surface step further includes: passing the core wire through the inner cavity of the mold to adjust the amount of coating agent carried by the core wire.
  • the method before extracting the core wire, the method further includes: cutting the coating on the core wire according to a predetermined length.
  • the present invention also provides a medical tube prepared by the method for preparing a medical tube as described above.
  • the medical tube and the preparation method thereof of the present invention have the following advantages:
  • the medical tubing provided by the present invention includes a polyimide matrix and polytetrafluoroethylene dispersed in the polyimide matrix.
  • the use of polytetrafluoroethylene Ethylene modifies polyimide, reduces the friction coefficient of the pipe, and improves the lubricity of the pipe;
  • the medical tubing provided by the present invention also includes a contrast agent dispersed in the polyimide matrix.
  • the tubing is formed in one step by the dipping and pulling method. There is no need to separately process the contrast ring after the tubing is formed, which simplifies the processing of the medical tubing Steps to improve production efficiency.
  • Figure 1 is a partial cross-sectional view of a medical tube provided by an embodiment of the present invention, and only one layer of coating is shown in the figure;
  • the purpose of this embodiment is to provide a method for preparing a medical tube, which is used to prepare a medical tube with a small surface friction coefficient and good surface lubricity.
  • the preparation method of the medical tube provided in this embodiment includes:
  • S1 Provide coating agent and core wire
  • S2 coating the coating agent on the outer surface of the core wire and performing an imidization reaction to form at least one coating layer on the core wire;
  • the coating agent is mainly prepared from raw materials such as polytetrafluoroethylene, surface modifier, and polyimide precursor solution.
  • the polytetrafluoroethylene itself is chemically inert and has good lubricating properties. It can be uniformly dispersed in the polyimide precursor solution under the action of a surface modifier, and is accompanied by the polyimide The precursor solution is attached to the outer surface of the core wire together, and then undergoes an imidization reaction to form a coating. In this way, the polytetrafluoroethylene can be uniformly dispersed in the coating.
  • the medical tubing in this embodiment uses polyimide (PI) as the continuous phase matrix material and polytetrafluoroethylene (PTFE) as the dispersant to modify the surface of the polyimide material to ensure that the medical tubing Based on the mechanical strength, reduce the friction coefficient of medical tubing and improve its lubricity.
  • PI polyimide
  • PTFE polytetrafluoroethylene
  • the core wire is an elongated material used to form a substrate for subsequent coating.
  • the material of the core wire can be metal, plastic, etc. Different core wire materials have different surface energies, and the force between the coating layer formed in the subsequent steps is also different, thereby affecting the performance of the core pulling.
  • the core wire should have high temperature resistance characteristics to facilitate subsequent formation of a coating.
  • the coating agent is used to adhere to the core wire and form the coating in a subsequent step.
  • the coating agent can be prepared, for example, by the following method: first, dissolving the surface modifier in a polar solvent, and dispersing ultrasonically to obtain a modified solution; then, dissolving polytetrafluoroethylene in the modifying solution , Fully stir and disperse to obtain a suspension; then, dry the suspension to obtain modified polytetrafluoroethylene particles; finally, disperse the obtained modified polytetrafluoroethylene particles in the polyimide precursor in a high-speed disperser
  • the body solution is the coating agent.
  • the polar solvent includes N,N-dimethylacetamide, trifluoroacetic acid, dimethylsulfoxide, acetonitrile, dimethylimide, hexamethylphosphoramide, methanol, ethanol, isopropanol At least one of pyridine, acetone, n-butanol and aniline.
  • the surface modifier includes at least one of an ionic surfactant, an amphoteric surfactant, or a silicone modifier.
  • an ionic surfactant such as Dow JR400 surfactant, Dow QP-100 surfactant, silicone oil, etc.
  • the polytetrafluoroethylene can be commercially available low molecular weight type micropowder products, such as MP1100, MP1300, MP1600 or MP1400F produced and sold by Chemours.
  • the weight of the surface modifier added to the polar solvent is 0.05%-0.2% of the total weight of the surface modifier and the polar solvent, such as 0.05%, 0.08%, 0.1% , 0.13%, 0.15%, 0.18% or 0.2% etc.
  • the concentration of the polytetrafluoroethylene in the suspension is 5%-25%, such as 5%, 10%, 15%, 20% or 25%.
  • the weight of the modified polytetrafluoroethylene particles is 2%-50% of the total weight of the coating agent, such as 2%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% etc.
  • the method further includes preparing the polyimide precursor solution, and the reactant used for preparing the polyimide precursor solution includes at least one aromatic dianhydride, at least one aromatic two Amine and at least one polar solvent.
  • the aromatic dianhydride can be selected from 3,3,4',4'-diphenyl ether tetracarboxylic dianhydride, 3,3,4',4'-benzophenone tetracarboxylic dianhydride, 3 ,3,4',4'-biphenyltetracarboxylic dianhydride and at least one of pyromellitic dianhydride;
  • the aromatic diamine can be 4,4'-diaminodiphenyl ether, 4,4 At least one of'-diaminodiphenylmethane, bis(3-aminophenoxy)benzophenone, p-phenylenediamine, m-phenylenediamine and 4,4'-diamino
  • the concentration of the polyimide precursor solution may be 5%-30%, and the viscosity may be 10-100 Pa ⁇ s.
  • the polyimide precursor solution can be prepared using existing methods, such as the preparation method disclosed in the patent number CN105860074B.
  • Polytetrafluoroethylene is a non-polar material and the polyimide precursor is a polar molecule.
  • the surface modifier is used to The surface properties of the molecules are modified to increase the surface affinity of polytetrafluoroethylene, and the modified polytetrafluoroethylene molecules are dispersed in the polyimide precursor solution to realize polytetrafluoroethylene molecules It is fully mixed with the polar molecules in the polyimide precursor solution, so that the surface of the polyimide molecule can be modified when the polyimide precursor solution undergoes imidization reaction to obtain polyimide, To improve the surface lubricity of medical tubing.
  • the amount of each raw material of the coating agent can be adjusted to obtain medical tubing with different surface friction coefficients. That is, if you need to obtain medical tubing with a small surface friction coefficient, you can increase the amount of polytetrafluoroethylene. On the contrary, reduce the amount of polytetrafluoroethylene.
  • the amount of surface modifier depends on the amount of polytetrafluoroethylene and polyimide. Adjust the relative amount of amine precursor solution.
  • the surface modifier can also be added to the polyimide precursor solution to modify the surface of the polyimide precursor molecules, and then polytetrafluoroethylene is added. Thereby improving the compatibility of the two.
  • the raw materials used to prepare the coating agent may also include a developer, and the developer may be directly added to the polyimide precursor solution and mixed uniformly by stirring. Generally speaking, the developer is added after the modified polytetrafluoroethylene and the polyimide precursor solution are uniformly mixed.
  • the developer may be an existing conventional developer, such as barium sulfate, iodine preparation, tungsten powder, bismuth oxychloride, and the like.
  • the amount of developer added is determined according to actual needs. Generally, the more the amount of developer added, the better the development effect.
  • the weight of the developer added to the coating agent may be 0.1% to 5% of the total weight of the coating agent.
  • the method may further include: cleaning the core wire.
  • the specific method for cleaning the core wire may include: firstly passing the core wire through a first cleaning tank containing a cleaning agent, and using the cleaning agent to clean the core wire.
  • the cleaning agent can be an organic cleaning agent, specifically an ethanol solution, such as a 75% ethanol solution; then the core wire is passed through a second cleaning tank containing pure water for Rinse the core wire to remove the cleaning agent attached to the core wire; finally, blow dry the core wire.
  • only two cleaning tanks are provided as an example for description. In practice, three or more cleaning tanks may also be provided.
  • first cleaning tank and the second cleaning tank may also be provided with ultrasonic devices to perform ultrasonic cleaning on the core wire to improve the cleaning effect.
  • the two ends of the core wire can be respectively arranged on a pay-off reel and a take-up reel, and a certain amount can be applied to the released core wire through the pay-off reel and the take-up reel. Tension, so that the released core wire is in a taut state to facilitate the operation of subsequent steps.
  • the pay-off speed of the pay-off reel can also be controlled by the take-up reel to control the moving speed of the core wire in the first cleaning tank and the second cleaning tank, and in subsequent steps
  • the moving speed of the core wire in the coating agent may be 0.2 m/min-10 m/min, for example.
  • the specific method of forming the coating may include:
  • the core wire is introduced into a dipping tank containing the coating agent through a guide wheel, so that the core wire is immersed in the coating agent so that the coating agent can adhere to the coating agent.
  • the core wire can also be passed through the cavity of the mold to control the amount of liquid on the core wire (ie, the amount of liquid attached to the core wire The amount of the coating agent solution), which in turn can control the thickness of the subsequent monolayer coating. It should be understood that, for those skilled in the art, it is common knowledge to control the amount of liquid on the core wire through a mold, and therefore will not be described in detail here.
  • a mold with a matching size can be selected according to the thickness of the single-layer coating to be formed.
  • the solvent volatilizes during the subsequent processing of the coating to reduce the outer diameter of the formed coating and a suitable mold should be selected accordingly.
  • the coating agent on the core wire undergoes an imidization reaction to form the coating.
  • the heat treatment can be performed in an oven.
  • the imidization treatment may have a preliminary molding process and a final molding process. Specifically, the core wire carrying the coating agent is passed through the oven to heat the core wire with the coating agent attached at a first temperature to perform a preliminary molding process, so that the solvent in the coating agent is volatilized and polymerized.
  • the imide precursor undergoes an imidization reaction to obtain polyimide molecules with overlapping molecular chains. During this process, the solvent volatilizes and the polytetrafluoroethylene forms solid particles.
  • the core wire is subjected to a terminal forming process, that is, the core wire is heated in an oven at a second temperature, wherein the second temperature is not lower than the first temperature.
  • the core wire with the coating agent attached is subjected to a preliminary molding process, and then immersed in the coating agent again, and then a preliminary molding process is performed again to obtain the initial tube;
  • the initial stage tube is subjected to a terminal forming treatment in an oven to complete the imidization reaction.
  • the first temperature may be 80°C to 300°C
  • the second temperature may be 300°C to 420°C, that is, the second temperature is not lower than the first temperature.
  • the oven can be subjected to five-stage program-controlled heating at 80°C, 120°C, 150°C, 200°C, and 250°C; during the final forming process, the oven can be subjected to 300°C, 320°C , 350°C, 380°C, 400°C five-stage programmable heating.
  • the polyimide precursor continues to undergo imidization reaction to finally form polyimide, especially when the temperature in the oven is higher than the melting point of polytetrafluoroethylene, the granular polytetrafluoroethylene
  • the vinyl fluoride is melted by heat and penetrates into the molecular chain of the polyimide to actually bond with the polyimide to finally form the coating, so as to achieve the purpose of modifying and improving the lubricity of the medical tube surface.
  • the oven is programmed to increase temperature during the preliminary molding process.
  • five steps of program-controlled temperature increase of 120°C, 150°C, 200°C, 250°C, and 300°C are set during the preliminary forming process.
  • the oven can be set to 320°C, 350°C, 380°C, 400°C, 420°C for five-stage programmable heating during the terminal forming process.
  • the bonding between the coatings becomes more uniform and the wall thickness decreases.
  • the above process is for the formation process when the medical tube has two layers of coating.
  • the coating agent and the preliminary forming process can be repeated, and finally the final forming process can be performed.
  • the preliminary forming process and the terminal forming process can be completed in sequence when the core wire passes through the oven by setting the temperature of each section in the oven.
  • a second layer of coating agent can be applied, followed by imidization, and then reciprocating until the desired Number of layers.
  • the concentration of the polyimide precursor solution can also be adjusted to further control The thickness of the final monolayer coating.
  • the thickness of the formed coating is controlled, it is achieved by adjusting the concentration of the polyimide precursor solution in combination with the mold. Specifically, when the concentration of the polyimide precursor solution is lower, under the control of the same mold, the thickness of the obtained single layer coating is smaller; on the contrary, when the polyimide precursor solution When the concentration is higher, under the control of the same mold, the thickness of the obtained single-layer coating is also larger.
  • the concentration of the polyimide precursor solution can be increased to increase the thickness of the formed single layer coating; or, based on the same mold, the thickness of the polyimide precursor solution can be reduced. Concentration to reduce the thickness of the coating formed. In this way, for coatings with different thickness requirements, the same mold can be used directly, and the concentration of the polyimide precursor solution can be adjusted one by one, which is beneficial to reduce the number of molds used and save costs.
  • the method further includes: detecting the coating.
  • detecting the coating For example, detecting the surface friction coefficient and outer diameter (equivalent to detecting the thickness of the formed coating) of the coating.
  • the detection process is usually performed after forming a plurality of coating layers.
  • the core wire can be extracted to form a hollow medical tube.
  • the length of the core wire is much greater than the final required length of the medical tube. Therefore, after the coating is formed and before the core wire is pulled out, it also includes: aligning the core wire with a predetermined length The coating is cut. The cutting procedure is performed before the core wire is withdrawn. Because the core wire runs through the center of the medical tube, the cutting pressure during the cutting process can prevent the tube from being damaged.
  • PTFE is dispersed in pipes 1-5 under the action of the modifier, while PTFE is not dispersed in comparative pipes and pipe 6, and the friction coefficient of pipes 1-5 is higher.
  • the comparative tube and tube 6 are smaller, that is, the surface lubricity of the medical tube made of a layer including polytetrafluoroethylene dispersed in this embodiment is improved.
  • the breaking force and breaking elongation of the pipe 1-5 still meet the requirements of use.
  • composition of the polyimide precursor solution, the type and amount of surface modifier, and the type of contrast agent involved in Table 1 are all the same.
  • the number of coating layers in each pipe is also the same, specifically five layers.
  • all performance parameters are obtained by conventional testing methods.
  • the present invention also provides a medical tube prepared by the method.
  • Figure 1 is a schematic diagram of the structure of the medical tube, and only one layer of the coating is shown in the figure.
  • the medical tube includes at least one layer of the coating 10, and the coating 10 includes a polyimide substrate 11 and polytetrafluoroethylene 12 dispersed in the polyimide substrate 11 .
  • the coating layer 10 further includes a contrast agent 13 dispersed in the polyimide matrix 11.
  • the medical tube in this embodiment is a round tube, its inner diameter is not less than 0.1 mm. And, the wall thickness of the medical tube is not less than 0.012 mm.
  • the total thickness of the tube wall of the medical tube can be adjusted by adjusting the number of layers of the coating 10.
  • the coating layer 10 can be provided with one layer, two layers, three layers, or more layers, but due to the limitation of the application environment, the number of layers of the coating layer 10 generally does not exceed twenty layers.
  • the thickness of each layer of coating 10 may be the same or different.
  • the present invention improves the surface lubricity of medical tubing made of polyimide on the one hand, and can reduce the damage of the medical tubing to the blood vessels during the introduction into the human Friction damage and reduce the frictional resistance in the process of drug or appliance delivery, which is convenient for medical staff to operate and improve the efficiency of interventional treatment; on the other hand, under the action of PTFE, the surface energy of medical tubing is reduced, which is convenient for The molded base is separated to facilitate the production of the catheter.
  • the medical catheter has the effect of auto-imaging during the imaging process. There is no need to process the developing ring or the operator to push the developer; at the same time, the dipping and pulling molding is adopted. The method enables the medical catheter to be formed in one step, simplifies the manufacturing process of the medical catheter, and improves the convenience.

Landscapes

  • Health & Medical Sciences (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Surgery (AREA)
  • Vascular Medicine (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Media Introduction/Drainage Providing Device (AREA)
  • Materials For Medical Uses (AREA)

Abstract

A medical tube preparation method and a medical tube prepared using same. The preparation method comprises dispersing polytetrafluoroethylene in a polyimide precursor solution, and modifying the surface of polyimide by using the polytetrafluoroethylene. On the one hand, the friction coefficient of the polyimide material is lowered, and the surface lubricity of the medical tube is improved, thereby reducing the surface resistance of the medical tube, decreasing the possibility of damage to human blood vessels during the process of introducing the medical tube into a human body, and facilitating the push of drugs or instruments into the human body; on the other hand, the difficulty in separation due to the action of the tube and a forming base during tube forming is also avoided.

Description

一种医疗管材的制备方法及医疗管材Preparation method of medical tube and medical tube 技术领域Technical field
本发明涉及医疗器械技术领域，具体涉及一种医疗管材的制备方法及医疗管材。The invention relates to the technical field of medical devices, in particular to a method for preparing a medical tube and a medical tube.
背景技术Background technique
微创伤介入治疗是在影像引导下，以最小的创伤将器具或药物置入到病变组织，以对其进行物理、机械或化学治疗的技术。微创伤介入治疗中，需要借助医用精密管材进行精准安全有效的传输，因而对精密管材的综合性能提出了较高的要求，包括具有较好的生物相容性、匹配的机械性能等。Minimally invasive interventional therapy is a technique in which instruments or drugs are inserted into diseased tissues with minimal trauma under the guidance of images to perform physical, mechanical or chemical treatments. In minimally traumatic interventional therapy, medical precision tubing is required for accurate, safe and effective transmission. Therefore, higher requirements are put forward for the comprehensive performance of precision tubing, including good biocompatibility and matching mechanical properties.
聚酰亚胺由于具有刚性结构，分子链排列紧密，相互作用较强，在将其应用于医用精密管材中时，使医用精密管材相应地具有较好的机械强度。但是，人体内的血管细微且复杂，因此对于医用精密管材不仅要求具有较高的可操作性，还需要良好的润滑性，以降低其在导入体内的过程中对血管的摩擦损伤以及推送药物或器具时的阻力。然而现有的聚酰亚胺材质的医用精密管材的摩擦系数较大，其并不满足润滑性的要求。同时，聚酰亚胺分子表面存在大量的极性基团，使得其在制造管材的过程中极易与成型基底的表面相互作用而不利于两者的分离。Polyimide has a rigid structure, closely arranged molecular chains, and strong interaction. When it is applied to medical precision tubing, the medical precision tubing has correspondingly better mechanical strength. However, the blood vessels in the human body are fine and complex. Therefore, medical precision tubing is not only required to have high maneuverability, but also needs good lubricity to reduce the frictional damage to the blood vessels during the introduction into the body and to push drugs or The resistance of the appliance. However, the existing medical precision tubing made of polyimide has a relatively large coefficient of friction, which does not meet the requirements of lubricity. At the same time, there are a large number of polar groups on the surface of the polyimide molecule, which makes it very easy to interact with the surface of the molding substrate in the process of manufacturing the pipe, which is not conducive to the separation of the two.
发明内容Summary of the invention
本发明的目的在于提供一种医疗管材的制备方法及医疗管材，该医疗管材的表面具有较低的摩擦系数，可降低管材导入体内过程中的摩擦力。The purpose of the present invention is to provide a method for preparing a medical tube and a medical tube. The surface of the medical tube has a low coefficient of friction and can reduce the friction during the process of introducing the tube into the body.
为实现上述目的，本发明提供的了一种医疗管材的制备方法，包括提供涂覆剂和芯线，所述涂覆剂包括聚酰亚胺前驱体溶液和分散于所述聚酰亚胺前驱体溶液中的聚四氟乙烯；In order to achieve the above objective, the present invention provides a method for preparing a medical tube, including providing a coating agent and a core wire, the coating agent includes a polyimide precursor solution and a solution dispersed in the polyimide precursor PTFE in body solution;
将所述涂覆剂涂覆于所述芯线的外表面并进行亚胺化处理，以在所述芯线上形成至少一层涂层；以及，Applying the coating agent on the outer surface of the core wire and performing an imidization treatment to form at least one coating layer on the core wire; and,
抽离所述芯线，得到所述医疗管材。Extract the core wire to obtain the medical tube.
可选地，所述涂覆剂还包括分散于所述聚酰亚胺前驱体溶液中的造影剂。Optionally, the coating agent further includes a contrast agent dispersed in the polyimide precursor solution.
可选地，将所述涂覆剂涂覆于所述芯线的外表面的步骤包括：Optionally, the step of coating the coating agent on the outer surface of the core wire includes:
将所述芯线浸渍于所述涂覆剂中，使所述涂覆剂附着于所述芯线的外表面。The core wire is immersed in the coating agent so that the coating agent is attached to the outer surface of the core wire.
可选地，所述亚胺化处理的步骤包括：Optionally, the step of imidization treatment includes:
在第一温度下，对涂覆有所述涂覆剂的所述芯线进行热处理；以及，Heat-treating the core wire coated with the coating agent at the first temperature; and,
在第二温度下，对涂覆有所述涂覆剂的所述芯线进行热处理；At a second temperature, heat treating the core wire coated with the coating agent;
其中，所述第二温度不低于所述第一温度。Wherein, the second temperature is not lower than the first temperature.
可选地，所述第一温度为80℃～300℃，所述第二温度为300℃～420℃。Optionally, the first temperature is 80°C to 300°C, and the second temperature is 300°C to 420°C.
可选地，提供涂覆剂的步骤包括：Optionally, the step of providing a coating agent includes:
使用表面改性剂对聚四氟乙烯进行表面改性；Use surface modifiers to modify the surface of PTFE;
将改性的所述聚四氟乙烯分散于所述聚酰亚胺前驱体溶液中。The modified polytetrafluoroethylene is dispersed in the polyimide precursor solution.
可选地，使用表面改性剂对聚四氟乙烯进行表面改性的步骤包括：Optionally, the step of using a surface modifier to modify the surface of polytetrafluoroethylene includes:
提供极性溶剂；Provide polar solvent;
将所述表面改性剂和所述聚四氟乙烯加入所述极性溶剂中，混合均匀后得到悬浮液；Adding the surface modifier and the polytetrafluoroethylene to the polar solvent and mixing uniformly to obtain a suspension;
干燥所述悬浮液，得到颗粒状的改性的聚四氟乙烯。The suspension is dried to obtain particulate modified polytetrafluoroethylene.
可选地，所述表面改性剂包括离子型表面活性剂、两性表面活性剂和硅氧烷类改性剂中的至少一种。Optionally, the surface modifier includes at least one of an ionic surfactant, an amphoteric surfactant, and a silicone modifier.
可选地，所述颗粒状的改性的聚四氟乙烯的重量为所述涂覆剂总重量的2％-50％。Optionally, the weight of the particulate modified polytetrafluoroethylene is 2%-50% of the total weight of the coating agent.
可选地，加入所述极性溶剂中的所述表面改性剂的重量为所述表面改性剂和所述极性溶剂总重量的0.05％-0.2％。Optionally, the weight of the surface modifier added to the polar solvent is 0.05%-0.2% of the total weight of the surface modifier and the polar solvent.
可选地，所述极性溶剂包括N，N-二甲基乙酰胺、三氟乙酸、二甲亚砜、乙腈、二甲基亚酰胺、六甲基磷酰胺、甲醇、乙醇、异丙醇、吡啶、丙酮、正丁醇和苯胺中的至少一种。Optionally, the polar solvent includes N,N-dimethylacetamide, trifluoroacetic acid, dimethylsulfoxide, acetonitrile, dimethylimide, hexamethylphosphoramide, methanol, ethanol, isopropanol At least one of pyridine, acetone, n-butanol and aniline.
可选地，所述悬浮液中的所述聚四氟乙烯的浓度为5％-25％。Optionally, the concentration of the polytetrafluoroethylene in the suspension is 5%-25%.
可选地，所述医疗管材的制备方法还包括：制备所述聚酰亚胺前驱体溶 液，用于制备所述聚酰亚胺前驱体溶液的反应物包括至少一种芳香二酐和至少一种芳香二胺。Optionally, the preparation method of the medical tube further includes: preparing the polyimide precursor solution, and the reactant for preparing the polyimide precursor solution includes at least one aromatic dianhydride and at least one Kind of aromatic diamine.
可选地，所述聚酰亚胺前驱体溶液的浓度为5％-30％，粘度为10-100Pa·s。Optionally, the concentration of the polyimide precursor solution is 5%-30%, and the viscosity is 10-100 Pa·s.
可选地，分散于所述聚酰亚胺前驱体溶液中的所述造影剂的重量为所述涂覆剂总重量的0.1％-5％。Optionally, the weight of the contrast agent dispersed in the polyimide precursor solution is 0.1% to 5% of the total weight of the coating agent.
可选地，将所述芯线浸渍于所述涂覆剂中，使所述涂覆剂附着于所述芯线的外表面之后，将所述涂覆剂涂覆于所述芯线的外表面的步骤还包括：使所述芯线穿过模具的内腔，以调控所述芯线携带的涂覆剂的量。Optionally, the core wire is immersed in the coating agent, and after the coating agent is attached to the outer surface of the core wire, the coating agent is applied to the outer surface of the core wire. The surface step further includes: passing the core wire through the inner cavity of the mold to adjust the amount of coating agent carried by the core wire.
可选地，在抽离所述芯线之前，还包括：按照预定长度对所述芯线上的涂层进行切割。Optionally, before extracting the core wire, the method further includes: cutting the coating on the core wire according to a predetermined length.
此外，为实现上述目的，本发明还提供了采用如前所述的医疗管材的制备方法制备而成的医疗管材。In addition, in order to achieve the above object, the present invention also provides a medical tube prepared by the method for preparing a medical tube as described above.
与现有技术相比，本发明的医疗管材及其制备方法具有如下优点：Compared with the prior art, the medical tube and the preparation method thereof of the present invention have the following advantages:
第一、本发明提供的医疗管材包括聚酰亚胺基体和分散于所述聚酰亚胺基体内的聚四氟乙烯，在保证医疗管材具备所需的机械强度的基础上，利用聚四氟乙烯对聚酰亚胺进行改性，降低管材的摩擦系数，提高管材的润滑性；First, the medical tubing provided by the present invention includes a polyimide matrix and polytetrafluoroethylene dispersed in the polyimide matrix. On the basis of ensuring that the medical tubing has the required mechanical strength, the use of polytetrafluoroethylene Ethylene modifies polyimide, reduces the friction coefficient of the pipe, and improves the lubricity of the pipe;
第二、本发明提供的医疗管材中还包括分散在聚酰亚胺基体内的造影剂，通过浸渍提拉法使管材一步成型，无需在管材成型后单独加工造影环，简化了医疗管材的加工步骤，提高了生产效率。Second, the medical tubing provided by the present invention also includes a contrast agent dispersed in the polyimide matrix. The tubing is formed in one step by the dipping and pulling method. There is no need to separately process the contrast ring after the tubing is formed, which simplifies the processing of the medical tubing Steps to improve production efficiency.
附图说明Description of the drawings
图1是本发明根据一实施例所提供的医疗管材的局部剖视图，图中仅示出一层涂层；Figure 1 is a partial cross-sectional view of a medical tube provided by an embodiment of the present invention, and only one layer of coating is shown in the figure;
图中：In the picture:
10-涂层；10- Coating;
11-聚酰亚胺基体，12-聚四氟乙烯，13-造影剂。11-polyimide matrix, 12-polytetrafluoroethylene, 13-contrast agent.
具体实施方式Detailed ways
为使本发明的目的、优点和特征更加清楚，以下结合附图对本发明提出的医疗管材及其制备方法的实施例作进一步详细说明。需说明的是，附图均采用非常简化的形式且均使用非精准的比例，仅用以方便、明晰地辅助说明本发明实施例的目的。In order to make the purpose, advantages and features of the present invention clearer, embodiments of the medical tube and its preparation method proposed by the present invention will be further described in detail below with reference to the accompanying drawings. It should be noted that the drawings are in a very simplified form and all use imprecise proportions, which are only used to conveniently and clearly assist in explaining the purpose of the embodiments of the present invention.
本实施例的目的在于提供一种医疗管材的制备方法，用于制备表面摩擦系数小，具有较好表面润滑性的医疗管材。本实施例提供的医疗管材的制备方法包括：The purpose of this embodiment is to provide a method for preparing a medical tube, which is used to prepare a medical tube with a small surface friction coefficient and good surface lubricity. The preparation method of the medical tube provided in this embodiment includes:
S1：提供涂覆剂和芯线；S1: Provide coating agent and core wire;
S2：将所述涂覆剂涂覆于所述芯线的外表面并进行亚胺化反应，以在所述芯线上形成至少一层涂层；S2: coating the coating agent on the outer surface of the core wire and performing an imidization reaction to form at least one coating layer on the core wire;
S3：抽离所述芯线，得到中空结构的医疗管材。其中，所述涂覆剂主要由聚四氟乙烯、表面改性剂、聚酰亚胺前驱体溶液等原料制备而成。S3: Pull out the core wire to obtain a medical tube with a hollow structure. Wherein, the coating agent is mainly prepared from raw materials such as polytetrafluoroethylene, surface modifier, and polyimide precursor solution.
所述聚四氟乙烯自身具有化学惰性以及较好的润滑性能，其能够在表面改性剂的作用下，均匀分散于所述聚酰亚胺前驱体溶液中，并随所述聚酰亚胺前驱体溶液一起附着于所述芯线的外表面，之后经亚胺化反应形成涂层。如此，所述聚四氟乙烯即可均匀分散于所述涂层中。The polytetrafluoroethylene itself is chemically inert and has good lubricating properties. It can be uniformly dispersed in the polyimide precursor solution under the action of a surface modifier, and is accompanied by the polyimide The precursor solution is attached to the outer surface of the core wire together, and then undergoes an imidization reaction to form a coating. In this way, the polytetrafluoroethylene can be uniformly dispersed in the coating.
即，本实施例中的医疗管材采用聚酰亚胺(PI)作为连续相基体材料，以聚四氟乙烯(PTFE)作为分散剂，相对聚酰亚胺材料的表面进行修饰，在保证医疗管材的机械强度的基础上，降低医疗管材的摩擦系数，提高其润滑性。That is, the medical tubing in this embodiment uses polyimide (PI) as the continuous phase matrix material and polytetrafluoroethylene (PTFE) as the dispersant to modify the surface of the polyimide material to ensure that the medical tubing Based on the mechanical strength, reduce the friction coefficient of medical tubing and improve its lubricity.
下面以具有两层涂层的医疗管材为例详细介绍所述医疗管材的制备方法，但不应以此作为对本发明的限制。The following takes a medical tube with two layers of coating as an example to introduce the preparation method of the medical tube in detail, but this should not be used as a limitation to the present invention.
首先，提供芯线和涂覆剂。First, provide the core wire and coating agent.
其中，所述芯线为细长的材料，用于构成后续形成涂层的基底。所述芯线的材质可为金属、塑料等，不同的芯线材料具有不同的表面能，与后续步骤形成的涂层间的作用力也不相同，从而影响到抽芯的性能。另外，所述芯线应具有耐高温的特性，以便于后续形成涂层。Wherein, the core wire is an elongated material used to form a substrate for subsequent coating. The material of the core wire can be metal, plastic, etc. Different core wire materials have different surface energies, and the force between the coating layer formed in the subsequent steps is also different, thereby affecting the performance of the core pulling. In addition, the core wire should have high temperature resistance characteristics to facilitate subsequent formation of a coating.
以及，所述涂覆剂用于在后续步骤中附着于所述芯线上并形成所述涂层。所述涂覆剂例如可通过以下方法制备：首先，将表面改性剂溶解于极性溶剂 中，经超声分散后得到改性溶液；之后，将聚四氟乙烯溶解于所述改性溶液中，充分搅拌分散得到悬浮液；然后，干燥所述悬浮液得到改性的聚四氟乙烯颗粒；最后，在高速分散机中将所得的改性的聚四氟乙烯颗粒分散于聚酰亚胺前驱体溶液即得所述涂覆剂。And, the coating agent is used to adhere to the core wire and form the coating in a subsequent step. The coating agent can be prepared, for example, by the following method: first, dissolving the surface modifier in a polar solvent, and dispersing ultrasonically to obtain a modified solution; then, dissolving polytetrafluoroethylene in the modifying solution , Fully stir and disperse to obtain a suspension; then, dry the suspension to obtain modified polytetrafluoroethylene particles; finally, disperse the obtained modified polytetrafluoroethylene particles in the polyimide precursor in a high-speed disperser The body solution is the coating agent.
具体而言，所述极性溶剂包括N，N-二甲基乙酰胺、三氟乙酸、二甲亚砜、乙腈、二甲基亚酰胺、六甲基磷酰胺、甲醇、乙醇、异丙醇、吡啶、丙酮、正丁醇和苯胺中的至少一种。Specifically, the polar solvent includes N,N-dimethylacetamide, trifluoroacetic acid, dimethylsulfoxide, acetonitrile, dimethylimide, hexamethylphosphoramide, methanol, ethanol, isopropanol At least one of pyridine, acetone, n-butanol and aniline.
所述表面改性剂包括离子型表面活性剂、两性表面活性剂或硅氧烷类改性剂中的至少一种。实践中，所述的表面改性剂可采用各类市售的离子型表面活性剂、两性表面活性剂、硅氧烷类表面活性剂等。具体可选的品种有陶氏JR400表面活性剂、陶氏QP-100表面活性剂、有机硅油等。The surface modifier includes at least one of an ionic surfactant, an amphoteric surfactant, or a silicone modifier. In practice, various commercially available ionic surfactants, amphoteric surfactants, silicone surfactants, etc. can be used as the surface modifier. Specific options include Dow JR400 surfactant, Dow QP-100 surfactant, silicone oil, etc.
所述聚四氟乙烯可采用市售的低分子量类型的微粉产品，例如科慕公司生产销售的MP1100、MP1300、MP1600或MP1400F等。The polytetrafluoroethylene can be commercially available low molecular weight type micropowder products, such as MP1100, MP1300, MP1600 or MP1400F produced and sold by Chemours.
以及，添加到所述极性溶剂中的所述表面改性剂的重量为所述表面改性剂和所述极性溶剂总重量的0.05％-0.2％，例如0.05％、0.08％、0.1％、0.13％、0.15％、0.18％或0.2％等。所述悬浮液中的所述聚四氟乙烯的浓度为5％-25％，例如5％、10％、15％、20％或25％等。所述涂覆剂中，所述改性的聚四氟乙烯颗粒的重量为所述涂覆剂总重量的2％-50％，例如2％、5％、8％、10％、15％、20％、25％、30％、35％、40％、45％或50％等。And, the weight of the surface modifier added to the polar solvent is 0.05%-0.2% of the total weight of the surface modifier and the polar solvent, such as 0.05%, 0.08%, 0.1% , 0.13%, 0.15%, 0.18% or 0.2% etc. The concentration of the polytetrafluoroethylene in the suspension is 5%-25%, such as 5%, 10%, 15%, 20% or 25%. In the coating agent, the weight of the modified polytetrafluoroethylene particles is 2%-50% of the total weight of the coating agent, such as 2%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% etc.
进一步地，在制备涂覆剂前还包括制备所述聚酰亚胺前驱体溶液，用于制备所述聚酰亚胺前驱体溶液的反应物包括至少一种芳香二酐、至少一种芳香二胺和至少一种极性溶剂。例如，所述芳香二酐可选自3,3,4’，4’-二苯醚四羧酸二酐、3,3,4’，4’-二苯甲酮四羧酸二酐、3,3,4’，4’-联苯四羧酸二酐和均苯四甲酸二酐中的至少一种；所述芳香二胺可为4，4’-二氨基二苯醚、4，4’-二氨基二苯甲烷、二(3-氨基苯氧基)二苯甲酮、对苯二胺、间苯二胺和4，4’-二氨基二苯砜中的至少一种；所述极性有机溶剂可为N，N-二甲基乙酰胺、三氟乙酸、二甲亚砜、乙腈、二甲基亚酰胺、六甲基磷酰胺、甲醇、乙醇、异丙醇、吡啶、丙酮、正丁醇和苯胺中的至少一种。更详细地，所述聚酰亚 胺前驱体溶液的浓度可为5％-30％，粘度为10-100Pa·s。聚酰亚胺前驱体溶液可采用现有方法进行制备，例如专利号为CN105860074B的专利中所公开的制备方法。Further, before preparing the coating agent, the method further includes preparing the polyimide precursor solution, and the reactant used for preparing the polyimide precursor solution includes at least one aromatic dianhydride, at least one aromatic two Amine and at least one polar solvent. For example, the aromatic dianhydride can be selected from 3,3,4',4'-diphenyl ether tetracarboxylic dianhydride, 3,3,4',4'-benzophenone tetracarboxylic dianhydride, 3 ,3,4',4'-biphenyltetracarboxylic dianhydride and at least one of pyromellitic dianhydride; the aromatic diamine can be 4,4'-diaminodiphenyl ether, 4,4 At least one of'-diaminodiphenylmethane, bis(3-aminophenoxy)benzophenone, p-phenylenediamine, m-phenylenediamine and 4,4'-diaminodiphenylsulfone; The polar organic solvent can be N,N-dimethylacetamide, trifluoroacetic acid, dimethylsulfoxide, acetonitrile, dimethylimide, hexamethylphosphoramide, methanol, ethanol, isopropanol, pyridine, acetone , At least one of n-butanol and aniline. In more detail, the concentration of the polyimide precursor solution may be 5%-30%, and the viscosity may be 10-100 Pa·s. The polyimide precursor solution can be prepared using existing methods, such as the preparation method disclosed in the patent number CN105860074B.
聚四氟乙烯为非极性材料而聚酰亚胺前驱体为极性分子，为将聚四氟乙烯均匀分散于聚酰亚胺前驱体溶液中，首先通过表面改性剂对聚四氟乙烯分子的表面性质进行改性以提高聚四氟乙烯的表面亲和性，再将改性后的聚四氟乙烯分子分散于所述聚酰亚胺前驱体溶液中，以实现聚四氟乙烯分子与聚酰亚胺前驱体溶液中的极性分子充分混合，从而可在聚酰亚胺前驱体溶液进行亚胺化反应得到聚酰亚胺时对所述聚酰亚胺分子的表面进行修饰，以改善医疗管材的表面润滑性。具体地，可通过对涂覆剂各原料的用量进行调整，以获得具有不同表面摩擦系数的医疗管材。即，若需要获得表面摩擦系数较小的医疗管材，可增加聚四氟乙烯的用量，反之，则减少聚四氟乙烯的用量，而表面改性剂的用量根据聚四氟乙烯和聚酰亚胺前驱体溶液的相对量来调整。Polytetrafluoroethylene is a non-polar material and the polyimide precursor is a polar molecule. In order to uniformly disperse the polytetrafluoroethylene in the polyimide precursor solution, the surface modifier is used to The surface properties of the molecules are modified to increase the surface affinity of polytetrafluoroethylene, and the modified polytetrafluoroethylene molecules are dispersed in the polyimide precursor solution to realize polytetrafluoroethylene molecules It is fully mixed with the polar molecules in the polyimide precursor solution, so that the surface of the polyimide molecule can be modified when the polyimide precursor solution undergoes imidization reaction to obtain polyimide, To improve the surface lubricity of medical tubing. Specifically, the amount of each raw material of the coating agent can be adjusted to obtain medical tubing with different surface friction coefficients. That is, if you need to obtain medical tubing with a small surface friction coefficient, you can increase the amount of polytetrafluoroethylene. On the contrary, reduce the amount of polytetrafluoroethylene. The amount of surface modifier depends on the amount of polytetrafluoroethylene and polyimide. Adjust the relative amount of amine precursor solution.
当然，在其他实施例中，也可以先将所述表面改性剂添加到聚酰亚胺前驱体溶液中以对聚酰亚胺前驱体分子进行表面改性，然后再添加聚四氟乙烯，从而改善两者的相容性。Of course, in other embodiments, the surface modifier can also be added to the polyimide precursor solution to modify the surface of the polyimide precursor molecules, and then polytetrafluoroethylene is added. Thereby improving the compatibility of the two.
另外，用于制备所述涂覆剂的原料还可以包括显影剂，所述显影剂可直接加入所述聚酰亚胺前驱体溶液，经搅拌混合均匀即可。一般而言，显影剂在改性的聚四氟乙烯与聚酰亚胺前驱体溶液混合均匀后加入。通过在涂覆剂中添加显影剂，以制得自身具有良好显影效果的医疗管材，无需在后续使用时额外加工显影环。所述显影剂可为现有常规显影剂，例如硫酸钡、碘制剂、钨粉、氯氧化铋等。以及，显影剂的加入量根据实际需要确定，通常，显影剂的加入量越多，显影效果越好。实践中，加入到所述涂覆剂中的显影剂的重量可为所述涂覆剂总重量的0.1％-5％。In addition, the raw materials used to prepare the coating agent may also include a developer, and the developer may be directly added to the polyimide precursor solution and mixed uniformly by stirring. Generally speaking, the developer is added after the modified polytetrafluoroethylene and the polyimide precursor solution are uniformly mixed. By adding a developer to the coating agent, a medical tube with a good development effect can be prepared without additional processing of the development ring during subsequent use. The developer may be an existing conventional developer, such as barium sulfate, iodine preparation, tungsten powder, bismuth oxychloride, and the like. And, the amount of developer added is determined according to actual needs. Generally, the more the amount of developer added, the better the development effect. In practice, the weight of the developer added to the coating agent may be 0.1% to 5% of the total weight of the coating agent.
较佳地，在所述芯线上涂覆所述涂覆剂前还可包括：清洗所述芯线。Preferably, before applying the coating agent on the core wire, the method may further include: cleaning the core wire.
清洗所述芯线的具体方法可包括：首先使所述芯线经过一第一清洗槽，所述第一清洗槽内容纳有清洗剂，利用所述清洗剂对所述芯线进行清洗。所 述清洗剂可为有机清洗剂，具体可为乙醇溶液，例如75％的乙醇溶液；然后使所述芯线经过一第二清洗槽，所述第二清洗槽内容纳有纯水，用于对所述芯线进行漂洗，以去除所述芯线上附着的清洗剂；最后吹干所述芯线。本实施例中仅以设置两个清洗槽为例进行说明，实践中还可以设置三个或更多个清洗槽。The specific method for cleaning the core wire may include: firstly passing the core wire through a first cleaning tank containing a cleaning agent, and using the cleaning agent to clean the core wire. The cleaning agent can be an organic cleaning agent, specifically an ethanol solution, such as a 75% ethanol solution; then the core wire is passed through a second cleaning tank containing pure water for Rinse the core wire to remove the cleaning agent attached to the core wire; finally, blow dry the core wire. In this embodiment, only two cleaning tanks are provided as an example for description. In practice, three or more cleaning tanks may also be provided.
进一步地，所述第一清洗槽和所述第二清洗槽内还可设置超声装置，以对所述芯线进行超声清洗，提高清洗效果。Furthermore, the first cleaning tank and the second cleaning tank may also be provided with ultrasonic devices to perform ultrasonic cleaning on the core wire to improve the cleaning effect.
详细来说，所述芯线的两端可分别设置在一放线卷轴和一收线卷轴上，并且还可通过所述放线卷轴和所述收线卷轴对释放出的芯线施加一定的张力，使释放出的芯线呈绷紧状态，以便于后续步骤的操作。以及还可通过所述收线卷轴控制所述放线卷轴的放线速率，以控制所述芯线在所述第一清洗槽和所述第二清洗槽中的移动速度，以及在后续步骤中所述芯线在涂覆剂中的移动速度。其中，所述芯线的移动速率例如可为0.2m/min-10m/min。In detail, the two ends of the core wire can be respectively arranged on a pay-off reel and a take-up reel, and a certain amount can be applied to the released core wire through the pay-off reel and the take-up reel. Tension, so that the released core wire is in a taut state to facilitate the operation of subsequent steps. And the pay-off speed of the pay-off reel can also be controlled by the take-up reel to control the moving speed of the core wire in the first cleaning tank and the second cleaning tank, and in subsequent steps The moving speed of the core wire in the coating agent. Wherein, the moving speed of the core wire may be 0.2 m/min-10 m/min, for example.
接着，在所述芯线上形成涂层。形成所述涂层的具体方法可包括：Next, a coating is formed on the core wire. The specific method of forming the coating may include:
首先，通过一导向轮将所述芯线引入一容纳有所述涂覆剂的浸渍槽中，以使所述芯线浸渍于所述涂覆剂中，从而所述涂覆剂可附着于所述芯线的外表面；之后，所述涂覆剂可在所述芯线外表面形成所述涂层。First, the core wire is introduced into a dipping tank containing the coating agent through a guide wheel, so that the core wire is immersed in the coating agent so that the coating agent can adhere to the coating agent. The outer surface of the core wire; afterwards, the coating agent may form the coating on the outer surface of the core wire.
可选地，所述芯线在经过所述涂覆剂后，还可使所述芯线穿过模具的内腔，以控制所述芯线上的带液量(即，芯线上附着的涂覆剂的溶液量)，进而可控制后续形成的单层涂层的厚度。应知晓，对于本领域技术人员而言，通过模具控制芯线上的带液量为公知常识，因而此处不作详细介绍。Optionally, after the core wire passes the coating agent, the core wire can also be passed through the cavity of the mold to control the amount of liquid on the core wire (ie, the amount of liquid attached to the core wire The amount of the coating agent solution), which in turn can control the thickness of the subsequent monolayer coating. It should be understood that, for those skilled in the art, it is common knowledge to control the amount of liquid on the core wire through a mold, and therefore will not be described in detail here.
另外，应当认识到的是，可以根据需要形成的单层涂层的厚度，对应选取尺寸匹配的模具。在具体的实施例中，还应考虑到涂层在后续的处理过程中，存在溶剂挥发从而使得所形成的涂层的***直径缩减的情况，并据此选择合适的模具。In addition, it should be realized that a mold with a matching size can be selected according to the thickness of the single-layer coating to be formed. In a specific embodiment, it should also be considered that the solvent volatilizes during the subsequent processing of the coating to reduce the outer diameter of the formed coating, and a suitable mold should be selected accordingly.
然后，对所述芯线上的涂覆剂进行热处理，以使所述涂覆剂发生亚胺化反应进而形成所述涂层。所述热处理可在一烘箱中进行。进一步地，所述亚胺化处理可具有一初步成型过程和一终端成型过程。具体地，使携带有涂覆 剂的芯线经过所述烘箱在第一温度下对附着有涂覆剂的芯线加热以进行初步成型处理，使所述涂覆剂中的溶剂挥发，同时聚酰亚胺前驱体发生亚胺化反应，得到分子链交叠缠绕的聚酰亚胺分子，此过程中因溶剂挥发，聚四氟乙烯形成固体颗粒。然后对所述芯线进行终端成型处理，即在烘箱中采用第二温度对芯线进行加热处理，其中，所述第二温度不低于所述第一温度。Then, heat treatment is performed on the coating agent on the core wire, so that the coating agent undergoes an imidization reaction to form the coating. The heat treatment can be performed in an oven. Further, the imidization treatment may have a preliminary molding process and a final molding process. Specifically, the core wire carrying the coating agent is passed through the oven to heat the core wire with the coating agent attached at a first temperature to perform a preliminary molding process, so that the solvent in the coating agent is volatilized and polymerized. The imide precursor undergoes an imidization reaction to obtain polyimide molecules with overlapping molecular chains. During this process, the solvent volatilizes and the polytetrafluoroethylene forms solid particles. Then the core wire is subjected to a terminal forming process, that is, the core wire is heated in an oven at a second temperature, wherein the second temperature is not lower than the first temperature.
具体地，在本实施例中，将所述附着有涂覆剂的芯线经初步成型处理后，再次浸渍于所述涂覆剂中，然后再进行一次初步成型处理，以得到初期管材；最后在烘箱中对所述初期管材进行终端成型处理完成亚胺化反应。Specifically, in this embodiment, the core wire with the coating agent attached is subjected to a preliminary molding process, and then immersed in the coating agent again, and then a preliminary molding process is performed again to obtain the initial tube; The initial stage tube is subjected to a terminal forming treatment in an oven to complete the imidization reaction.
本实施例中，所述第一温度可为80℃-300℃，所述第二温度可为300℃～420℃，即第二温度不低于第一温度。具体而言，初期成型处理时，可对所述烘箱进行80℃、120℃、150℃、200℃、250℃五段程控升温；终端成型处理时，可对所述烘箱进行300℃、320℃、350℃、380℃、400℃五段程控升温。在进行终端处理时，聚酰亚胺前驱体继续进行亚胺化反应以最终形成聚酰亚胺，特别地，当烘箱内的温度在高于聚四氟乙烯的熔点时，颗粒状的聚四氟乙烯受热融化并在聚酰亚胺的分子链中渗透而与聚酰亚胺发生实际粘结最终形成所述涂层，达到修饰改善医疗管材表面润滑性的目的。In this embodiment, the first temperature may be 80°C to 300°C, and the second temperature may be 300°C to 420°C, that is, the second temperature is not lower than the first temperature. Specifically, during the initial molding process, the oven can be subjected to five-stage program-controlled heating at 80°C, 120°C, 150°C, 200°C, and 250°C; during the final forming process, the oven can be subjected to 300°C, 320°C , 350℃, 380℃, 400℃ five-stage programmable heating. During the terminal treatment, the polyimide precursor continues to undergo imidization reaction to finally form polyimide, especially when the temperature in the oven is higher than the melting point of polytetrafluoroethylene, the granular polytetrafluoroethylene The vinyl fluoride is melted by heat and penetrates into the molecular chain of the polyimide to actually bond with the polyimide to finally form the coating, so as to achieve the purpose of modifying and improving the lubricity of the medical tube surface.
应知晓，在其他实施例中，初步成型处理时对烘箱进行程控升温时也可以有其他选择，例如初步成型处理时设置120℃、150℃、200℃、250℃、300℃五段程控升温。以及，终端成型处理时可对烘箱设置320℃、350℃、380℃、400℃、420℃五段程控升温。一般来说，在进行初步成型和终端成型时，随着温度的提高，各涂层间的结合更为均一，同时壁厚也会降低。It should be understood that in other embodiments, there are other options when the oven is programmed to increase temperature during the preliminary molding process. For example, five steps of program-controlled temperature increase of 120°C, 150°C, 200°C, 250°C, and 300°C are set during the preliminary forming process. In addition, the oven can be set to 320℃, 350℃, 380℃, 400℃, 420℃ for five-stage programmable heating during the terminal forming process. Generally speaking, during preliminary molding and terminal molding, as the temperature increases, the bonding between the coatings becomes more uniform and the wall thickness decreases.
需要说明的是，上述过程是针对医疗管材具有两层涂层时的形成过程。当需要形成更多层涂层时，则可以重复执行涂覆所述涂覆剂和初步成型处理过程，最后进行终端成型处理过程即可。若所述医疗管材仅有一层涂层时，可通过烘箱内各段温度的设置，在芯线通过烘箱时依次完成所述初步成型处理过程和所述终端成型处理过程。另外，对于具有多层涂层的医疗管材，也可以在每一层涂层完成终端成型后，再涂覆第二层涂覆剂，然后进行亚胺化处理，之后以此往复直至达到需要的层数。It should be noted that the above process is for the formation process when the medical tube has two layers of coating. When more layers of coating need to be formed, the coating agent and the preliminary forming process can be repeated, and finally the final forming process can be performed. If the medical tube has only one layer of coating, the preliminary forming process and the terminal forming process can be completed in sequence when the core wire passes through the oven by setting the temperature of each section in the oven. In addition, for medical tubing with multi-layer coatings, after each layer of coating is finished forming the terminal, a second layer of coating agent can be applied, followed by imidization, and then reciprocating until the desired Number of layers.
另外，由于在执行亚胺化处理的过程中，因溶剂挥发导致最终形成的涂层厚度的缩减，因此，在具体实施例中，还可通过调整聚酰亚胺前驱体溶液的浓度来进一步调控最终所形成的单层涂层的厚度。In addition, since the thickness of the final coating layer is reduced due to solvent volatilization during the imidization process, in a specific embodiment, the concentration of the polyimide precursor solution can also be adjusted to further control The thickness of the final monolayer coating.
即，在对所形成的涂层的厚度进行管控时，是通过调整聚酰亚胺前驱体溶液的浓度，并结合模具实现的。具体的，当所述聚酰亚胺前驱体溶液的浓度越低，则在相同模具的控制下，所得到的单层涂层的厚度越小；反之，当所述聚酰亚胺前驱体溶液的浓度较高时，则在相同模具的管控下，所得到的单层涂层的厚度也越大。That is, when the thickness of the formed coating is controlled, it is achieved by adjusting the concentration of the polyimide precursor solution in combination with the mold. Specifically, when the concentration of the polyimide precursor solution is lower, under the control of the same mold, the thickness of the obtained single layer coating is smaller; on the contrary, when the polyimide precursor solution When the concentration is higher, under the control of the same mold, the thickness of the obtained single-layer coating is also larger.
换言之，基于相同的模具，可以通过提高聚酰亚胺前驱体溶液的浓度，以增加所形成的单层涂层的厚度；或者，基于相同的模具，可以通过降低聚酰亚胺前驱体溶液的浓度，以减小所形成的涂层的厚度。如此一来，在针对不同厚度需求的涂层而言，即可以直接利用同一模具，并调整聚酰亚胺前驱体溶液的浓度一一实现，有利于减少模具的使用数量，节省成本。In other words, based on the same mold, the concentration of the polyimide precursor solution can be increased to increase the thickness of the formed single layer coating; or, based on the same mold, the thickness of the polyimide precursor solution can be reduced. Concentration to reduce the thickness of the coating formed. In this way, for coatings with different thickness requirements, the same mold can be used directly, and the concentration of the polyimide precursor solution can be adjusted one by one, which is beneficial to reduce the number of molds used and save costs.
可选地，在形成所述涂层后，还包括：对所述涂层进行检测。例如，检测所述涂层的表面摩擦系数和外径(相当于检测所形成的涂层的厚度)等。这里，通常是在形成多个涂层之后执行所述检测过程。Optionally, after forming the coating, the method further includes: detecting the coating. For example, detecting the surface friction coefficient and outer diameter (equivalent to detecting the thickness of the formed coating) of the coating. Here, the detection process is usually performed after forming a plurality of coating layers.
接着，在所述涂层形成后，即可抽离所述芯线，以形成中空的医疗管材。Then, after the coating is formed, the core wire can be extracted to form a hollow medical tube.
实践中，所述芯线的长度远大于最终所需要的医疗管材的长度，因此在形成所述涂层之后，抽离所述芯线之前，还包括：按照预定长度对所述芯线上的涂层进行切割。在抽离所述芯线之前执行切割程序，因医疗管材的中心贯穿有芯线，可避免切割过程中的切割压力对管材造成损伤。In practice, the length of the core wire is much greater than the final required length of the medical tube. Therefore, after the coating is formed and before the core wire is pulled out, it also includes: aligning the core wire with a predetermined length The coating is cut. The cutting procedure is performed before the core wire is withdrawn. Because the core wire runs through the center of the medical tube, the cutting pressure during the cutting process can prevent the tube from being damaged.
接下来根据具体的实验数据，对不同的医疗管材的性能进行说明。具体请参见表1所示。Next, according to specific experimental data, the performance of different medical tubing materials is explained. Please refer to Table 1 for details.
表1医疗管材的综合性能Table 1 Comprehensive performance of medical tubing
Figure PCTCN2020080771-appb-000001
Figure PCTCN2020080771-appb-000001
Figure PCTCN2020080771-appb-000002
Figure PCTCN2020080771-appb-000002
如表1所示，管材1-5中均在改性剂的作用下分散有聚四氟乙烯，而对比管材和管材6中则未分散聚四氟乙烯，且管材1-5的摩擦系数较对比管材及管材6要小，即，本实施例中采用包括分散有聚四氟乙烯的层制作的医疗管材的表面润滑性得到了改善。同时，管材1-5的破断力、断裂伸长率仍满足使用要求。另外，通过管材2-5的比较可看到，改性的聚四氟乙烯的添加量越多，医疗管材的摩擦系数越小。As shown in Table 1, PTFE is dispersed in pipes 1-5 under the action of the modifier, while PTFE is not dispersed in comparative pipes and pipe 6, and the friction coefficient of pipes 1-5 is higher. The comparative tube and tube 6 are smaller, that is, the surface lubricity of the medical tube made of a layer including polytetrafluoroethylene dispersed in this embodiment is improved. At the same time, the breaking force and breaking elongation of the pipe 1-5 still meet the requirements of use. In addition, it can be seen from the comparison of tubes 2-5 that the more modified polytetrafluoroethylene is added, the lower the friction coefficient of the medical tube.
表1所涉及的聚酰亚胺前驱体溶液的组成成分、表面改性剂的种类和用量、造影剂的种类均相同。各管材中涂层的层数也相同，具体为五层。另外，所有性能参数均采用常规测试方法得到。The composition of the polyimide precursor solution, the type and amount of surface modifier, and the type of contrast agent involved in Table 1 are all the same. The number of coating layers in each pipe is also the same, specifically five layers. In addition, all performance parameters are obtained by conventional testing methods.
基于前述制备方法，本发明还提供了采用该方法制备得到的医疗管材。如图1所示为所述医疗管材的结构示意图，图中仅示出一层所述涂层。Based on the foregoing preparation method, the present invention also provides a medical tube prepared by the method. Figure 1 is a schematic diagram of the structure of the medical tube, and only one layer of the coating is shown in the figure.
如图1所示，所述医疗管材包括至少一层所述涂层10，所述涂层10包括聚酰亚胺基体11和分散于所述聚酰亚胺基体11中的聚四氟乙烯12。As shown in FIG. 1, the medical tube includes at least one layer of the coating 10, and the coating 10 includes a polyimide substrate 11 and polytetrafluoroethylene 12 dispersed in the polyimide substrate 11 .
进一步地，所述涂层10还包括分散于所述聚酰亚胺基体11中的造影剂13。Furthermore, the coating layer 10 further includes a contrast agent 13 dispersed in the polyimide matrix 11.
更为具体地，本实施例所述医疗管材为圆管时，其内径不小于0.1mm。 以及，所述医疗管材的管壁厚度不小于0.012mm。其中，所述医疗管材的管壁的总厚度可通过调整所述涂层10的层数来进行调控。实践中，所述涂层10可设置为一层、两层、三层、或更多层，但受应用环境的限制，所述涂层10的层数一般不超过二十层。另外，还需要说明的是，每一层涂层10的厚度可以相同也可以不同。More specifically, when the medical tube in this embodiment is a round tube, its inner diameter is not less than 0.1 mm. And, the wall thickness of the medical tube is not less than 0.012 mm. Wherein, the total thickness of the tube wall of the medical tube can be adjusted by adjusting the number of layers of the coating 10. In practice, the coating layer 10 can be provided with one layer, two layers, three layers, or more layers, but due to the limitation of the application environment, the number of layers of the coating layer 10 generally does not exceed twenty layers. In addition, it should be noted that the thickness of each layer of coating 10 may be the same or different.
综上所述，本发明通过在聚酰亚胺基体中分散聚四氟乙烯，一方面改善了聚酰亚胺材质的医疗管材的表面润滑性，可降低医疗管材在导入人体过程中对血管的摩擦损伤，以及降低药物或器具推送过程中的摩擦阻力，便于医务人员操作，提高介入治疗的效率；另一方面，在聚四氟乙烯的作用下，减小了医疗管材的表面能，便于与成型基底进行分离，便于导管的制作。另外，还通过在聚酰亚胺基体中原位添加造影剂，使得医疗导管在造影过程中具备自显影的效果，无需再加工显影环，或由操作人员推送显影剂；同时采用浸渍提拉成型的方法使得医疗导管一步成型，简化了医疗导管的制作过程，提高便捷性。In summary, by dispersing polytetrafluoroethylene in the polyimide matrix, the present invention improves the surface lubricity of medical tubing made of polyimide on the one hand, and can reduce the damage of the medical tubing to the blood vessels during the introduction into the human Friction damage and reduce the frictional resistance in the process of drug or appliance delivery, which is convenient for medical staff to operate and improve the efficiency of interventional treatment; on the other hand, under the action of PTFE, the surface energy of medical tubing is reduced, which is convenient for The molded base is separated to facilitate the production of the catheter. In addition, by adding a contrast agent in-situ to the polyimide matrix, the medical catheter has the effect of auto-imaging during the imaging process. There is no need to process the developing ring or the operator to push the developer; at the same time, the dipping and pulling molding is adopted. The method enables the medical catheter to be formed in one step, simplifies the manufacturing process of the medical catheter, and improves the convenience.
虽然本发明披露如上，但并不局限于此。本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样，倘若本发明的这些修改和变型属于本发明权利要求及其等同技术的范围之内，则本发明也意图包含这些改动和变型在内。Although the present invention is disclosed as above, it is not limited to this. Those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. In this way, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalent technologies, the present invention is also intended to include these modifications and variations.

Claims (18)

  1. 一种医疗管材的制备方法，其特征在于，包括：A method for preparing medical tubing, which is characterized in that it comprises:
    提供涂覆剂和芯线，所述涂覆剂包括聚酰亚胺前驱体溶液和分散于所述聚酰亚胺前驱体溶液中的聚四氟乙烯；Providing a coating agent and a core wire, the coating agent including a polyimide precursor solution and polytetrafluoroethylene dispersed in the polyimide precursor solution;
    将所述涂覆剂涂覆于所述芯线的外表面并进行亚胺化处理，以在所述芯线上形成至少一层涂层；以及，Applying the coating agent on the outer surface of the core wire and performing an imidization treatment to form at least one coating layer on the core wire; and,
    抽离所述芯线，得到所述医疗管材。Extract the core wire to obtain the medical tube.
  2. 根据权利要求1所述的医疗管材的制备方法，其特征在于，所述涂覆剂还包括分散于所述聚酰亚胺前驱体溶液中的造影剂。The method for preparing a medical tube according to claim 1, wherein the coating agent further comprises a contrast agent dispersed in the polyimide precursor solution.
  3. 根据权利要求1或2所述的医疗管材的制备方法，其特征在于，将所述涂覆剂涂覆于所述芯线的外表面的步骤包括：The method for preparing a medical tube according to claim 1 or 2, wherein the step of applying the coating agent on the outer surface of the core wire comprises:
    将所述芯线浸渍于所述涂覆剂中，使所述涂覆剂附着于所述芯线的外表面。The core wire is immersed in the coating agent so that the coating agent is attached to the outer surface of the core wire.
  4. 根据权利要求1所述的医疗管材的制备方法，其特征在于，所述亚胺化处理的步骤包括：The method for preparing medical tubing according to claim 1, wherein the step of imidization treatment comprises:
    在第一温度下，对涂覆有所述涂覆剂的所述芯线进行热处理；以及，Heat-treating the core wire coated with the coating agent at the first temperature; and,
    在第二温度下，对涂覆有所述涂覆剂的所述芯线进行热处理；At a second temperature, heat treating the core wire coated with the coating agent;
    其中，所述第二温度不低于所述第一温度。Wherein, the second temperature is not lower than the first temperature.
  5. 根据权利要求4所述的医疗管材的制备方法，其特征在于，所述第一温度为80℃～300℃，所述第二温度为300℃～420℃。The method for preparing medical tubing according to claim 4, wherein the first temperature is 80°C to 300°C, and the second temperature is 300°C to 420°C.
  6. 根据权利要求1或2所述的医疗管材的制备方法，其特征在于，提供涂覆剂的步骤包括：The method for preparing a medical tube according to claim 1 or 2, wherein the step of providing a coating agent comprises:
    使用表面改性剂对聚四氟乙烯进行表面改性；Use surface modifiers to modify the surface of PTFE;
    将改性的所述聚四氟乙烯分散于所述聚酰亚胺前驱体溶液中。The modified polytetrafluoroethylene is dispersed in the polyimide precursor solution.
  7. 根据权利要求6所述的医疗管材的制备方法，其特征在于，使用表面改性剂对聚四氟乙烯进行表面改性的步骤包括：The method for preparing a medical tube according to claim 6, wherein the step of using a surface modifier to modify the surface of polytetrafluoroethylene comprises:
    提供极性溶剂；Provide polar solvent;
    将所述表面改性剂和所述聚四氟乙烯加入所述极性溶剂中，混合均匀后得到悬浮液；Adding the surface modifier and the polytetrafluoroethylene to the polar solvent and mixing uniformly to obtain a suspension;
    干燥所述悬浮液，得到颗粒状的改性的聚四氟乙烯。The suspension is dried to obtain particulate modified polytetrafluoroethylene.
  8. 根据权利要求6所述的医疗管材的制备方法，其特征在于，所述表面改性剂包括离子型表面活性剂、两性表面活性剂和硅氧烷类改性剂中的至少一种。The method for preparing medical tubing according to claim 6, wherein the surface modifier comprises at least one of an ionic surfactant, an amphoteric surfactant, and a silicone modifier.
  9. 根据权利要求7所述的医疗管材的制备方法，其特征在于，所述颗粒状的改性的聚四氟乙烯的重量为所述涂覆剂总重量的2％-50％。7. The method for preparing medical tubing according to claim 7, wherein the weight of the particulate modified polytetrafluoroethylene is 2%-50% of the total weight of the coating agent.
  10. 根据权利要求7所述的医疗管材的制备方法，其特征在于，加入所述极性溶剂中的所述表面改性剂的重量为所述表面改性剂和所述极性溶剂总重量的0.05％-0.2％。The method for preparing medical tubing according to claim 7, wherein the weight of the surface modifier added to the polar solvent is 0.05 of the total weight of the surface modifier and the polar solvent. %-0.2%.
  11. 根据权利要求7所述的医疗管材的制备方法，其特征在于，所述极性溶剂包括N，N-二甲基乙酰胺、三氟乙酸、二甲亚砜、乙腈、二甲基亚酰胺、六甲基磷酰胺、甲醇、乙醇、异丙醇、吡啶、丙酮、正丁醇和苯胺中的至少一种。The method for preparing medical tubing according to claim 7, wherein the polar solvent comprises N,N-dimethylacetamide, trifluoroacetic acid, dimethylsulfoxide, acetonitrile, dimethylimide, At least one of hexamethylphosphoramide, methanol, ethanol, isopropanol, pyridine, acetone, n-butanol, and aniline.
  12. 根据权利要求7所述的医疗管材的制备方法，其特征在于，所述悬浮液中的所述聚四氟乙烯的浓度为5％-25％。The method for preparing medical tubing according to claim 7, wherein the concentration of the polytetrafluoroethylene in the suspension is 5%-25%.
  13. 根据权利要求1或2所述的医疗管材的制备方法，其特征在于，所述医疗管材的制备方法还包括：制备所述聚酰亚胺前驱体溶液，用于制备所述聚酰亚胺前驱体溶液的反应物包括至少一种芳香二酐和至少一种芳香二胺。The method for preparing a medical tube according to claim 1 or 2, wherein the method for preparing the medical tube further comprises: preparing the polyimide precursor solution for preparing the polyimide precursor The reactants of the body solution include at least one aromatic dianhydride and at least one aromatic diamine.
  14. 根据权利要求13所述的医疗管材的制备方法，其特征在于，所述聚酰亚胺前驱体溶液的浓度为5％-30％，粘度为10-100Pa·s。The method for preparing medical tubing according to claim 13, wherein the concentration of the polyimide precursor solution is 5%-30%, and the viscosity is 10-100 Pa·s.
  15. 根据权利要求2所述的医疗管材的制备方法，其特征在于，分散于所述聚酰亚胺前驱体溶液中的所述造影剂的重量为所述涂覆剂总重量的0.1％-5％。The method for preparing medical tubing according to claim 2, wherein the weight of the contrast agent dispersed in the polyimide precursor solution is 0.1%-5% of the total weight of the coating agent .
  16. 根据权利要求3所述的医疗管材的制备方法，其特征在于，将所述芯线浸渍于所述涂覆剂中，使所述涂覆剂附着于所述芯线的外表面之后，将 所述涂覆剂涂覆于所述芯线的外表面的步骤还包括：使所述芯线穿过模具的内腔，以调控所述芯线携带的涂覆剂的量。The method for preparing a medical tube according to claim 3, wherein the core wire is immersed in the coating agent, the coating agent is attached to the outer surface of the core wire, and then the The step of coating the coating agent on the outer surface of the core wire further includes: passing the core wire through the inner cavity of the mold to adjust the amount of the coating agent carried by the core wire.
  17. 根据权利要求1所述的医疗管材的制备方法，其特征在于，在抽离所述芯线之前，还包括：按照预定长度对所述芯线上的涂层进行切割。The method for preparing a medical tube according to claim 1, characterized in that, before the core wire is withdrawn, it further comprises: cutting the coating on the core wire according to a predetermined length.
  18. 采用如权利要求1-17中任一项所述的医疗管材的制备方法制备而成的医疗管材。A medical tube prepared by the method for preparing a medical tube according to any one of claims 1-17.
PCT/CN2020/080771 2019-06-28 2020-03-24 Medical tube preparation method and medical tube WO2020258945A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910580298.0A CN110292663A (en) 2019-06-28 2019-06-28 A kind of preparation method and medical treatment tubing of medical treatment tubing
CN201910580298.0 2019-06-28

Publications (1)

Publication Number Publication Date
WO2020258945A1 true WO2020258945A1 (en) 2020-12-30

Family

ID=68029606

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/080771 WO2020258945A1 (en) 2019-06-28 2020-03-24 Medical tube preparation method and medical tube

Country Status (2)

Country Link
CN (1) CN110292663A (en)
WO (1) WO2020258945A1 (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110292663A (en) * 2019-06-28 2019-10-01 脉通医疗科技(嘉兴)有限公司 A kind of preparation method and medical treatment tubing of medical treatment tubing
WO2021242835A1 (en) * 2020-05-27 2021-12-02 Zeus Industrial Products, Inc. Ptfe liners with reduced coefficient of friction
CN114452446A (en) * 2020-11-10 2022-05-10 脉通医疗科技(嘉兴)有限公司 Medical tube and preparation method thereof
CN114479451A (en) * 2020-11-11 2022-05-13 脉通医疗科技(嘉兴)有限公司 Composite pipe and preparation method thereof
CN114536827A (en) * 2020-11-25 2022-05-27 脉通医疗科技(嘉兴)有限公司 Composite pipe and preparation method thereof
CN115678273B (en) * 2021-07-26 2024-03-19 浙江脉通智造科技(集团)有限公司 Modified graphene oxide, composite pipe and preparation method thereof
CN114874623B (en) * 2022-05-17 2023-06-20 中国科学院化学研究所 Polyimide resin slurry, polyimide catheter and preparation method and application thereof
CN115670769B (en) * 2023-01-04 2023-11-03 杭州糖吉医疗科技有限公司 Digestive tract membranous tube and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06298952A (en) * 1993-04-16 1994-10-25 Nitto Denko Corp Tubular article
JP2000298411A (en) * 1999-04-15 2000-10-24 Canon Inc Hard fixing roller, its production and fixing device using the same
JP2003340946A (en) * 2002-05-29 2003-12-02 Nissei Electric Co Ltd Polyimide multi-layer tube
CN1897990A (en) * 2003-12-22 2007-01-17 株式会社I.S.T. Medical tube and its manufacturing method
CN101120289A (en) * 2005-02-21 2008-02-06 株式会社I.S.T Tubular object and its manufacturing process
CN110292663A (en) * 2019-06-28 2019-10-01 脉通医疗科技(嘉兴)有限公司 A kind of preparation method and medical treatment tubing of medical treatment tubing

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06258969A (en) * 1993-03-05 1994-09-16 Canon Inc Thermal fixing device

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06298952A (en) * 1993-04-16 1994-10-25 Nitto Denko Corp Tubular article
JP2000298411A (en) * 1999-04-15 2000-10-24 Canon Inc Hard fixing roller, its production and fixing device using the same
JP2003340946A (en) * 2002-05-29 2003-12-02 Nissei Electric Co Ltd Polyimide multi-layer tube
CN1897990A (en) * 2003-12-22 2007-01-17 株式会社I.S.T. Medical tube and its manufacturing method
CN101120289A (en) * 2005-02-21 2008-02-06 株式会社I.S.T Tubular object and its manufacturing process
CN110292663A (en) * 2019-06-28 2019-10-01 脉通医疗科技(嘉兴)有限公司 A kind of preparation method and medical treatment tubing of medical treatment tubing

Also Published As

Publication number Publication date
CN110292663A (en) 2019-10-01

Similar Documents

Publication Publication Date Title
WO2020258945A1 (en) Medical tube preparation method and medical tube
Xu et al. A universal strategy for growing a tenacious hydrogel coating from a sticky initiation layer
JP4570873B2 (en) Medical device with polymer-coated inner lumen
JP2803017B2 (en) Antithrombotic medical material and medical device, and their manufacturing method, manufacturing apparatus, and plasma processing apparatus
WO2007046348A1 (en) Medical catheter tubes and process for production thereof
Ullrich et al. Swimming characteristics of helical microrobots in fibrous environments
JP2009525814A (en) Inline application of coating
Wang et al. Controllable microfluidic fabrication of microstructured materials from nonspherical particles to helices
JP2007229452A (en) Medical tube and its manufacturing method
WO2005061020A1 (en) Medical tube and process for producing the same
CN105733317A (en) Preparation method of functionalized carbon nanotube powder
WO2020258944A1 (en) Medical tube material and manufacturing method therefor
Xiong et al. A new strategy for improvement of interface and mechanical properties of carbon fiber/epoxy composites by grafting graphene oxide onto carbon fiber with hyperbranched polymers via thiol‐ene click chemistry
WO2021103747A1 (en) Medical pipe material and preparation method thereof
CN109045351A (en) A kind of magnesium alloy based on surface treatment and fibroin albumen connection method
CN114479451A (en) Composite pipe and preparation method thereof
JP2005205183A (en) Medical tube and its manufacturing method
Pei et al. Facile fabrication of superhydrophobic surface with palygorskite-poly (2-(perfluorohexyl) ethyl methacrylate) composite microgels
CN114452446A (en) Medical tube and preparation method thereof
CN115678273B (en) Modified graphene oxide, composite pipe and preparation method thereof
CN106377801A (en) Super-smooth intravascular catheter coating and preparation method thereof
JPH0374174B2 (en)
CN114536827A (en) Composite pipe and preparation method thereof
CN111016207A (en) Flexible and low-density PTFE (Polytetrafluoroethylene) stretched pipe as well as manufacturing process and application thereof
JP2002045428A (en) Thin ptfe tube for catheter, manufacturing method therefor and catheter tube

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20833353

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20833353

Country of ref document: EP

Kind code of ref document: A1