CN115350336B - Developing catheter - Google Patents

Developing catheter Download PDF

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Publication number
CN115350336B
CN115350336B CN202210968195.3A CN202210968195A CN115350336B CN 115350336 B CN115350336 B CN 115350336B CN 202210968195 A CN202210968195 A CN 202210968195A CN 115350336 B CN115350336 B CN 115350336B
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pebax
polysilsesquioxane
particles
master batch
dispersing agent
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CN115350336A (en
Inventor
冯猛
黄兴
刘成其
张宝辉
杨巧云
杨凤凯
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Shenzhen Jdd Tech New Material Co ltd
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Shenzhen Jdd Tech New Material Co ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L29/00Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/14Materials characterised by their function or physical properties, e.g. lubricating compositions
    • A61L29/18Materials at least partially X-ray or laser opaque
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L29/00Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/12Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L29/126Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix

Abstract

The application discloses a developing catheter, which comprises a catheter body, wherein the catheter body is mainly prepared by extruding the following raw materials in percentage by mass of the catheter body through an extrusion molding process: 60% -80% of first resin master batch, 15% -40% of second resin master batch and 0.1% -0.5% of dispersing agent; the first resin master batch is mainly formed by melting, blending and granulating first Pebax particles and barium sulfate with a polysilsesquioxane dispersing agent combined on the surface; the second resin master batch comprises second Pebax particles and third Pebax particles, the dispersing agent comprises polyethylene glycol, and the molecular weight of the polyethylene glycol is 200-8000. The application modifies the existing catheter body Pebax polymer, reduces the processing difficulty of the extrusion molding process, ensures that the prepared catheter body has smooth surface, no adverse phenomena such as burrs, pits and the like, and has uniform barium sulfate dispersion.

Description

Developing catheter
Technical Field
The application relates to the technical field of medical instruments, in particular to a developing catheter.
Background
The developing catheter is a necessary instrument for vascular interventional therapy, is a long polymer catheter and is used for moving to a lesion organ (part) through an artery and a vein to generate a contrast effect, displaying the range, the part and the degree of the lesion, and can be used as a channel for therapeutic drugs and interventional instruments to enter the blood vessel.
The conventional medical developing catheter generally comprises a catheter body made of a high-molecular polymer material and a barium sulfate developer dispersed in the high-molecular polymer catheter body. In order to achieve the development effect of clinical use, the addition mass of the barium sulfate needs to be more than 30 percent. The polymers of the catheter body are typically Pebax thermoplastic multi-block copolymers that provide different hardness products by combining hard segment linear polyamide segments and soft segment polyether segments of different types and proportions, wherein the polyether soft segments provide ductility and flexibility and the polyamide hard segments provide physical crosslinking.
The visualization catheter is a long catheter, and different portions of the catheter body have different requirements for hardness, for example, the front end of the catheter body needs to be softer to smoothly enter the blood vessel to reach the lesion, and the rear end of the catheter body needs to have a certain hardness to maintain sufficient support.
In the prior art, when the Pebax with high hard segment ratio is doped with high content of barium sulfate (more than 30 percent), the Pebax polymer with high hard segment ratio has poor flowability, poor compatibility with the barium sulfate, and over-high content of the barium sulfate, so that the barium sulfate is easy to agglomerate and disperse unevenly in the Pebax, and when the catheter body is prepared by an extrusion molding process, the Pebax has poor flowability, short duration of a processing process and easy foaming due to high hard segment ratio of the Pebax, and the toughness of the Pebax is damaged by the doping of the barium sulfate, so that the extrusion molding of a product is seriously influenced, the surface roughness of the prepared catheter body, uneven wall thickness, burrs, pits and other adverse phenomena are generated, so that the development effect is poor, and the vessel is not smooth and easy to damage.
Disclosure of Invention
The application aims to overcome the defects in the prior art, and provides a developing catheter which is used for modifying the Pebax polymer of the existing catheter body, reducing the processing difficulty of an extrusion molding process, ensuring that the prepared catheter body has smooth surface, no adverse phenomena such as burrs, pits and the like, and uniformly dispersed barium sulfate.
In order to achieve the above purpose, the technical scheme of the application is as follows:
the developing catheter comprises a catheter body and is characterized in that the catheter body is mainly prepared by extruding the following raw materials in percentage by mass of the catheter body through an extrusion molding process:
60% -80% of first resin master batch, 15% -40% of second resin master batch and 0.1% -0.5% of dispersing agent;
the first resin master batch is mainly formed by melting, blending and granulating first Pebax particles and barium sulfate with a polysilsesquioxane dispersing agent combined on the surface; wherein the melt index of the first Pebax particles is 8g/10 min-10 g/10min; the weight percentage of the first Pebax particles is 40-60% of the weight of the first resin master batch, and the weight percentage of the barium sulfate with the polysilsesquioxane dispersing agent combined on the surface is 35-60% of the weight percentage of the first resin master batch; the mass of the polysilsesquioxane dispersing agent is 0.5-1.5% of the mass of the barium sulfate;
the second resin master batch comprises second Pebax particles and third Pebax particles, wherein the melt fingers of the second Pebax particles are 8g/10 min-10 g/10min, the melt fingers of the third Pebax particles are 4g/10 min-7 g/10min, the mass of the second Pebax particles accounts for 80-95% of the mass of the second resin master batch, and the mass of the third Pebax particles accounts for 5-20% of the mass of the second resin master batch;
the dispersing agent comprises polyethylene glycol, and the molecular weight of the polyethylene glycol is 200-8000.
The implementation of the embodiment of the application has the following beneficial effects:
in the embodiment of the application, the structural general formula of the polysilsesquioxane dispersing agent is RSiO 3/2 The structural formula is as follows:the center of the inorganic core is an inorganic core composed of silicon-oxygen frameworks alternately connected with Si-O, si atoms on eight vertex angles of the inorganic core are respectively connected with organic groups R, the organic groups R are used for carrying out cross-linking reaction with first Pebax particles, on one hand, the organic groups R can be bent and intertwined with Pebax polymers, the compatibility of barium sulfate and Pebax is improved, the dispersibility of the barium sulfate in the Pebax is improved, on the other hand, the cage-shaped silicon-oxygen inorganic core has inorganic characteristics like the barium sulfate, can cover and lock the barium sulfate, improves the dispersibility of the barium sulfate, avoids the agglomeration of the barium sulfate, and further, because the cage-shaped silicon-oxygen inorganic core Si-O has a large thermal stability effect in an extrusion molding process, avoids processing degradation and can improve the stability and biocompatibility of the extrusion process. .
When the first resin master batch is prepared, on one hand, the polysilsesquioxane dispersing agent is used for modifying the barium sulfate, so that the dispersibility of the barium sulfate is enhanced, the toughness of the Pebax polymer is prevented from being damaged, and on the other hand, the first Pebax particles with good fluidity are used for dispersing the barium sulfate, so that the dispersibility of the barium sulfate is further improved.
The second resin master batch comprises second Pebax particles with better fluidity and softer properties and third Pebax particles with poor fluidity but high hardness, the hardness of the developing conduit is regulated by regulating the content of the second Pebax particles and the third Pebax particles, and in the application, a larger amount of second Pebax particles with better fluidity and softer properties are still adopted to improve the fluidity of the whole polymer so as to fully disperse the barium sulfate and provide higher fluidity and toughness to reduce the difficulty of the extrusion molding process.
In addition, by adding the dispersing agent polyethylene glycol, the fluidity of the polymer is improved, the dispersibility of barium sulfate is enhanced, the difficulty of the extrusion molding process is reduced, and the polyethylene glycol and the Pebax polymer are crosslinked in the extrusion molding process, so that the hardness and toughness of the catheter body are improved. According to the application, the low-molecular-weight liquid dispersing agent polyethylene glycol is added, so that the viscosity of the Pebax polymer can be greatly reduced in the initial adding stage, the fluidity and toughness of the Pebax polymer are enhanced, and the extrusion molding is facilitated; meanwhile, the polyethylene glycol contains ether groups, so that stronger hydrogen bonds can be formed with hydroxyl groups on the surface of the barium sulfate, and the uniform dispersibility of the barium sulfate in the Pebax is improved; along with the rise of temperature and the extrusion acting force of the extruder, polyethylene glycol and the Pebax polymer undergo a crosslinking reaction, so that the hardness of the catheter body is enhanced, namely, the polyether soft segment is used for crosslinking the Pebax polymer, so that the hardness of the developing catheter is enhanced, the toughness is not lost, and the smooth, uniform wall thickness, burr-free and pitted catheter body is extruded in the extrusion process.
Detailed Description
The technical solutions of the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The application discloses a developing catheter, which comprises a catheter body, wherein the catheter body is mainly prepared by extruding the following raw materials in percentage by mass of the catheter body through an extrusion molding process:
60% -80% of first resin master batch, 15% -40% of second resin master batch and 0.1% -0.5% of dispersing agent.
In the scheme, the first resin master batch is mainly formed by melting, blending and granulating first Pebax particles with good fluidity and barium sulfate with polysilsesquioxane dispersing agent combined on the surface; wherein the melt index of the first Pebax particles is 8g/10 min-10 g/10min; the weight percentage of the first Pebax particles is 40-60% of the weight percentage of the first resin master batch, and the weight percentage of the barium sulfate with the polysilsesquioxane dispersing agent combined on the surface is 35-60% of the weight percentage of the first resin master batch; the mass of the polysilsesquioxane dispersing agent is 0.5-1.5% of the mass of the barium sulfate.
In the present application, the polysilsesquioxane dispersant has the structural formula RSiO 3/2 The structural formula is as follows:the center of the inorganic core is an inorganic core composed of silicon-oxygen frameworks alternately connected with Si-O, si atoms on eight vertex angles of the inorganic core are respectively connected with organic groups R, the organic groups R are used for carrying out cross-linking reaction with first Pebax particles, on one hand, the organic groups R can be bent and intertwined with Pebax polymers, the compatibility of barium sulfate and Pebax is improved, the dispersibility of the barium sulfate in the Pebax is improved, on the other hand, the cage-shaped silicon-oxygen inorganic core has inorganic characteristics like the barium sulfate, can cover and lock the barium sulfate, improves the dispersibility of the barium sulfate, avoids the agglomeration of the barium sulfate, and further, because the cage-shaped silicon-oxygen inorganic core Si-O has a large thermal stability effect in an extrusion molding process, avoids processing degradation and can improve the stability and biocompatibility of the extrusion process.
In the preparation of the first resin master batch, on the one hand, barium sulfate is modified by polysilsesquioxane dispersing agent, and on the other hand, barium sulfate is dispersed by using first Pebax particles with good fluidity, so that the dispersibility of the barium sulfate is further improved.
The second resin master batch comprises second Pebax particles and third Pebax particles, wherein the melt fingers of the second Pebax particles are 8g/10 min-10 g/10min, the melt fingers of the third Pebax particles are 4g/10 min-7 g/10min, the mass of the second Pebax particles accounts for 80% -95% of the mass of the second resin master batch, and the mass of the third Pebax particles accounts for 5% -20% of the mass of the second resin master batch. The second resin master batch comprises second Pebax particles with better fluidity and softer properties and third Pebax particles with poor fluidity but high hardness, the hardness of the developing conduit is regulated by regulating the content of the second Pebax particles and the third Pebax particles, and in the application, a larger amount of second Pebax particles with better fluidity and softer properties are still adopted to improve the fluidity of the whole polymer so as to fully disperse the barium sulfate and provide higher fluidity and toughness to reduce the difficulty of the extrusion molding process.
The dispersing agent comprises polyethylene glycol, the molecular weight of the polyethylene glycol is 200-8000, and the dispersing agent polyethylene glycol has the functions of improving the fluidity of the polymer and enhancing the dispersibility of barium sulfate on one hand, and improving the hardness and toughness of the catheter body by crosslinking with the Pebax polymer in the extrusion molding process on the other hand. According to the application, the low-molecular-weight liquid dispersing agent polyethylene glycol is added, so that the viscosity of the Pebax polymer can be greatly reduced in the initial adding stage, the fluidity and toughness of the Pebax polymer are enhanced, and the extrusion molding is facilitated; meanwhile, the polyethylene glycol contains ether groups, so that stronger hydrogen bonds can be formed with hydroxyl groups on the surface of the barium sulfate, and the uniform dispersibility of the barium sulfate in the Pebax is improved. Along with the rise of temperature and the extrusion acting force of the extruder, polyethylene glycol and the Pebax polymer undergo a crosslinking reaction, so that the hardness of the catheter body is enhanced, namely, the polyether soft segment is used for crosslinking the Pebax polymer, so that the hardness of the developing catheter is enhanced, the toughness is not lost, and the smooth, uniform wall thickness, burr-free and pitted catheter body is extruded in the extrusion process.
Further, in some embodiments, the end group of the organic group R in the polysilsesquioxane dispersant is an epoxy group, and the epoxy group and the amino group in Pebax can be subjected to chemical crosslinking reaction, so that the binding force with Pebax is increased, and the dispersibility of barium sulfate is further improved.
Specifically, the polysilsesquioxane dispersant may include: gamma-glycidoxysilpropyl cage type polysilsesquioxane (CAS: 68611-45-0), epoxycyclohexyl isobutyl polysilsesquioxane (CAS: 445379-56-6), epoxycyclohexyl polysilsesquioxane (CAS: 187333-74-0).
Further, in some embodiments, the first Pebax particle comprises one or more of Pebax3533 particle, pebax2533 particle, and Pebax 4533 particle, and the second Pebax particle comprises one or more of Pebax3533 particle, pebax2533 particle, and Pebax 4533 particle; the tensile modulus of the first Pebax particles and the second Pebax particles is less than 100Mpa, so that the melt index is low, the fluidity is good, the particles are soft, the processing of an extrusion molding process is facilitated, the processing duration is prolonged, and bubbles are avoided.
In some embodiments, the third Pebax particle comprises one or more of Pebax 7233 particle, pebax 7033 particle, pebax 6333 particle, pebax 5533 particle, and Pebax 4033 particle; the tensile modulus of the third Pebax particle is more than 100MPa, so that the hardness of the catheter body can be regulated.
In the above embodiment, the present application selects the existing medical Pebax raw material, and modifies the polymer of the catheter body by mixing the Pebax raw material with different physical properties.
In some embodiments, the polyethylene glycol comprises one or more of PEG-200, PEG-400, PEG-600, PEG-800, PEG-1000, PEG-1500, PEG-4000, PEG-6000, and PEG-8000.
In some embodiments, the barium sulfate is nano-barium sulfate, and the particle size of the barium sulfate is 10 microns or less (2500 mesh or more), preferably 10nm to 1 μm.
In another embodiment, the catheter body is extruded by an extrusion process from the following materials in mass percent of the catheter body:
60 to 80 percent of first resin master batch, 15 to 40 percent of second resin master batch, 0.1 to 0.5 percent of dispersing agent and 0.1 to 0.5 percent of lubricant.
The lubricant comprises one or two of stearic acid amide and methyl silicone oil, the lubricant assists the polymer to complete the extrusion molding process more smoothly, the catheter body with smooth surface and uniform wall thickness is obtained, the lubricant has low boiling point and low content, can be completely volatilized in the extrusion molding process, and avoids residue from affecting medical indexes of the catheter body.
In some embodiments, the first resin master batch further comprises an inorganic antibacterial agent with a polysilsesquioxane dispersing agent bonded on the surface, namely the first resin master batch is mainly formed by melt blending and granulating first Pebax particles, barium sulfate with the polysilsesquioxane dispersing agent bonded on the surface and the inorganic antibacterial agent with the polysilsesquioxane dispersing agent bonded on the surface; the mass of the inorganic antibacterial agent with the polysilsesquioxane dispersing agent combined on the surface accounts for 2-6% of the mass of the first resin master batch, the mass of the polysilsesquioxane dispersing agent is 0.5-1.5% of the mass of the inorganic antibacterial agent, the inorganic antibacterial agent is nano inorganic antibacterial, and the particle size is below 10 microns, preferably 10 nm-1 mu m.
In the prior art, the developing catheter lacks strong antibacterial performance, and the outer surface of the catheter body is coated with the bactericide before use, so that the operation still has the risk of incomplete sterilization or secondary infection in the operation process after sterilization is finished, and in practical clinical application, particularly under the condition of proper temperature and humidity, bacteria are easily propagated on the surface of the catheter body, and the recovery of patients is seriously threatened. The scheme adds the inorganic antibacterial agent into the catheter body, so that the catheter body has long-acting antibacterial performance.
In order to avoid the decomposition of the antibacterial agent by heating in the extrusion molding process, the application adopts inorganic antibacterial agent, which can comprise TiO 2 、ZnO、CdS、WO 3 、SnO 2 And ZrO(s) 2 One or more than two of the inorganic antibacterial agents are n-type semiconductor materials, and have antibacterial activity under photocatalysis, wherein nano TiO 2 Is the most common photocatalysis type antibacterial agent at present, in particular to anatase TiO 2 . The material has low toxicity, safety to human body, no irritation to skin, strong antibacterial ability, broad antibacterial spectrum, and instant antibacterial effectAnd (5) fruits. At the same time, tiO 2 Is a white inorganic pigment with non-toxic, optimal opacity, optimal whiteness and brightness.
Nanometer TiO 2 Has good killing effect on bacteria (Escherichia coli, salmonella and Pseudomonas), viruses (MS 2 phage, RNA phage, phil 164), bacterial spores (Bacillus subtilis), fungi and parasites, and the like, and in addition, the nano TiO 2 Also has good anti-aging effect on the polymer.
Because the inorganic antibacterial agent has small particle size, large specific surface and high surface hydroxyl content, the inorganic antibacterial agent is extremely easy to agglomerate. Before preparing the polymer/nano composite material by adopting a simple blending method, the surface of the inorganic antibacterial agent is modified by adopting a polysilsesquioxane dispersing agent so as to improve the dispersibility in the polymer and the compatibility with the polymer. The combination between the polysilsesquioxane dispersing agent and the nano inorganic antibacterial agent and the polymer is the same as the effect of the polysilsesquioxane dispersing agent on barium sulfate, and is not described in detail herein.
The application also provides a preparation method of the developing catheter, which comprises the following steps:
step 1: the preparation method of the first resin master batch comprises the following steps:
step 11: barium sulfate having a polysilsesquioxane dispersant incorporated on the surface thereof was prepared.
In some embodiments, the process for preparing barium sulfate with a polysilsesquioxane dispersant incorporated on the surface is:
step 111: barium sulfate and polysilsesquioxane dispersant were dispersed in absolute ethanol, dispersion.
Step 112: heating the dispersion to 80-100 ℃, continuously stirring, filtering, washing, drying and grinding after the reaction is finished to obtain the barium sulfate with the surface combined with the polysilsesquioxane dispersing agent.
In this step, heating causes the O atoms in the RO-groups in the polysilsesquioxane dispersant to bond with the hydroxyl groups on the barium sulfate surface via hydrogen bonds.
Step 12: and mixing the first Pebax particles and barium sulfate with the polysilsesquioxane dispersing agent on the surface, and adding the mixture into a double-screw extruder for melt blending and granulating to obtain the first resin master batch.
In this step, the advantage of melt granulation using a twin screw extruder is that the shear and dispersion are uniform.
In some embodiments, the processing parameters of the twin screw extruder are: setting a first section 160 ℃, a second section 165 ℃, a third section 170 ℃, a fourth section 175 ℃, a fifth section 185 ℃, a sixth section 180 ℃, a seventh section 180 ℃, an eighth section 180 ℃, a ninth section 180 ℃, a die head 180 ℃ and a main machine rotating speed: 350rpm, and the feeding speed is 20 rpm-30 rpm.
When the antibacterial catheter body is prepared, in this step, the first Pebax particles, the barium sulfate with the polysilsesquioxane dispersing agent bonded to the surface, and the inorganic antibacterial agent with the polysilsesquioxane dispersing agent bonded to the surface are mixed and then added into a twin-screw extruder to perform melt blending granulation, and the preparation method of the inorganic antibacterial agent with the polysilsesquioxane dispersing agent bonded to the surface is the same as that of the barium sulfate with the polysilsesquioxane dispersing agent bonded to the surface.
Step 2: and mixing the first resin master batch, the second resin master batch and the dispersing agent, and then adding the mixture into a single screw extruder for melt blending extrusion to obtain the developing guide tube.
In this step, a single screw extruder is used for processing because shearing processing by a twin screw extruder results in advanced degradation of a part of the raw materials.
In some embodiments, the single screw extruder comprises a first working section, a second working section, a third working section, a fourth working section, a fifth working section, and a sixth working section, the first working section temperature is 165 ℃, the second working section temperature is 165 ℃, the third working section temperature is 170 ℃, the fourth working section temperature is 170 ℃, the fifth working section temperature is 175 ℃, the sixth working section temperature is 180 ℃, the extruder screw speed is 18rpm, the melt pressure is 1bar, the blow amount: 5.3 hundred Pa.
In the above-described scheme, the temperature of each working section is set according to the melting point or melting temperature of the polymer.
The following are specific examples.
Example 1
1) 500 g of nano barium sulfate is weighed and dispersed in 2000mL of absolute ethyl alcohol, and the suspension is stirred at normal temperature for 1h at high speed and then dispersed for 30min by ultrasonic waves; then dripping ethanol solution containing 5 g of polysilsesquioxane dispersing agent gamma-glycidoxy-silicapropyl cage-type polysilsesquioxane, stirring at a constant temperature of 80 ℃ for 4 hours at a high speed, ending the reaction, filtering, washing with absolute ethanol, drying at 100 ℃ for 24 hours, and crushing and grinding to obtain the barium sulfate with modified surface.
1) Weigh 10g of nano TiO 2 Dispersing in 100mL absolute ethanol, stirring the suspension at normal temperature for 1h at high speed, and dispersing with ultrasonic waves for 30min; then dripping ethanol solution containing 0.2 g polysilsesquioxane dispersant gamma-glycidoxypropyl cage-type polysilsesquioxane, stirring at constant temperature of 80 ℃ for 4 hours at high speed, ending the reaction, filtering, washing with absolute ethanol, drying at 100 ℃ for 24 hours, crushing and grinding to obtain the TiO with modified surface 2
2) 50% of barium sulfate powder modified by Pebax3533 49% and coupling agent, and TiO modified by coupling agent 2 1% of powder is added into a high-speed mixer and stirred and mixed for 8 minutes. And adding the mixed materials into a double-screw extruder for melt blending, extrusion and granulation to obtain the first resin master batch.
3) 70% of a first resin master batch, 29% of a second resin master batch (comprising 3533 90% of Pebax and 553310%) of Pebax, 0.5% of PEG-400 dispersing agent and 0.5% of polyethylene wax lubricant are added into a high-speed mixer, mixed for 8 minutes, and the mixed materials are added into a single screw extruder to be melt, blended and extruded, so that the developing guide tube is obtained. The control system of the precise extrusion equipment adopts an Italy inlet Jeffer control system, which is convenient for precisely monitoring the processing temperature and melt pressure of each region of the extrusion screw, and the system can automatically adjust the rotating speed of a host machine according to monitoring data, the processing temperature of each region and timely adjust the glue outlet amount, thereby ensuring the dimensional stability of products and having excellent performance. The Pebax catheter with thin wall, small pipe diameter, small tolerance and precise size is manufactured by a vacuum and micro-blowing process by being provided with a micro-blowing system with an air source at an adjustable American inlet. The extrusion processing conditions are as follows: the first working section temperature was 165 ℃, the second working section temperature was 165 ℃, the third working section temperature was 170 ℃, the fourth working section temperature was 170 ℃, the fifth working section temperature was 175 ℃, the sixth working section temperature was 180 ℃, the extruder screw speed was 18rpm, the melt pressure was 1bar, and the blow amount: 5.3 hundred Pa.
Example 2
Example 2 differs from example 1 only in that the modified barium sulfate polysilsesquioxane dispersant gamma-glycidyl ether oxosilylpropyl cage-type polysilsesquioxane has a mass of 1.5% of that of nano barium sulfate, namely 500 g of nano barium sulfate is weighed and dispersed in 2000mL of absolute ethyl alcohol, and the suspension is stirred at normal temperature for 1h at high speed and then dispersed by ultrasonic waves for 30min; then dripping ethanol solution containing 7.5 g of polysilsesquioxane dispersant gamma-glycidoxy-silicapropyl cage-type polysilsesquioxane, stirring at constant temperature of 80 ℃ for 4 hours at high speed, ending the reaction, filtering, washing with absolute ethanol, drying at 100 ℃ for 24 hours, and crushing and grinding to obtain the barium sulfate with modified surface.
The remainder were identical.
Example 3
Example 3 differs from example 1 only in that the gamma-glycidoxypropyl cage polysilsesquioxane of the modified barium sulfate is 0.5% of the nano barium sulfate by weight, namely 500 g of nano barium sulfate is weighed and dispersed in 2000mL of absolute ethyl alcohol, and the suspension is stirred at normal temperature for 1h at high speed and then dispersed by ultrasonic waves for 30min; then dripping ethanol solution containing 2.5 g of polysilsesquioxane dispersant gamma-glycidoxy-silicapropyl cage-type polysilsesquioxane, stirring at constant temperature of 80 ℃ for 4 hours at high speed, ending the reaction, filtering, washing with absolute ethanol, drying at 100 ℃ for 24 hours, and crushing and grinding to obtain the barium sulfate with modified surface.
The remainder were identical.
Comparative example 1
Comparative example 1 differs from example 1 only in that: barium sulfate and TiO 2 Neither is modified.
Comparative example 2
Comparative example 2 differs from example 1 only in that: barium sulfate and TiO with stearic acid lubricating dispersant 2 And (5) modifying. The modification method comprises the following steps: baSO is carried out 4 Adding the suspension into a three-neck flask, stirring and heating to 45deg.C, dissolving stearic acid in ethanol, slowly adding a certain amount of BaSO under stirring 4 Continuously stirring and heating the suspension in a three-neck flask after the dripping is finished, stopping reacting for 1-2 hours, cooling, filtering and vacuum drying to obtain the stearic acid modified nano BaSO 4 Powder (modifier 1.0 wt%).
Comparative example 3
Comparative example 3 differs from example 1 only in that: barium sulfate and TiO with isopropyl titanate as titanate coupling agent 2 And (5) modifying. The modification method comprises the following steps: baSO is carried out 4 The suspension was added to a three-necked flask, heated to 80 ℃ with stirring, and the titanate coupling agent was slowly added with stirring. Stirring at constant temperature, and condensing and refluxing; stopping the reaction after 1 to 2 hours, and obtaining the titanate coupling agent modified nano BaSO after cooling, filtering and vacuum drying 4 Powder (modifier 1.0 wt%).
Comparative example 4
Comparative example 4 differs from example 1 only in that: barium sulfate and TiO with silane coupling agent (KH-550) 2 And (5) modifying. The modification method comprises the following steps: the BaSO4 suspension was added to a three-necked flask, heated to 80 ℃ with stirring, and KH-550 silane coupling agent was slowly added with stirring. Stirring at constant temperature, and condensing and refluxing; stopping the reaction after 1 to 2 hours, and obtaining the silane coupling agent modified nano BaSO after cooling, filtering and vacuum drying 4 Powder (modifier 1.0 wt%).
Comparative example 5
Comparative example 5 differs from example 1 only in that: barium sulfate and TiO with 2% silane coupling agent (KH-550) 2 And (5) modifying. The modification method comprises the following steps: barium sulfate and TiO with silane coupling agent (KH-550) 2 And (5) modifying. The modification method comprises the following steps: adding the BaSO4 suspension into a three-neck flask, stirring and heating to 80 ℃, and slowly adding under stirringKH-550 silane coupling agent. Stirring at constant temperature, and condensing and refluxing; stopping the reaction after 1 to 2 hours, and obtaining the silane coupling agent modified nano BaSO after cooling, filtering and vacuum drying 4 Powder (modifier used in an amount of 2.0 wt%).
Comparative example 6
Comparative example 6 differs from example 1 only in that a polyethylene glycol dispersant was not used.
Test case
The developing catheters prepared in each example and each comparative example are subjected to performance test, and whether burrs and tingling exist on the surface quality of the catheter is firstly observed; secondly, carrying out fatigue resistance test on the developing catheter, wherein the specific process is as follows: the test was performed with reference to YY0285.4-2017, wherein the catheter fatigue resistance properties: the pressure of 1.5MPa is continuously acted for 1min, and then the pressure of the catheter is relieved, the repeated action is better than 12 times, 10-11 times are good, 8-9 times are middle, and 0-7 times are bad. Thirdly, observing the developing effect of the developing catheter: referring to YY/T0586-2016, scanning the developing catheter by a portable X-ray scanner, observing and recording the developing condition of the catheter, and sequentially classifying the developing catheter into five grades of excellent, good, medium, poor and no developing according to the developing definition; fourth, tensile modulus was measured on the resulting developing tube, and tensile strength was measured using ISO 527 standard. The results are shown in Table 1.
Table 1: performance index of developing conduit
From table 1 it can be seen that: 1) Comparing example 1 with comparative examples 1-5, it can be seen that only the gamma-glycidoxysiloxapropyl cage polysilsesquioxane of the present application significantly modifies the polymer because the binding force between the gamma-glycidoxysiloxapropyl cage polysilsesquioxane and the polymer is a chemical bonding force, while other coupling agents are mostly physisorbed; although the silane coupling agent of comparative example 5 also significantly modified the polymer, the addition amount of the silane coupling agent was too large and did not meet the medical index. 2) Comparing example 1 with comparative example 6, it can be seen that the dispersant polyethylene glycol reduces the difficulty of the extrusion process, and a catheter body with smooth surface and uniform distribution of barium sulfate can be obtained.
The above examples illustrate only a few embodiments of the application, which are described in detail and are not to be construed as limiting the scope of the claims. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of protection of the present application is to be determined by the appended claims.

Claims (10)

1. The developing catheter comprises a catheter body and is characterized in that the catheter body is mainly prepared by extruding the following raw materials in percentage by mass of the catheter body through an extrusion molding process:
60% -80% of first resin master batch, 15% -40% of second resin master batch and 0.1% -0.5% of dispersing agent;
the first resin master batch is mainly formed by melting, blending and granulating first Pebax particles and barium sulfate with a polysilsesquioxane dispersing agent combined on the surface; wherein the melt index of the first Pebax particles is 8g/10 min-10 g/10min; the weight percentage of the first Pebax particles is 40-60% of the weight of the first resin master batch, and the weight percentage of the barium sulfate with the polysilsesquioxane dispersing agent combined on the surface is 35-60% of the weight percentage of the first resin master batch; the mass of the polysilsesquioxane dispersing agent is 0.5-1.5% of the mass of the barium sulfate;
the second resin master batch comprises second Pebax particles and third Pebax particles, wherein the melt fingers of the second Pebax particles are 8g/10 min-10 g/10min, the melt fingers of the third Pebax particles are 4g/10 min-7 g/10min, the mass of the second Pebax particles accounts for 80-95% of the mass of the second resin master batch, and the mass of the third Pebax particles accounts for 5-20% of the mass of the second resin master batch;
the dispersing agent comprises polyethylene glycol, and the molecular weight of the polyethylene glycol is 200-8000;
the end group of the organic group in the polysilsesquioxane dispersant is an epoxy group.
2. The visualization catheter of claim 1, wherein the visualization catheter comprises a catheter,
the first Pebax particles comprise one or more than two of Pebax3533 particles, pebax2533 particles and Pebax 4533 particles;
the second Pebax particles comprise one or more than two of Pebax3533 particles, pebax2533 particles and Pebax 4533 particles;
the third Pebax particle comprises one or more than two of Pebax 7233 particle, pebax 7033 particle, pebax 6333 particle, pebax 5533 particle and Pebax 4033 particle;
the polyethylene glycol comprises one or more of PEG-200, PEG-400, PEG-600, PEG-800, PEG-1000, PEG-1500, PEG-4000, PEG-6000 and PEG-8000;
the polysilsesquioxane dispersing agent comprises one or more than two of gamma-glycidyl ether oxygen silicon propyl cage type polysilsesquioxane, epoxy cyclohexyl isobutyl polysilsesquioxane and epoxy cyclohexyl polysilsesquioxane.
3. The developing catheter according to claim 1 or 2, wherein the catheter body is extruded mainly from the following raw materials in mass percent of the catheter body by an extrusion process:
60% -80% of first resin master batch, 15% -40% of second resin master batch, 0.1% -0.5% of dispersing agent and 0.1% -0.5% of lubricant;
the lubricant comprises one or two of stearic acid amide and methyl silicone oil.
4. A developing catheter according to claim 3, wherein the first resin master batch is mainly formed by melt blending and granulating first Pebax particles, barium sulfate with polysilsesquioxane dispersing agent bonded on the surface, and inorganic antibacterial agent with polysilsesquioxane dispersing agent bonded on the surface; the inorganic antibacterial agent with the polysilsesquioxane dispersing agent combined on the surface accounts for 2-6% of the mass of the first resin master batch, and the mass of the polysilsesquioxane dispersing agent accounts for 0.5-1.5% of the mass of the inorganic antibacterial agent.
5. The visualization catheter of claim 4, wherein the inorganic antimicrobial agent comprises TiO 2 、ZnO、CdS、WO 3 、SnO 2 And ZrO(s) 2 One or two or more of them.
6. The developing catheter according to claim 1, wherein the preparation method of the first resin master batch comprises the following processes:
preparing barium sulfate with polysilsesquioxane dispersing agent combined on the surface;
and mixing the first Pebax particles with the barium sulfate with the polysilsesquioxane dispersing agent bonded on the surface, and adding the mixture into a double-screw extruder for melt blending and granulating to obtain the first resin master batch.
7. The developing conduit according to claim 6, wherein the processing parameters of the twin screw extruder are: setting a first section 160 ℃, a second section 165 ℃, a third section 170 ℃, a fourth section 175 ℃, a fifth section 185 ℃, a sixth section 180 ℃, a seventh section 180 ℃, an eighth section 180 ℃, a ninth section 180 ℃, a die head 180 ℃ and a main machine rotating speed: 350rpm, and the feeding speed is 20 rpm-30 rpm.
8. The developing catheter of claim 6, wherein the process of preparing the barium sulfate with polysilsesquioxane dispersant bonded to the surface is: dispersing barium sulfate and polysilsesquioxane dispersing agent in absolute ethyl alcohol to obtain a dispersing liquid; and heating the dispersion liquid to 80-100 ℃, continuously stirring, and filtering, washing, drying and grinding after the reaction is finished to obtain the barium sulfate with the polysilsesquioxane dispersing agent combined on the surface.
9. The developing catheter of claim 1, wherein the catheter body is extruded by an extrusion process comprising:
and mixing the first resin master batch, the second resin master batch and the dispersing agent, and then adding the mixture into a single screw extruder for melt blending extrusion.
10. The developing conduit of claim 9, wherein the single screw extruder comprises a first working section, a second working section, a third working section, a fourth working section, a fifth working section, and a sixth working section, the temperature of the first working section being: the first working section temperature was 165 ℃, the second working section temperature was 165 ℃, the third working section temperature was 170 ℃, the fourth working section temperature was 170 ℃, the fifth working section temperature was 175 ℃, the sixth working section temperature was 180 ℃, the extruder screw speed was 18rpm, the melt pressure was 1bar, and the blow amount: 5.3 hundred Pa.
CN202210968195.3A 2022-08-12 2022-08-12 Developing catheter Active CN115350336B (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09192229A (en) * 1996-01-19 1997-07-29 Nichias Corp Manufacture of catheter tube containing contrast medium
WO2000009170A1 (en) * 1998-08-10 2000-02-24 Bracco Research S.A. Combination of a positive mri contrast agent with a negative mri contrast agent
JP2002541051A (en) * 1999-04-09 2002-12-03 ジェイ・エム・ヒューバー・コーポレーション Surface-treated barium sulfate and method for preparing the same
JP2005218602A (en) * 2004-02-05 2005-08-18 Nichias Corp Production method of tube containing contrast medium
CN103948968A (en) * 2014-05-13 2014-07-30 天津德岩科技有限公司 In-vivo implanted composite material with X-ray developing performance and preparation method of in-vivo implanted composite material
CN105176296A (en) * 2015-10-12 2015-12-23 中国科学院宁波材料技术与工程研究所 High-temperature resistant coating based on polysilsesquioxane modification and application thereof
CN108276638A (en) * 2017-12-29 2018-07-13 深圳职业技术学院 A kind of tubing and preparation method thereof with X-ray developing function
CN110467212A (en) * 2019-08-30 2019-11-19 南宁众创空间科技有限公司 A kind of method of modifying of nano barium sulfate

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09192229A (en) * 1996-01-19 1997-07-29 Nichias Corp Manufacture of catheter tube containing contrast medium
WO2000009170A1 (en) * 1998-08-10 2000-02-24 Bracco Research S.A. Combination of a positive mri contrast agent with a negative mri contrast agent
JP2002541051A (en) * 1999-04-09 2002-12-03 ジェイ・エム・ヒューバー・コーポレーション Surface-treated barium sulfate and method for preparing the same
JP2005218602A (en) * 2004-02-05 2005-08-18 Nichias Corp Production method of tube containing contrast medium
CN103948968A (en) * 2014-05-13 2014-07-30 天津德岩科技有限公司 In-vivo implanted composite material with X-ray developing performance and preparation method of in-vivo implanted composite material
CN105176296A (en) * 2015-10-12 2015-12-23 中国科学院宁波材料技术与工程研究所 High-temperature resistant coating based on polysilsesquioxane modification and application thereof
CN108276638A (en) * 2017-12-29 2018-07-13 深圳职业技术学院 A kind of tubing and preparation method thereof with X-ray developing function
CN110467212A (en) * 2019-08-30 2019-11-19 南宁众创空间科技有限公司 A kind of method of modifying of nano barium sulfate

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