An anti-adhesion and low-temperature resistant material, its preparation method and application

By introducing fluorine-containing POSS and polysiloxane into medical polymer materials and adopting specific preparation processes, the problem of material flexibility decreases under low temperature conditions is solved, and efficient anti-adhesion and low temperature resistance is achieved, and it is suitable for a variety of medical products.

CN119529447BActive Publication Date: 2025-07-01HENAN TUOREN MEDICAL TECH CO LTD +1
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Patent Information

Application Number
CN202411860980.2
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2024-12-17
Publication Date
2025-07-01
Estimated Expiration
2044-12-17

AI Technical Summary

Technical Problem

The flexibility of existing medical polymer materials decreases under low temperature conditions, which is prone to cracking and fracture problems, and it is difficult to effectively prevent blood clots and bacteria from growing.

Method used

The combination of polyvinyl chloride resin, fluorine-containing POSS, polysiloxane, composite heat stabilizer, epoxy soybean oil, cross-linking additive MBS, wax powder, polyethylene oxide and anionic surfactant was prepared by a high-mixer stirring, heating stirring, melt kneading and extrusion granulation.

Benefits of technology

The material can have an elongation of break of more than 40% at -10℃, an elongation of break of more than 300% at 25℃, a glass transition temperature below -21℃, a low dynamic friction coefficient, and an increase of water contact angle to 140°. It has excellent low temperature resistance and anti-adhesion properties, and is suitable for a variety of medical products.

✦ Generated by Eureka AI based on patent content.

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Patent Text Reader

Abstract

The present invention provides an anti-adhesion and low-temperature resistant material. In terms of parts by mass, the raw materials include 100 parts of polyvinyl chloride resin, 1-5 parts of fluorinated octavinylcage polyhedral oligomeric silsesquioxane (fluorinated POSS), 3-8 parts of polysiloxane, 5-10 parts of composite heat stabilizer, 5-10 parts of epoxidized soybean oil, 30-70 parts of plasticizer, 1-5 parts of cross-linking aid MBS, 0.5-1.5 parts of polyethylene oxide, 0.5-1.5 parts of polyethylene oxide, 0.5-5 parts of wax powder, and 0.1-0.5 parts of anionic surfactant. The anti-adhesion and low-temperature resistant material has a breaking elongation at -10°C of more than 40%, a breaking elongation at 25°C of more than 300%, a glass transition temperature below -21°C, a dynamic friction coefficient as low as 0.33, and a water contact angle increased to 140°. At the same time, the present invention also provides the preparation and application methods of this material.
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Description

Technical Field

[0001] The present invention relates to a medical polymer material, specifically, to an anti-adhesion and low-temperature resistant material and its preparation method and application. Background Art

[0002] Polyvinyl chloride material (PVC) is widely used in medical devices that come into contact with human blood and tissues due to its excellent mechanical properties, chemical corrosion resistance, and wear resistance. For example, disposable medical supplies such as hemodialysis systems, extracorporeal circulation systems, and catheters bring many conveniences to treatment and nursing and can prevent cross-infection. However, when used as a medical catheter, the PVC material has a large surface polarity, and the surface is prone to adsorb proteins, bacteria, and some biological cells, etc., causing wound infections, inflammations, and thrombus formation. In particular, when blood contacts the surface of a medical device, plasma proteins will quickly adsorb to the material surface and bind to the glycoprotein receptors of platelets, leading to platelet activation, blood coagulation crosslinking, and complement activation, and finally forming a thrombus. When the catheter surface remains with nutrient solution or blood, it will cause a large number of bacteria to grow, and at the same time, blood coagulation or residual liquid will cause valve adhesion and catheter blockage. Therefore, biomedical materials usually face the test of blood coagulation problems.

[0003] In response to this problem, a large number of modification studies on medical polymer materials have been carried out at home and abroad. For example, blending and copolymerization modification of PVC resins, surface modification of PVC materials or products, etc. However, these medical polymer materials all have some defects.

[0004] For example: A modified PVC pellet for hemodialysis tubing disclosed in Chinese Patent CN105061928A uses phthalate plasticizers and lead salt stabilizers, which has certain safety risks; A medical catheter and its preparation method disclosed in Chinese Patent CN116061354A uses laser or chemical etching to process micron-scale and nanoscale alternating textures on the mold surface, and a medical catheter is obtained through an injection molding process; The micron-scale and nanoscale alternating physical textures on the inner and outer surfaces of the medical catheter make it have hydrophobic, antibacterial, and anticoagulant effects. It does not improve the performance of the material itself, and its biocompatibility still needs to be improved; An anti-adhesion polymer material and its preparation method disclosed in Chinese Patent CN115746475A blend and granulate an acrylate-based amphoteric copolymer and a polymer polymer to obtain an anti-adhesion polymer material. However, the low-temperature resistance of the material is not considered. At lower temperatures, the flexibility of the material is greatly reduced, and the risk of cracking and breaking of the product is relatively high. If this situation occurs during the patient's use, it will pose a threat to the patient's life safety.

[0005] In order to solve the above existing problems, people have been seeking an ideal technical solution. Summary of the Invention

[0006] The object of the present invention is to overcome the deficiencies of the prior art, and thus provide an anti-adhesion and low-temperature resistant material, its preparation method and application.

[0007] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0008] An anti-adhesion and low-temperature resistant material, by mass, the raw materials include 100 parts of polyvinyl chloride resin, 1-5 parts of fluorinated octavinylcage polyhedral oligomeric silsesquioxane (fluorinated POSS), 3-8 parts of polysiloxane, 5-10 parts of composite heat stabilizer, 5-10 parts of epoxidized soybean oil, 30-70 parts of plasticizer, 1-5 parts of crosslinking aid MBS, 0.5-1.5 parts of polyethylene oxide, 0.5-5 parts of wax powder and 0.1-0.5 parts of anionic surfactant.

[0009] By mass, the raw materials of the fluorinated octavinylcage polyhedral oligomeric silsesquioxane include 10 parts of cage polyhedral oligomeric silsesquioxane (POSS), 2-15 parts of 1H,1H,2H,2H-perfluorodecanethiol, 0.1-1 part of 2,2-dimethoxyphenylacetophenone and 100-150 parts of dichloromethane;

[0010] The preparation method of the fluorinated octavinylcage polyhedral oligomeric silsesquioxane includes the following steps:

[0011] Dissolve the cage polyhedral oligomeric silsesquioxane, 1H,1H,2H,2H-perfluorodecanethiol, and 2,2-dimethoxyphenylacetophenone in dichloromethane solution; react under ultraviolet light irradiation of 300-500W for 10-20 min, and centrifuge to obtain a white precipitate; after washing and drying, obtain the fluorinated octavinylcage polyhedral oligomeric silsesquioxane.

[0012] The average degree of polymerization of the polyvinyl chloride resin is 1000-1800; the number-average molecular weight of the polysiloxane is 1000-15000; the number-average molecular weight of the polyethylene oxide is 1×10 5 ~1×10 6 .

[0013] The composite heat stabilizer includes a main stabilizer and an auxiliary stabilizer with a mass ratio of (2-4):1, wherein the main stabilizer is stabilizer 1010 and stabilizer 168 with a mass ratio of 2:1; the auxiliary stabilizer is phosphite.

[0014] The plasticizer is one or a combination of at least two of diisooctyl cyclohexane-1,2-dicarboxylate, diisononyl cyclohexane-1,2-dicarboxylate, and tributyl acetylcitrate.

[0015] The wax powder is polyamide wax and maleic anhydride grafted PE wax with a mass ratio of 1:(1-2); the anionic surfactant is one of secondary alkyl sulfonate, sodium dodecylbenzenesulfonate, and sodium dodecyl sulfate, and is compounded with polystyrene sulfonic acid with a mass ratio of 1:(2-3).

[0016] A preparation method of an anti-adhesion and low-temperature resistant material, which comprises the following steps:

[0017] Add polyvinyl chloride resin, fluorinated octavinylcage polyhedral oligomeric silsesquioxane, polysiloxane, composite heat stabilizer, epoxidized soybean oil, crosslinking aid MBS, wax powder, polyethylene oxide, and anionic surfactant into a high-speed mixer, and stir evenly at 500-800 rpm to obtain mixture a;

[0018] Raise the temperature to 40-50°C, add a plasticizer to mixture a, continue to stir at 800-1100 rpm and raise the temperature to 80-100°C to obtain mixture b;

[0019] Cool to 20-30°C, melt and knead at 80-170°C, carry out plasticization and extrusion, and finally granulate to obtain the anti-adhesion and low-temperature resistant material.

[0020] Use a single-screw or twin-screw extruder to melt and knead at 80-170°C, the screw speed is 40-100 rmp, the temperature of the feeding section of the screw is 80-120°C, the temperature of the plasticizing and melting section is 130-150°C, and the temperature of the die head discharging section is 150-170°C.

[0021] An application method of the anti-adhesion and low-temperature resistant material, and the anti-adhesion and low-temperature resistant material is used for continuous renal replacement therapy tubes, extracorporeal membrane oxygenation tubes, extracorporeal circulation tubes, vascular access for dialysis indwelling needles, and vascular access for disposable arteriovenous puncture devices.

[0022] The anti-adhesion and low-temperature resistant material is extruded and formed by a pipe extruder; the temperature of the heating area of the pipe extruder is 145°C-175°C, the temperature of the mold is 130°C-150°C, and the temperature of the cooling water tank is 40°C-60°C.

[0023] The present invention has prominent substantive features and significant progress compared with the prior art. Specifically, the present invention provides an anti-adhesion and low-temperature resistant material. The elongation at break at -10°C can reach more than 40%, the elongation at break at 25°C can reach more than 300%, the glass transition temperature is below -21°C, the dynamic friction coefficient is as low as 0.33, and the water contact angle increases to 140°. It has excellent low-temperature resistance and anti-adhesion properties and is suitable for medical products such as continuous renal replacement therapy tubes, extracorporeal membrane oxygenation tubes, extracorporeal circulation tubes, vascular access for dialysis indwelling needles, and vascular access for disposable arteriovenous puncture devices. At the same time, the present invention also provides a preparation method for the anti-adhesion and low-temperature resistant material. This method is simple and easy to operate and is suitable for industrial promotion. Detailed Embodiments

[0024] The technical solutions of the present invention will be further described in detail below through specific embodiments.

[0025] Example 1

[0026] This example provides an anti-adhesion and low-temperature resistant material. By mass, the raw materials include 100 parts of polyvinyl chloride resin, 3 parts of fluorinated POSS, 5 parts of polysiloxane, 6 parts of composite heat stabilizer, 8 parts of epoxidized soybean oil, 50 parts of isononyl cyclohexane-1,2-dicarboxylate, 3 parts of crosslinking aid MBS, 0.5 part of polyethylene oxide, 2 parts of wax powder, and 0.3 part of anionic surfactant.

[0027] Among them, by mass, the raw materials of fluorinated POSS include 10 parts of POSS, 0.5 part of 2,2-dimethoxyphenylacetophenone, 5 parts of 1H,1H,2H,2H-perfluorodecanethiol, and 125 parts of dichloromethane. The composite heat stabilizer includes a main stabilizer and an auxiliary stabilizer with a mass ratio of 3:1. The main stabilizer is stabilizer 1010 and stabilizer 168 with a mass ratio of 2:1; the auxiliary stabilizer is phosphite; the wax powder is polyamide wax and maleic anhydride grafted PE wax with a mass ratio of 1:1.5; the anionic surfactant is secondary alkyl sulfonate and polystyrene sulfonic acid with a mass ratio of 1:2; the crosslinking aid is a core-shell structured methyl methacrylate, butadiene, styrene terpolymer (MBS crosslinking aids PA40 and PA60 from Nippon Zeon Co., Ltd.), and the mass ratio of PA40 to PA60 is 2:1. The average degree of polymerization of the polyvinyl chloride resin is 1000; the number-average molecular weight of the polysiloxane is 10000; the number-average molecular weight of the polyethylene oxide is 1×10 5 。

[0028] The fluorinated POSS is prepared by the following method: Dissolve POSS, 2,2-dimethoxyphenylacetophenone, and 1H,1H,2H,2H-perfluorodecanethiol in dichloromethane to form a solution. After stirring evenly, react under 300W ultraviolet light irradiation for 12 min; centrifuge the obtained white precipitate; filter out the white solid precipitate with a negative pressure filtration device, wash it with dichloromethane, and filter it three times repeatedly with the negative pressure filtration device. Vacuum-dry the filtered solid powder at 45 °C for 6 h to obtain the fluorinated POSS.

[0029] This example also provides a preparation method of the anti-adhesion and low-temperature resistant material, which includes the following steps:

[0030] Weigh polyvinyl chloride resin, fluorinated POSS, polysiloxane, composite heat stabilizer, epoxidized soybean oil, crosslinking aid MBS, wax powder, polyethylene oxide, and anionic surfactant according to the above parts by mass, add them to a high-speed mixer, and mix and stir evenly at a rotation speed of 500 - 800 rpm to obtain mixture a; raise the temperature to 45 °C, add diisononyl cyclohexane-1,2-dicarboxylate (DINCH) to mixture a, continue stirring at 800 - 1100 rpm and raise the temperature to 90 °C to obtain mixture b. When the material is cooled to 30 °C, the obtained mixture b is melt-kneaded at 80 - 170 °C using a screw extruder, plasticized, extruded, granulated, dehydrated, air-dried, vibrated through a sieve, and then air-dried again to obtain the anti-adhesion and low-temperature resistant material. Among them, the main machine screw rotation speed is 40 - 100 rmp, the temperature of the screw feeding section is 80 - 120 °C, the temperature of the plasticizing and melting section is 130 - 150 °C, and the temperature of the die head discharging section is 150 - 170 °C. The material is plasticized, air-cooled, and granulated by the extruder.

[0031] The anti-adhesion and low-temperature resistant material can be extruded and formed by a pipe extruder to obtain a medical catheter. Among them, the temperature of the heating area of the pipe extruder is 145 °C - 175 °C, the mold temperature is 130 °C - 150 °C, and the temperature of the cooling water tank is 50 °C. The inner and outer diameters of the catheter are 6.75 mm for the outer diameter and 4.5 mm for the inner diameter.

[0032] Example 2

[0033] This example provides an anti-adhesion and low-temperature resistant material. By parts by mass, the raw materials include 100 parts of polyvinyl chloride resin, 5 parts of fluorinated POSS, 8 parts of polysiloxane, 6 parts of composite heat stabilizer, 7 parts of epoxidized soybean oil, 60 parts of diisononyl cyclohexane-1,2-dicarboxylate, 4 parts of crosslinking aid MBS, 1.5 parts of polyethylene oxide, 3 parts of wax powder, and 0.3 parts of anionic surfactant.

[0034] Among them, based on parts by mass, the raw materials of fluorinated POSS include 10 parts of POSS, 0.13 part of 2,2-dimethoxyphenylacetophenone, 15 parts of 1H,1H,2H,2H-perfluorodecanethiol, and 134 parts of dichloromethane. The composite heat stabilizer includes a main stabilizer and an auxiliary stabilizer with a mass ratio of 2:1. The main stabilizer is stabilizer 1010 and stabilizer 168 with a mass ratio of 2:1; the auxiliary stabilizer is phosphite; the wax powder is polyamide wax and maleic anhydride grafted PE wax with a mass ratio of 1:1; the anionic surfactant is secondary alkyl sulfonate and polystyrene sulfonic acid with a mass ratio of 1:3; the crosslinking aid is a methyl methacrylate, butadiene, styrene terpolymer with a core-shell structure (MBS crosslinking aids PA40 and PA60 from Nippon Zeon Co., Ltd.), and the mass ratio of PA40 to PA60 is 2:1. The average degree of polymerization of the polyvinyl chloride resin is 1800; the number-average molecular weight of the polysiloxane is 15000; the number-average molecular weight of the polyethylene oxide is 1×10 6 .

[0035] The fluorinated POSS is prepared by the following method: Dissolve POSS, 2,2-dimethoxyphenylacetophenone, and 1H,1H,2H,2H-perfluorodecanethiol in dichloromethane to form a solution. After stirring evenly, react under 300W ultraviolet light irradiation for 15 min; centrifuge the obtained white precipitate; filter out the white solid precipitate with a negative pressure filtration device, wash it with dichloromethane, and filter it three times repeatedly with the negative pressure filtration device. Vacuum dry the filtered solid powder at 45°C for 6 h to obtain fluorinated POSS.

[0036] This embodiment also provides a preparation method of the anti-adhesion and low-temperature resistant material, which includes the following steps:

[0037] Weigh polyvinyl chloride resin, fluorinated POSS, polysiloxane, composite heat stabilizer, epoxy soybean oil, crosslinking aid MBS, wax powder, polyethylene oxide, and anionic surfactant according to the above parts by mass, add them to a high-speed mixer, and mix and stir evenly at a speed of 500-800 rpm to obtain mixture a; when the temperature rises to 45°C, add diisononyl cyclohexane-1,2-dicarboxylate (DINCH) to mixture a, continue to stir at 800-1100 rpm and heat up to 90°C to obtain mixture b. When the material is cooled to 30°C, the obtained mixture b is melt-kneaded using a screw extruder at 80-170°C, plasticized, extruded, granulated, dehydrated, air-dried, vibration sieved, and then air-dried again to obtain the anti-adhesion and low-temperature resistant material. Among them, the main screw speed is 40-100 rmp, the temperature of the feeding section of the screw is 80-120°C, the temperature of the plasticizing and melting section is 130-150°C, and the temperature of the die head discharging section is 150-170°C. The material is plasticized, air-cooled, and granulated by the extruder.

[0038] The anti-adhesion and low-temperature resistant material can be extruded into a medical catheter by a pipe extruder. Among them, the temperature of the heating area of the pipe extruder is 145°C to 175°C, the mold temperature is 130°C to 150°C, and the temperature of the cooling water tank is 45°C. The inner and outer diameters of the catheter are 6.75 mm for the outer diameter and 4.5 mm for the inner diameter.

[0039] Example 3

[0040] This example provides an anti-adhesion and low-temperature resistant material. By mass fraction, the raw materials include 100 parts of polyvinyl chloride resin, 1 part of fluorinated POSS, 3 parts of polysiloxane, 5 parts of composite heat stabilizer, 6 parts of epoxidized soybean oil, 40 parts of tributyl acetylcitrate (ATBC), 1 part of cross-linking aid MBS, 0.8 part of polyethylene oxide, 0.5 part of wax powder, and 0.1 part of anionic surfactant.

[0041] Among them, by mass fraction, the raw materials of fluorinated POSS include 10 parts of POSS, 0.71 part of 2,2-dimethoxyphenylacetophenone, 9 parts of 1H,1H,2H,2H-perfluorodecanethiol, and 125 parts of dichloromethane. The composite heat stabilizer includes a main stabilizer and an auxiliary stabilizer with a mass ratio of 4:1. The main stabilizer is stabilizer 1010 and stabilizer 168 with a mass ratio of 2:1; the auxiliary stabilizer is phosphite; the wax powder is polyamide wax and maleic anhydride grafted PE wax with a mass ratio of 1:2; the anionic surfactant is secondary alkyl sulfonate and polystyrene sulfonic acid with a mass ratio of 1:2.5; the cross-linking aid is a core-shell structured methyl methacrylate, butadiene, styrene terpolymer (MBS cross-linking aids PA40 and PA60 from Nippon Zeon Co., Ltd.), and the mass ratio of PA40 to PA60 is 2:1. The average degree of polymerization of the polyvinyl chloride resin is 1500; the number average molecular weight of the polysiloxane is 12000; the number average molecular weight of the polyethylene oxide is 1×10 6 。

[0042] The fluorinated POSS is prepared by the following method: Dissolve POSS, 2,2-dimethoxyphenylacetophenone, and 1H,1H,2H,2H-perfluorodecanethiol in dichloromethane to form a solution, and react under 380W ultraviolet light irradiation for 13 min; centrifuge the obtained white precipitate; filter out the white solid precipitate with a negative pressure filtration device, wash it with dichloromethane, and filter it three times repeatedly with the negative pressure filtration device. Vacuum dry the filtered solid powder at 45°C for 6 h to obtain fluorinated POSS.

[0043] This example also provides a preparation method of the anti-adhesion and low-temperature resistant material, which includes the following steps:

[0044] Weigh polyvinyl chloride resin, fluorine-containing POSS, polysiloxane, composite heat stabilizer, epoxidized soybean oil, crosslinking aid MBS, wax powder, polyethylene oxide, and anionic surfactant according to the above parts by mass, add them to a high-speed mixer, and mix and stir evenly at a rotation speed of 500 - 800 rpm to obtain mixture a; raise the temperature to 45°C, add tributyl acetylcitrate (ATBC) to mixture a, continue to stir at 800 - 1100 rpm and raise the temperature to 90°C to obtain mixture b. When the material is cooled to 30°C, the obtained mixture b is melt-kneaded at 80 - 170°C using a screw extruder, plasticized, extruded, granulated, dehydrated, air-dried, vibration sieved, and then air-dried again to obtain the anti-adhesion and low-temperature resistant material. Among them, the main machine screw rotation speed is 40 - 100 rmp, the temperature of the screw feeding section is 80 - 120°C, the temperature of the plasticizing and melting section is 130 - 150°C, and the temperature of the die head discharging section is 150 - 170°C. The material is plasticized, air-cooled, and granulated by the extruder.

[0045] The anti-adhesion and low-temperature resistant material can be extruded and formed by a pipe extruder to obtain a medical catheter. Among them, the temperature of the heating area of the pipe extruder is 145°C - 175°C, the die temperature is 130°C - 150°C, and the temperature of the cooling water tank is 60°C. The inner and outer diameters of the catheter are 6.75 mm for the outer diameter and 4.5 mm for the inner diameter.

[0046] Example 4

[0047] This example provides an anti-adhesion and low-temperature resistant material. Calculated by parts by mass, the raw materials include 100 parts of polyvinyl chloride resin, 3.5 parts of fluorine-containing POSS, 5 parts of polysiloxane, 5 parts of composite heat stabilizer, 7 parts of epoxidized soybean oil, 25 parts of diisononyl cyclohexane-1,2-dicarboxylate (DINCH), 20 parts of diisooctyl cyclohexane-1,2-dicarboxylate (DEHCH), 2 parts of crosslinking aid MBS, 1.1 parts of polyethylene oxide, 2.5 parts of wax powder, and 0.2 parts of anionic surfactant.

[0048] Among them, based on parts by mass, the raw materials of fluorinated POSS include 10 parts of POSS, 0.45 part of 2,2-dimethoxyphenylacetophenone, 7.8 parts of 1H,1H,2H,2H-perfluorodecanethiol, and 137 parts of dichloromethane. The composite heat stabilizer includes a main stabilizer and an auxiliary stabilizer with a mass ratio of 2:1. The main stabilizer is stabilizer 1010 and stabilizer 168 with a mass ratio of 2:1; the auxiliary stabilizer is phosphite; the wax powder is polyamide wax and maleic anhydride grafted PE wax with a mass ratio of 1:1.5; the anionic surfactant is secondary alkyl sulfonate and polystyrene sulfonic acid with a mass ratio of 1:3; the crosslinking aid is a methyl methacrylate, butadiene, styrene terpolymer with a core-shell structure (MBS crosslinking aids PA40 and PA60 from Nippon Zeon Co., Ltd.), and the mass ratio of PA40 to PA60 is 2:1. The average degree of polymerization of the polyvinyl chloride resin is 1200; the number average molecular weight of the polysiloxane is 12000; the number average molecular weight of the polyethylene oxide is 5×10 5 .

[0049] The fluorinated POSS is prepared by the following method: Dissolve POSS, 2,2-dimethoxyphenylacetophenone, and 1H,1H,2H,2H-perfluorodecanethiol in dichloromethane to form a solution, and react under ultraviolet light irradiation of 330 W for 11 min; Centrifuge the obtained white precipitate; Filter out the white solid precipitate with a negative pressure suction filtration device, wash it with dichloromethane, and filter it three times repeatedly with the negative pressure suction filtration device. Vacuum dry the filtered solid powder at 45°C for 6 h to obtain fluorinated POSS.

[0050] This example also provides a preparation method of the anti-adhesion and low-temperature resistant material, which includes the following steps:

[0051] Weigh the polyvinyl chloride resin, fluorinated POSS, polysiloxane, composite heat stabilizer, epoxidized soybean oil, crosslinking aid MBS, wax powder, polyethylene oxide, and anionic surfactant according to the above parts by mass, add them to a high-speed mixer, and mix and stir evenly at a speed of 500-800 rpm to obtain mixture a; When the temperature rises to 45°C, add diisooctyl cyclohexane-1,2-dicarboxylate (DEHCH) and diisononyl cyclohexane-1,2-dicarboxylate (DINCH) to mixture a, continue to stir at 800-1100 rpm and heat up to 90°C to obtain mixture b. When the material is cooled to 30°C, the obtained mixture b is melt-kneaded using a screw extruder at 80-170°C, plasticized, extruded, granulated, dehydrated, air-dried, vibration sieved, and then air-dried again to obtain the anti-adhesion and low-temperature resistant material. Among them, the main screw speed is 40-100 rmp, the temperature of the feeding section of the screw is 80-120°C, the temperature of the plasticizing and melting section is 130-150°C, and the temperature of the die head discharging section is 150-170°C. The material is plasticized, air-cooled, and granulated by the extruder.

[0052] The anti-adhesion and low-temperature resistant material can be extruded into a medical catheter by a pipe extruder. Among them, the temperature of the heating area of the pipe extruder is 145°C to 175°C, the mold temperature is 130°C to 150°C, and the temperature of the cooling water tank is 45°C. The inner and outer diameters of the catheter are 6.75 mm for the outer diameter and 4.5 mm for the inner diameter.

[0053] Example 5

[0054] This example provides an anti-adhesion and low-temperature resistant material. By mass, the raw materials include 100 parts of polyvinyl chloride resin, 2 parts of fluorinated POSS, 4 parts of polysiloxane, 6 parts of composite heat stabilizer, 7 parts of epoxidized soybean oil, 25 parts of diisononyl cyclohexane-1,2-dicarboxylate (DINCH), 35 parts of tributyl acetylcitrate (ATBC), 3.5 parts of crosslinking aid MBS, 1 part of polyethylene oxide, 1 part of wax powder, and 0.2 part of anionic surfactant.

[0055] Among them, by mass, the raw materials of fluorinated POSS include 10 parts of POSS, 0.33 part of 2,2-dimethoxyphenylacetophenone, 3 parts of 1H,1H,2H,2H-perfluorodecanethiol, and 100 parts of dichloromethane. The composite heat stabilizer includes a main stabilizer and an auxiliary stabilizer with a mass ratio of 3:1. The main stabilizer is stabilizer 1010 and stabilizer 168 with a mass ratio of 2:1; the auxiliary stabilizer is phosphite; the wax powder is polyamide wax and maleic anhydride grafted PE wax with a mass ratio of 1:1; the anionic surfactant is secondary alkyl sulfonate and polystyrene sulfonic acid with a mass ratio of 1:3; the crosslinking aid is a methyl methacrylate, butadiene, styrene terpolymer with a core-shell structure (MBS crosslinking aids PA40 and PA60 from Nippon Zeon Co., Ltd.), and the mass ratio of PA40 to PA60 is 2:1. The average degree of polymerization of the polyvinyl chloride resin is 1600; the number average molecular weight of the polysiloxane is 12000; the number average molecular weight of the polyethylene oxide is 1×10 6 。

[0056] The fluorinated POSS is prepared by the following method: Dissolve POSS, 2,2-dimethoxyphenylacetophenone, and 1H,1H,2H,2H-perfluorodecanethiol in dichloromethane to form a solution, and react under 300W ultraviolet light irradiation for 10 min; centrifuge the obtained white precipitate; filter out the white solid precipitate with a negative pressure suction filtration device, wash it with dichloromethane, and filter it three times repeatedly with the negative pressure suction filtration device. Vacuum dry the filtered solid powder at 45°C for 6 h to obtain fluorinated POSS.

[0057] This example also provides a preparation method for the anti-adhesion and low-temperature resistant material, which includes the following steps:

[0058] Weigh polyvinyl chloride resin, fluorinated POSS, polysiloxane, composite heat stabilizer, epoxidized soybean oil, crosslinking aid MBS, wax powder, polyethylene oxide, and anionic surfactant according to the above parts by mass, and add them to a high-speed mixer. Stir evenly at a rotation speed of 500 - 800 rpm to obtain mixture a. Raise the temperature to 45°C, add diisononyl cyclohexane-1,2-dicarboxylate (DINCH) and tributyl acetylcitrate (ATBC) to mixture a, and continue stirring at 800 - 1100 rpm and raise the temperature to 90°C to obtain mixture b. When the material is cooled to 30°C, the obtained mixture b is melt-kneaded using a screw extruder at 80 - 170°C, plasticized, extruded, granulated, dehydrated, air-dried, vibrated through a sieve, and then air-dried again to obtain the anti-adhesion and low-temperature resistant material. Among them, the rotation speed of the main machine screw is 40 - 100 rmp, the temperature of the feeding section of the screw is 80 - 120°C, the temperature of the plasticizing and melting section of the screw is 130 - 150°C, and the temperature of the die head discharging section is 150 - 170°C. The material is plasticized, air-cooled, and granulated by the extruder.

[0059] The anti-adhesion and low-temperature resistant material can be extruded and formed by a pipe extruder to obtain a medical catheter. Among them, the temperature of the heating area of the pipe extruder is 145°C - 175°C, the die temperature is 130°C - 150°C, and the temperature of the cooling water tank is 45°C. The inner and outer diameters of the catheter are 6.75 mm for the outer diameter and 4.5 mm for the inner diameter.

[0060] Example 6

[0061] This example provides an anti-adhesion and low-temperature resistant material. Calculated by parts by mass, the raw materials include 100 parts of polyvinyl chloride resin, 2.5 parts of fluorinated POSS, 6 parts of polysiloxane, 8 parts of composite heat stabilizer, 9 parts of epoxidized soybean oil, 30 parts of diisooctyl cyclohexane-1,2-dicarboxylate (DEHCH), 35 parts of tributyl acetylcitrate (ATBC), 5 parts of crosslinking aid MBS, 1.2 parts of polyethylene oxide, 4 parts of wax powder, and 0.4 part of anionic surfactant.

[0062] Among them, in terms of parts by mass, the raw materials of fluorinated POSS include 10 parts of POSS, 0.53 part of 2,2-dimethoxyphenylacetophenone, 14 parts of 1H,1H,2H,2H-perfluorodecanethiol, and 100 parts of dichloromethane. The composite heat stabilizer includes a main stabilizer and an auxiliary stabilizer with a mass ratio of 4:1. The main stabilizer is stabilizer 1010 and stabilizer 168 with a mass ratio of 2:1; the auxiliary stabilizer is phosphite; the wax powder is polyamide wax and maleic anhydride grafted PE wax with a mass ratio of 1:1; the anionic surfactant is secondary alkyl sulfonate and polystyrene sulfonic acid with a mass ratio of 1:2; the crosslinking aid is a methyl methacrylate, butadiene, styrene terpolymer with a core-shell structure (MBS crosslinking aids PA40 and PA60 from Nippon Zeon Co., Ltd.), and the mass ratio of PA40 to PA60 is 2:1. The average degree of polymerization of the polyvinyl chloride resin is 1500; the number-average molecular weight of the polysiloxane is 10000; the number-average molecular weight of the polyethylene oxide is 3×10 5 .

[0063] The fluorinated POSS is prepared by the following method: Dissolve POSS, 2,2-dimethoxyphenylacetophenone, and 1H,1H,2H,2H-perfluorodecanethiol in dichloromethane to form a solution, and react under 500W ultraviolet light irradiation for 20 min; centrifuge the obtained white precipitate; filter out the white solid precipitate with a negative pressure suction filtration device, wash it with dichloromethane, and filter it three times repeatedly with the negative pressure suction filtration device. Vacuum dry the filtered solid powder at 45°C for 6 h to obtain fluorinated POSS.

[0064] This example also provides a preparation method of the anti-adhesion and low-temperature resistant material, which includes the following steps:

[0065] Weigh polyvinyl chloride resin, fluorinated POSS, polysiloxane, composite heat stabilizer, epoxy soybean oil, crosslinking aid MBS, wax powder, polyethylene oxide, and anionic surfactant according to the above parts by mass, add them to a high-speed mixer, and mix and stir evenly at a speed of 500-800 rpm to obtain mixture a; raise the temperature to 45°C, add diisooctyl cyclohexane-1,2-dicarboxylate (DEHCH) and tributyl acetylcitrate (ATBC) to mixture a, continue to stir at 800-1100 rpm and raise the temperature to 90°C to obtain mixture b. When the material is cooled to 30°C, the obtained mixture b is melt-kneaded using a screw extruder at 80-170°C, plasticized, extruded, granulated, dehydrated, air-dried, vibrated and sieved, and then air-dried again to obtain the anti-adhesion and low-temperature resistant material. Among them, the main screw speed is 40-100 rmp, the temperature of the feeding section of the screw is 80-120°C, the temperature of the plasticizing and melting section is 130-150°C, and the temperature of the die head discharging section is 150-170°C. The material is plasticized, air-cooled and granulated by the extruder.

[0066] The anti-adhesion and low-temperature resistant material can be extruded into a medical catheter by a pipe extruder. Among them, the temperature of the heating area of the pipe extruder is 145°C to 175°C, the mold temperature is 130°C to 150°C, and the temperature of the cooling water tank is 50°C. The inner and outer diameters of the catheter are 6.75 mm for the outer diameter and 4.5 mm for the inner diameter.

[0067] Example 7

[0068] This example provides an anti-adhesion and low-temperature resistant material. By mass, the raw materials include 100 parts of polyvinyl chloride resin, 4.5 parts of fluorinated POSS, 4 parts of polysiloxane, 5.5 parts of composite heat stabilizer, 7 parts of epoxidized soybean oil, 55 parts of diisooctyl cyclohexane-1,2-dicarboxylate (DEHCH), 2.5 parts of crosslinking aid MBS, 0.9 part of polyethylene oxide, 3.5 parts of wax powder, and 0.4 part of anionic surfactant.

[0069] Among them, by mass, the raw materials of fluorinated POSS include 10 parts of POSS, 0.5 part of 2,2-dimethoxyphenylacetophenone, 5 parts of 1H,1H,2H,2H-perfluorodecanethiol, and 125 parts of dichloromethane. The composite heat stabilizer includes a main stabilizer and an auxiliary stabilizer with a mass ratio of 2:1. The main stabilizer is stabilizer 1010 and stabilizer 168 with a mass ratio of 2:1; the auxiliary stabilizer is phosphite; the wax powder is polyamide wax and maleic anhydride grafted PE wax with a mass ratio of 1:1; the anionic surfactant is secondary alkyl sulfonate and polystyrene sulfonic acid with a mass ratio of 1:2; the crosslinking aid is a core-shell structured methyl methacrylate, butadiene, styrene terpolymer (MBS crosslinking aids PA40 and PA60 from Nippon Zeon Co., Ltd.), and the mass ratio of PA40 to PA60 is 2:1. The average degree of polymerization of the polyvinyl chloride resin is 1500; the number average molecular weight of the polysiloxane is 9000; the number average molecular weight of the polyethylene oxide is 3×10 5 .

[0070] The fluorinated POSS is prepared by the following method: Dissolve POSS, 2,2-dimethoxyphenylacetophenone, and 1H,1H,2H,2H-perfluorodecanethiol in dichloromethane to form a solution, and react under 320W ultraviolet light irradiation for 14 min; centrifuge the obtained white precipitate; filter out the white solid precipitate with a negative pressure filtration device, wash it with dichloromethane, and filter it three times repeatedly with the negative pressure filtration device. Vacuum dry the filtered solid powder at 45°C for 6 h to obtain fluorinated POSS.

[0071] This example also provides a preparation method of the anti-adhesion and low-temperature resistant material, which includes the following steps:

[0072] Weigh polyvinyl chloride resin, fluorine-containing POSS, polysiloxane, composite heat stabilizer, epoxidized soybean oil, crosslinking aid MBS, wax powder, polyethylene oxide, and anionic surfactant according to the above parts by mass, add them to a high-speed mixer, and mix and stir evenly at a rotation speed of 500 - 800 rpm to obtain mixture a; raise the temperature to 45°C, add diisooctyl cyclohexane-1,2-dicarboxylate (DEHCH) to mixture a, continue to stir at 800 - 1100 rpm and raise the temperature to 90°C to obtain mixture b. When the material is cooled to 30°C, the obtained mixture b is melt-kneaded using a screw extruder at 80 - 170°C, plasticized, extruded, granulated, dehydrated, air-dried, vibrated and sieved, and then air-dried again to obtain the anti-adhesion and low-temperature resistant material. Among them, the rotation speed of the main machine screw is 40 - 100 rmp, the temperature of the feeding section of the screw is 80 - 120°C, the temperature of the plasticizing and melting section of the screw is 130 - 150°C, and the temperature of the die head discharging section is 150 - 170°C. The material is plasticized, air-cooled and granulated by the extruder.

[0073] The anti-adhesion and low-temperature resistant material can be extruded and formed by a pipe extruder to obtain a medical catheter. Among them, the temperature of the heating area of the pipe extruder is 145°C - 175°C, the die temperature is 130°C - 150°C, and the temperature of the cooling water tank is 55°C. The inner and outer diameters of the catheter are 6.75 mm for the outer diameter and 4.5 mm for the inner diameter.

[0074] Example 8

[0075] This example provides an anti-adhesion and low-temperature resistant material. Calculated by parts by mass, the raw materials include 100 parts of polyvinyl chloride resin, 5 parts of fluorine-containing POSS, 8 parts of polysiloxane, 8 parts of composite heat stabilizer, 10 parts of epoxidized soybean oil, 35 parts of diisononyl cyclohexane-1,2-dicarboxylate (DINCH), 20 parts of tributyl acetylcitrate (ATBC), 5 parts of crosslinking aid MBS, 1.4 parts of polyethylene oxide, 5 parts of wax powder, and 0.5 part of anionic surfactant.

[0076] Among them, in terms of parts by mass, the raw materials of fluorinated POSS include 10 parts of POSS, 0.7 part of 2,2-dimethoxyphenylacetophenone, 9 parts of 1H,1H,2H,2H-perfluorodecanethiol, and 125 parts of dichloromethane. The composite heat stabilizer includes a main stabilizer and an auxiliary stabilizer with a mass ratio of 3:1. The main stabilizer is stabilizer 1010 and stabilizer 168 with a mass ratio of 2:1; the auxiliary stabilizer is phosphite; the wax powder is polyamide wax and maleic anhydride grafted PE wax with a mass ratio of 1:2; the anionic surfactant is secondary alkyl sulfonate and polystyrene sulfonic acid with a mass ratio of 1:3; the crosslinking aid is a methyl methacrylate, butadiene, styrene terpolymer with a core-shell structure (MBS crosslinking aids PA40 and PA60 from Nippon Zeon Co., Ltd.), and the mass ratio of PA40 to PA60 is 2:1. The average degree of polymerization of the polyvinyl chloride resin is 1300; the number-average molecular weight of the polysiloxane is 11000; the number-average molecular weight of the polyethylene oxide is 1×10 6 .

[0077] The fluorinated POSS is prepared by the following method: Dissolve POSS, 2,2-dimethoxyphenylacetophenone, and 1H,1H,2H,2H-perfluorodecanethiol in dichloromethane to form a solution, and react under ultraviolet light irradiation of 350W for 16 min; centrifuge the obtained white precipitate; filter out the white solid precipitate with a negative pressure suction filtration device, wash it with dichloromethane, and filter it three times repeatedly with the negative pressure suction filtration device, and vacuum dry the filtered solid powder at 45°C for 6 h to obtain fluorinated POSS.

[0078] This embodiment also provides a preparation method of the anti-adhesion and low-temperature resistant material, which includes the following steps:

[0079] Weigh polyvinyl chloride resin, fluorinated POSS, polysiloxane, composite heat stabilizer, epoxy soybean oil, crosslinking aid MBS, wax powder, polyethylene oxide, and anionic surfactant according to the above parts by mass, add them to a high-speed mixer, and mix and stir evenly at a speed of 500-800 rpm to obtain mixture a; when the temperature rises to 45°C, add diisononyl cyclohexane-1,2-dicarboxylate (DINCH) and tributyl acetylcitrate (ATBC) to mixture a, continue to stir at 800-1100 rpm and heat up to 90°C to obtain mixture b. When the material is cooled to 30°C, the obtained mixture b is melt-kneaded using a screw extruder at 80-170°C, plasticized, extruded, granulated, dehydrated, air-dried, vibrated and sieved, and then air-dried again to obtain the anti-adhesion and low-temperature resistant material. Among them, the main screw speed is 40-100 rmp, the temperature of the feeding section of the screw is 80-120°C, the temperature of the plasticizing and melting section is 130-150°C, and the temperature of the die head discharging section is 150-170°C. The material is plasticized, air-cooled and granulated by the extruder.

[0080] The anti-adhesion and low-temperature resistant material can be extruded into a medical catheter through a pipe extruder. Among them, the temperature of the heating area of the pipe extruder is 145°C to 175°C, the die temperature is 130°C to 150°C, and the temperature of the cooling water tank is 45°C. The inner and outer diameters of the catheter are 6.75 mm for the outer diameter and 4.5 mm for the inner diameter.

[0081] Example 9

[0082] This example provides an anti-adhesion and low-temperature resistant material. By mass, the raw materials include 100 parts of polyvinyl chloride resin, 2 parts of fluorinated POSS, 5 parts of polysiloxane, 5.5 parts of composite heat stabilizer, 6 parts of epoxidized soybean oil, 35 parts of diisooctyl cyclohexane-1,2-dicarboxylate (DEHCH), 25 parts of tributyl acetylcitrate (ATBC), 3 parts of crosslinking aid MBS, 1.2 parts of polyethylene oxide, 2 parts of wax powder, and 0.2 part of anionic surfactant.

[0083] Among them, by mass, the raw materials of fluorinated POSS include 10 parts of POSS, 0.5 part of 2,2-dimethoxyphenylacetophenone, 10 parts of 1H,1H,2H,2H-perfluorodecanethiol, and 105 parts of dichloromethane. The composite heat stabilizer includes a main stabilizer and an auxiliary stabilizer with a mass ratio of 4:1. The main stabilizer is stabilizer 1010 and stabilizer 168 with a mass ratio of 2:1; the auxiliary stabilizer is phosphite; the wax powder is polyamide wax and maleic anhydride grafted PE wax with a mass ratio of 1:1; the anionic surfactant is secondary alkyl sulfonate and polystyrene sulfonic acid with a mass ratio of 1:3; the crosslinking aid is a core-shell structured methyl methacrylate, butadiene, styrene terpolymer (MBS crosslinking aids PA40 and PA60 from Nippon Zeon Co., Ltd.), and the mass ratio of PA40 to PA60 is 2:1. The average degree of polymerization of the polyvinyl chloride resin is 1100; the number average molecular weight of the polysiloxane is 10000; the number average molecular weight of the polyethylene oxide is 2×10 5 .

[0084] The fluorinated POSS is prepared by the following method: Dissolve POSS, 2,2-dimethoxyphenylacetophenone, and 1H,1H,2H,2H-perfluorodecanethiol in dichloromethane to form a solution, and react under 400W ultraviolet light irradiation for 14 min; centrifuge the obtained white precipitate; filter out the white solid precipitate with a negative pressure filtration device, wash it with dichloromethane, and filter it three times repeatedly with the negative pressure filtration device. Vacuum dry the filtered solid powder at 45°C for 6 h to obtain fluorinated POSS.

[0085] This example also provides a preparation method of the anti-adhesion and low-temperature resistant material, which includes the following steps:

[0086] Weigh polyvinyl chloride resin, fluorine-containing POSS, polysiloxane, composite heat stabilizer, epoxidized soybean oil, crosslinking aid MBS, wax powder, polyethylene oxide, and anionic surfactant according to the above parts by mass, add them to a high-speed mixer, and mix and stir evenly at a rotation speed of 500 - 800 rpm to obtain mixture a; raise the temperature to 45°C, add diisononyl cyclohexane-1,2-dicarboxylate (DINCH) and tributyl acetylcitrate (ATBC) to mixture a, continue to stir at 800 - 1100 rpm and raise the temperature to 90°C to obtain mixture b. When the material is cooled to 30°C, the obtained mixture b is melt-kneaded at 80 - 170°C using a screw extruder, plasticized, extruded, granulated, dehydrated, air-dried, vibrated and sieved, and then air-dried again to obtain the anti-adhesion and low-temperature resistant material. Among them, the rotation speed of the main machine screw is 40 - 100 rmp, the temperature of the feeding section of the screw is 80 - 120°C, the temperature of the plasticizing and melting section is 130 - 150°C, and the temperature of the die head discharging section is 150 - 170°C. The material is plasticized, air-cooled and granulated by the extruder.

[0087] The anti-adhesion and low-temperature resistant material can be extruded and formed by a pipe extruder to obtain a medical catheter. Among them, the temperature of the heating area of the pipe extruder is 145°C - 175°C, the die temperature is 130°C - 150°C, and the temperature of the cooling water tank is 55°C. The inner and outer diameters of the catheter are 6.75 mm for the outer diameter and 4.5 mm for the inner diameter.

[0088] Example 10

[0089] This example provides an anti-adhesion and low-temperature resistant material. Calculated by parts by mass, the raw materials include 100 parts of polyvinyl chloride resin, 1.5 parts of fluorine-containing POSS, 7 parts of polysiloxane, 7 parts of composite heat stabilizer, 9 parts of epoxidized soybean oil, 35 parts of diisooctyl cyclohexane-1,2-dicarboxylate (DEHCH), 30 parts of diisononyl cyclohexane-1,2-dicarboxylate (DINCH), 4 parts of crosslinking aid MBS, 1.3 parts of polyethylene oxide, 2 parts of wax powder, and 0.4 part of anionic surfactant.

[0090] Among them, in terms of parts by mass, the raw materials of fluorinated POSS include 10 parts of POSS, 1 part of 2,2-dimethoxyphenylacetophenone, 15 parts of 1H,1H,2H,2H-perfluorodecanethiol, and 146 parts of dichloromethane. The composite heat stabilizer includes a main stabilizer and an auxiliary stabilizer with a mass ratio of 4:1. The main stabilizer is stabilizer 1010 and stabilizer 168 with a mass ratio of 2:1; the auxiliary stabilizer is phosphite; the wax powder is polyamide wax and maleic anhydride grafted PE wax with a mass ratio of 1:1; the anionic surfactant is secondary alkyl sulfonate and polystyrene sulfonic acid with a mass ratio of 1:3; the crosslinking aid is a methyl methacrylate, butadiene, styrene terpolymer with a core-shell structure (MBS crosslinking aids PA40 and PA60 from Nippon Zeon Co., Ltd.), and the mass ratio of PA40 to PA60 is 2:1. The average degree of polymerization of the polyvinyl chloride resin is 1000; the number average molecular weight of the polysiloxane is 12000; the number average molecular weight of the polyethylene oxide is 1×10 6 .

[0091] The fluorinated POSS is prepared by the following method: Dissolve POSS, 2,2-dimethoxyphenylacetophenone, and 1H,1H,2H,2H-perfluorodecanethiol in dichloromethane to form a solution, and react under ultraviolet light of 500W for 18 min; centrifuge the obtained white precipitate; filter out the white solid precipitate with a negative pressure filtration device, wash it with dichloromethane, and filter it three times repeatedly with the negative pressure filtration device, and vacuum dry the filtered solid powder at 45°C for 6 h to obtain fluorinated POSS.

[0092] This example also provides a preparation method of the anti-adhesion and low-temperature resistant material, which includes the following steps:

[0093] Weigh the polyvinyl chloride resin, fluorinated POSS, polysiloxane, composite heat stabilizer, epoxy soybean oil, crosslinking aid MBS, wax powder, polyethylene oxide, and anionic surfactant according to the above parts by mass, add them to a high-speed mixer, and mix and stir evenly at a speed of 500-800 rpm to obtain mixture a; when the temperature rises to 45°C, add diisooctyl cyclohexane-1,2-dicarboxylate (DEHCH) and diisononyl cyclohexane-1,2-dicarboxylate (DINCH) to mixture a, and continue to stir at 800-1100 rpm and heat up to 90°C to obtain mixture b. When the material is cooled to 30°C, the obtained mixture b is melt-kneaded using a screw extruder at 80-170°C, plasticized, extruded, granulated, dehydrated, air-dried, vibrated and sieved, and then air-dried again to obtain the anti-adhesion and low-temperature resistant material. Among them, the main screw speed is 40-100 rmp, the temperature of the feeding section of the screw is 80-120°C, the temperature of the plasticizing and melting section is 130-150°C, and the temperature of the die head discharging section is 150-170°C. The material is plasticized, air-cooled and granulated by the extruder.

[0094] The anti-adhesion and low-temperature resistant material can be extruded into a medical catheter through a pipe extruder. Among them, the temperature of the heating area of the pipe extruder is 145°C to 175°C, the die temperature is 130°C to 150°C, and the temperature of the cooling water tank is 50°C. The inner and outer diameters of the catheter are 6.75 mm for the outer diameter and 4.5 mm for the inner diameter.

[0095] Example 11

[0096] This example provides an anti-adhesion and low-temperature resistant material. In terms of parts by mass, the raw materials include 100 parts of polyvinyl chloride resin, 4 parts of fluorinated POSS, 4 parts of polysiloxane, 5 parts of composite heat stabilizer, 6 parts of epoxidized soybean oil, 60 parts of tributyl acetylcitrate (ATBC), 2 parts of cross-linking aid MBS, 0.6 part of polyethylene oxide, 1 part of wax powder, and 0.4 part of anionic surfactant.

[0097] Among them, in terms of parts by mass, the raw materials of fluorinated POSS include 10 parts of POSS, 0.6 part of 2,2-dimethoxyphenylacetophenone, 4 parts of 1H,1H,2H,2H-perfluorodecanethiol, and 100 parts of dichloromethane. The composite heat stabilizer includes a main stabilizer and an auxiliary stabilizer with a mass ratio of 2:1. The main stabilizer is stabilizer 1010 and stabilizer 168 with a mass ratio of 2:1; the auxiliary stabilizer is phosphite; the wax powder is polyamide wax and maleic anhydride grafted PE wax with a mass ratio of 1:2; the anionic surfactant is sodium dodecylbenzenesulfonate and polystyrene sulfonic acid with a mass ratio of 1:2; the cross-linking aid is a methyl methacrylate, butadiene, styrene terpolymer with a core-shell structure (MBS cross-linking aids PA40 and PA60 from Nippon Zeon Co., Ltd.), and the mass ratio of PA40 to PA60 is 2:1. The average degree of polymerization of the polyvinyl chloride resin is 1200; the number average molecular weight of the polysiloxane is 15000; the number average molecular weight of the polyethylene oxide is 1×10 6 .

[0098] The fluorinated POSS is prepared by the following method: Dissolve POSS, 2,2-dimethoxyphenylacetophenone, and 1H,1H,2H,2H-perfluorodecanethiol in dichloromethane to form a solution, and react under ultraviolet light irradiation of 430 W for 11 min; centrifuge the obtained white precipitate; filter out the white solid precipitate with a negative pressure filtration device, wash it with dichloromethane, and filter it three times repeatedly with the negative pressure filtration device. Vacuum dry the filtered solid powder at 45°C for 6 h to obtain fluorinated POSS.

[0099] This example also provides a preparation method for the anti-adhesion and low-temperature resistant material, which includes the following steps:

[0100] Weigh polyvinyl chloride resin, fluorine-containing POSS, polysiloxane, composite heat stabilizer, epoxidized soybean oil, crosslinking aid MBS, wax powder, polyethylene oxide, and anionic surfactant according to the above parts by mass, add them to a high-speed mixer, and mix and stir evenly at a rotation speed of 500 - 800 rpm to obtain mixture a; raise the temperature to 45°C, add tributyl acetylcitrate (ATBC) to mixture a, continue stirring at 800 - 1100 rpm and raise the temperature to 90°C to obtain mixture b. When the material is cooled to 30°C, the obtained mixture b is melt-kneaded at 80 - 170°C using a screw extruder, plasticized, extruded, granulated, dehydrated, air-dried, vibrated through a sieve, and then air-dried again to obtain the anti-adhesion and low-temperature-resistant material. Among them, the rotation speed of the main machine screw is 40 - 100 rmp, the temperature of the feeding section of the screw is 80 - 120°C, the temperature of the plasticizing and melting section of the screw is 130 - 150°C, and the temperature of the die head discharging section is 150 - 170°C. The material is plasticized, air-cooled, and granulated by the extruder.

[0101] The anti-adhesion and low-temperature-resistant material can be extruded and formed by a pipe extruder to obtain a medical catheter. Among them, the temperature of the heating area of the pipe extruder is 145°C - 175°C, the temperature of the mold is 130°C - 150°C, and the temperature of the cooling water tank is 45°C. The inner and outer diameters of the catheter are 6.75 mm for the outer diameter and 4.5 mm for the inner diameter.

[0102] Example 12

[0103] This example provides an anti-adhesion and low-temperature-resistant material. Calculated by parts by mass, the raw materials include 100 parts of polyvinyl chloride resin, 4.5 parts of fluorine-containing POSS, 6 parts of polysiloxane, 6 parts of composite heat stabilizer, 8 parts of epoxidized soybean oil, 45 parts of diisononyl cyclohexane-1,2-dicarboxylate (DINCH), 2.5 parts of crosslinking aid MBS, 0.7 part of polyethylene oxide, 3 parts of wax powder, and 0.2 part of anionic surfactant.

[0104] Among them, in terms of parts by mass, the raw materials of fluorinated POSS include 10 parts of POSS, 0.6 part of 2,2-dimethoxyphenylacetophenone, 12 parts of 1H,1H,2H,2H-perfluorodecanethiol, and 131 parts of dichloromethane. The composite heat stabilizer includes a main stabilizer and an auxiliary stabilizer with a mass ratio of 3:1. The main stabilizer is stabilizer 1010 and stabilizer 168 with a mass ratio of 2:1; the auxiliary stabilizer is phosphite; the wax powder is polyamide wax and maleic anhydride grafted PE wax with a mass ratio of 1:1.5; the anionic surfactant is sodium dodecyl sulfate and polystyrene sulfonic acid with a mass ratio of 1:2; the crosslinking aid is a methyl methacrylate, butadiene, styrene terpolymer with a core-shell structure (MBS crosslinking aids PA40 and PA60 from Nippon Zeon Co., Ltd.), and the mass ratio of PA40 to PA60 is 2:1. The average degree of polymerization of the polyvinyl chloride resin is 1200; the number average molecular weight of the polysiloxane is 13000; the number average molecular weight of the polyethylene oxide is 7×10 5 .

[0105] The fluorinated POSS is prepared by the following method: Dissolve POSS, 2,2-dimethoxyphenylacetophenone, and 1H,1H,2H,2H-perfluorodecanethiol in dichloromethane to form a solution, and react under 380W ultraviolet light irradiation for 13 min; Centrifuge the obtained white precipitate; Filter out the white solid precipitate with a negative pressure suction filtration device, wash it with dichloromethane, and filter it three times repeatedly with the negative pressure suction filtration device. Vacuum dry the filtered solid powder at 45°C for 6 h to obtain fluorinated POSS.

[0106] This embodiment also provides a preparation method of the anti-adhesion and low-temperature resistant material, which includes the following steps:

[0107] Weigh the polyvinyl chloride resin, fluorinated POSS, polysiloxane, composite heat stabilizer, epoxy soybean oil, crosslinking aid MBS, wax powder, polyethylene oxide, and anionic surfactant according to the above parts by mass, add them to a high-speed mixer, and mix and stir evenly at a speed of 500-800 rpm to obtain mixture a; Raise the temperature to 45°C, add diisooctyl cyclohexane-1,2-dicarboxylate (DEHCH) and diisononyl cyclohexane-1,2-dicarboxylate (DINCH) to mixture a, continue to stir at 800-1100 rpm and raise the temperature to 90°C to obtain mixture b. When the material is cooled to 30°C, the obtained mixture b is melt-kneaded at 80-170°C using a screw extruder, plasticized, extruded, granulated, dehydrated, air-dried, vibrated and sieved, and then air-dried again to obtain the anti-adhesion and low-temperature resistant material. Among them, the main screw speed is 40-100 rmp, the temperature of the feeding section of the screw is 80-120°C, the temperature of the plasticizing and melting section is 130-150°C, and the temperature of the die head discharging section is 150-170°C. The material is plasticized, air-cooled and granulated by the extruder.

[0108] The anti-adhesion and low-temperature resistant material can be extruded into a medical catheter by a pipe extruder. Among them, the temperature of the heating area of the pipe extruder is 145°C to 175°C, the mold temperature is 130°C to 150°C, and the temperature of the cooling water tank is 50°C. The inner and outer diameters of the catheter are 6.75 mm for the outer diameter and 4.5 mm for the inner diameter.

[0109] Comparative Example 1

[0110] Comparative Example 1 is basically the same as Example 12, except that: 4.5 parts of fluorinated POSS in Example 12 are replaced with 4.5 parts of solid powder A.

[0111] The solid powder A is prepared by the following method: By mass, 10 parts of POSS, 0.05 part of 2,2-dimethoxyphenylacetophenone, and 2 parts of 1H,1H,2H,2H-perfluorodecanethiol are dissolved in 100 parts of dichloromethane to form a solution, and the reaction is carried out for 13 min under irradiation with 380 W ultraviolet light; the obtained white precipitate is centrifuged; the white solid precipitate is filtered out with a negative pressure suction filtration device, washed with dichloromethane, and filtered three times repeatedly with the negative pressure suction filtration device, and the filtered solid powder is vacuum dried at 45°C for 6 h to obtain solid powder A.

[0112] Comparative Example 2

[0113] Comparative Example 2 is basically the same as Example 12, except that: 4.5 parts of fluorinated POSS in Example 12 are replaced with 4.5 parts of solid powder B.

[0114] The solid powder B is prepared by the following method: By mass, 10 parts of POSS, 0.26 part of 2,2-dimethoxyphenylacetophenone, and 2 parts of 1H,1H,2H,2H-perfluorodecanethiol are dissolved in 100 parts of dichloromethane to form a solution, and after stirring evenly, the reaction is carried out for 13 min under irradiation with 230 W ultraviolet light; the obtained white precipitate is centrifuged; the white solid precipitate is filtered out with a negative pressure suction filtration device, washed with dichloromethane, and filtered three times repeatedly with the negative pressure suction filtration device, and the filtered solid powder is vacuum dried at 45°C for 6 h to obtain solid powder B.

[0115] Comparative Example 3

[0116] Comparative Example 3 is basically the same as Example 11, except that: 4 parts of polysiloxane in Example 11 are removed.

[0117] Comparative Example 4

[0118] Comparative Example 4 is basically the same as Example 10, except that: 4 parts by mass of crosslinking aid MBS in Example 10 are removed.

[0119] Comparative Example 5

[0120] Comparative Example 5 is basically the same as Example 9, except that: the 2 parts of wax powder in Example 9 are replaced by 2 parts of polyethylene wax, where the polyamide wax and maleic anhydride grafted PE wax are in a mass ratio of 1:1.

[0121] Comparative Example 6

[0122] Comparative Example 6 is basically the same as Example 8, except that: the 0.5 part of anionic surfactant in Example 8 is removed.

[0123] Comparative Example 7

[0124] Comparative Example 7 is basically the same as Example 7, except that: the 5.5 parts of composite heat stabilizer in Example 7 are replaced by 5.5 parts by mass of calcium-zinc heat stabilizer.

[0125] Comparative Example 8

[0126] Comparative Example 8 is basically the same as Example 6, except that: the anti-adhesion and low-temperature resistant material in Example 6 can be extruded and formed by a pipe extruder to obtain a medical catheter; among them, the temperature of the heating area of the pipe extruder is 145°C to 175°C, the die temperature is 130°C to 150°C, and the temperature of the cooling water tank is adjusted to 10°C; the inner and outer diameters of the catheter are 6.75 mm for the outer diameter and 4.5 mm for the inner diameter.

[0127] Comparative Example 9

[0128] A PVC polymer material, in parts by mass, includes the following raw materials: 100 parts of polyvinyl chloride resin, 5.5 parts of calcium-zinc heat stabilizer, 7 parts of epoxidized soybean oil, 3.5 parts of polyethylene wax powder, and 55 parts of diisooctyl cyclohexane-1,2-dicarboxylate (DEHCH).

[0129] The PVC polymer material is prepared by the following method:

[0130] Weigh the above raw materials and add them to a high-speed mixer, stir at a speed of 500 - 800 rpm to obtain a homogeneous mixture a; heat up to 45°C, control the speed at 800 - 1100 rpm, add diisooctyl cyclohexane-1,2-dicarboxylate (DEHCH) to mixture a, heat up to 90°C and continue to stir evenly to obtain mixture b; cool to 30°C, and use a screw extruder to melt and knead the obtained mixture b at 80 - 170°C for plasticization and extrusion, and finally pelletize; among them, the main screw speed is 40 - 100 rmp, the temperature of the feeding section of the screw is 80 - 120°C, the temperature of the plasticization and melting section is 130 - 150°C, and the temperature of the die head discharging section is 150 - 170°C; after pelletizing, dehydrate, air-dry, vibrate and screen, and then air-dry again to obtain the PVC polymer material.

[0131] The PVC material for the PVC polymer material is extruded by a pipe extruder to obtain a PVC conduit. The temperature of the heating area of the pipe extruder is 150°C to 175°C, the die temperature is 130°C to 150°C, and the temperature of the cooling water tank is 10°C. The inner and outer diameters of the conduit are set to an outer diameter of 6.75 mm and an inner diameter of 4.5 mm.

[0132] Comparative Example 10

[0133] Comparative Example 10 is basically the same as Example 5, except that: polyethylene oxide in Example 5 is removed.

[0134] The above examples and comparative examples are subjected to performance tests, and the test results are shown in Table 1. The performance test methods in the above examples and comparative examples are as follows:

[0135] (1) Platelet counting method: According to the ratio of adding 0.01 mL of calcium chloride solution and 0.01 mL of low-concentration heparin sodium solution to every 1 mL of blood, the three are mixed evenly. Put the test sample, negative control, and blank control into test tubes, and add the previously mixed whole blood to each test tube according to the ratio of 1 mL of blood in contact with every 12 cm2 of the sample. The blank control is blood that has not contacted the material. All test tubes are oscillated in a water bath at 37°C and 60 rpm for 1 h. After incubation for 1 h, add EDTA with a final concentration of 5 mmol / L to each test tube to terminate the reaction, gently mix each test tube, transfer all the blood to another test tube with the same label, and place it on ice for standby. After each test tube is gently rotated and inverted at least 8 times, it is put into a blood analyzer for detection, the platelet value is read, and the platelet adhesion rate is calculated according to formula (1).

[0136] C = (B - A) / B (1)

[0137] A: The average value of platelet count of the test sample;

[0138] B: The average value of platelet count of the blank control.

[0139] The size of the platelet adhesion rate reflects the situation of the sample adhering to blood cells. The smaller the platelet adhesion rate, the better the anti-blood (cell) adhesion effect of the sample.

[0140] (2) Protein adhesion ELISA method: After the sample is washed with phosphate buffer solution (PBS), it is placed in a 100 μg / ml BSA solution and soaked at a constant temperature of 37 °C for 3 h. The soaked sample is taken out with tweezers and then thoroughly rinsed with PBS buffer solution to wash off the unadsorbed BSA protein on the surface. A 0.1% (mass fraction) SDS detergent is prepared with PBS buffer solution. A certain volume of the cleaning solution is measured with a pipette, and the rinsed sample is soaked in the detergent and ultrasonically cleaned for 30 min. The protein solution obtained after cleaning is added to a 96-well plate with a pipette gun, Bradford reagent is added, and the 96-well plate is placed in an ELISA reader to measure the absorbance of the solution at an absorption wavelength of 595 nm. Finally, the surface adsorption amount is calculated according to the standard curve, and each sample is measured 3 times and the average value is taken. The surface adsorption amount reflects the protein adhesion effect, and the less the surface adsorption amount, the better the anti-protein adhesion effect.

[0141] (3) Fluorescent protein labeling method: The material sterilized by ultraviolet light for 20 min is soaked in a 0.5 mg / ml fluorescently labeled bovine serum albumin (BSA-FITC) solution for 2 hours to allow the protein to adsorb on the material surface. Then it is gently washed five times with phosphate buffer solution (PBS) to remove the protein molecules that are not tightly bound. A confocal laser scanning microscope is used to take fluorescent images of the material surface. The fluorescent dots reflect the protein adhesion effect, and the fewer the fluorescent dots, the better the anti-protein adhesion effect.

[0142] (4) Contact angle measurement: Five points are selected from each catheter sample piece to cut out 2*2 cm 2 sample pieces, and the water contact angle is measured on a contact angle measuring instrument. The water droplet volume is set to 8 μl / time, and the average value of the 5-point measurements is taken as the test result of the sample piece. The size of the contact angle reflects the hydrophilicity of the material. The smaller the contact angle, the better the hydrophilicity of the material.

[0143] (5) Oscillation treatment liquid ultraviolet absorbance measurement: Samples of the same specification are placed in purified water and oscillated in a constant temperature water bath (37 °C, 60 rpm) for 7 days. The oscillated treatment liquid is taken, and within 5 h, a 1 cm cuvette is used with the blank control solution as the reference to measure the absorbance within a certain wavelength range. The size of the absorbance reflects the precipitation and shedding of the modified sample. The larger the absorbance, the more serious the precipitation and shedding, and the worse the corresponding coating firmness.

[0144] (6) The anti-adhesion and low-temperature resistant material is made into a film, and the tensile properties of the test specimen are tested according to the method of GB / T 1040.2-2006. The thickness of the test sample is 1 mm.

[0145] (7) The ultraviolet absorbance is tested according to the chemical analysis method in GB / T 14233.1-2008 to test the precipitation of additives in the material.

[0146] (8) The cytotoxicity was determined according to the standard: GB / T 16886.5-2017 Biological evaluation of medical devices - Part 5: Tests for in vitro cytotoxicity.

[0147] (9) The glass transition temperature was determined according to GB / T 19466.2-2004 Plastics - Differential scanning calorimetry (DSC) - Part 2: Determination of the glass transition temperature.

[0148] (10) The dynamic friction coefficient was obtained by testing with a friction coefficient tester.

[0149] Table 1 Test results of Examples 1-12 and Comparative Examples 1-10

[0150]

[0151]

[0152]

[0153] Referring to Table 1 and comparing Example 7 with Comparative Example 7, it can be seen that the composite stabilizer used in the present invention has good thermal stability while not containing metal calcium ions, greatly weakening the activity of coagulation factor 4 and avoiding the generation of coagulation.

[0154] Referring to Table 1 and comparing Example 12 with Comparative Examples 1-2, it can be seen that the introduction of fluorinated POSS into the PVC material in the present invention greatly reduces the surface energy of the material, reduces the adhesion of biological cells on the surface. At the same time, since the fluorinated POSS is a microscopic cage structure containing a large number of silicon-oxygen bonds, it not only has good biocompatibility but also can act as a nucleating agent, facilitating the orderly arrangement of the PVC molecular chains, making the arrangement of the microscopic molecular chains on the material surface more compact and the macroscopic and microscopic structures more flat, and not easily adsorbing proteins, biological tissues and cells.

[0155] Referring to Table 1 and comparing Example 11 with Comparative Example 3, it can be seen that the introduction of polysiloxane in the present invention not only improves the biocompatibility of the material but also can play a lubricating role in the PVC material. At the same time, due to the high flexibility of the polysiloxane molecular chain, the low-temperature flexibility of the PVC material is improved, promoting the interaction between the fluorinated POSS and the various components in the PVC, enabling the fluorinated POSS to be dispersed in the PVC matrix.

[0156] Referring to Table 1 and comparing Example 9 with Comparative Example 5, it can be seen that the addition of polyamide wax and maleic anhydride grafted PE wax in the present invention can not only play a role in processing lubrication but also reduce the glass transition temperature of the material, improve the low-temperature resistance, and is an important compatibilizer, further promoting the compatibility of the fluorinated POSS and other components and not easily precipitating.

[0157] Referring to Table 1 and comparing Example 8 with Comparative Example 6, it can be seen that in the present invention, the addition of an anionic surfactant makes the material surface exhibit a negative charge, and through the electrostatic repulsion effect, it is possible to hinder the adsorption of various negatively charged components (such as hemoglobin, platelets, some plasma proteins, etc.) in the blood environment, thus being beneficial to anticoagulation.

[0158] Referring to Table 1 and comparing Example 10 with Comparative Example 4, it can be seen that the methyl methacrylate, butadiene, styrene terpolymer (MBS) with a core-shell structure added in the present invention can act as a cross-linking site between the molecular chains of PVC, polysiloxane, plasticizer, fluorinated POSS, etc., promoting the compatibility of each component and improving the low-temperature flexibility and anti-bleeding property of the material.

[0159] Referring to Table 1 and comparing Example 6 with Comparative Examples 8-9, it can be seen that in the extrusion molding step of the pipe extruder in the present invention, the temperature of the cooling water tank is a relatively high temperature of 40°C to 60°C, enabling the PVC pipeline extruded from the die orifice to have sufficient time to crystallize, with more sufficient crystallization and a smoother and flatter surface. In addition, due to the relatively high cooling temperature, which is higher than the glass transition temperature, fluorinated POSS, polysiloxane, and anionic surfactant can be enriched on the surface, further enhancing the biocompatibility and anti-adhesion effect.

[0160] Referring to Table 1 and comparing Example 5 with Comparative Example 10, it can be seen that the polyethylene oxide added in the present invention can prevent thrombin from adsorbing on the material surface, further enhancing the anti-adhesion effect of the material.

[0161] In summary, the present invention combines polyvinyl chloride resin, composite heat stabilizer, plasticizer, epoxy soybean oil with fluorinated POSS, modified wax powder, surfactant, polysiloxane, etc., and adopts the preparation processes of melt blending granulation and extrusion, along with matching process parameters, to obtain an anti-adhesive and low-temperature-resistant material with excellent properties. The elongation at break at -10°C can reach more than 40%, the elongation at break at 25°C can reach more than 300%, and the glass transition temperature is below -21°C, which can greatly improve the low-temperature flexibility of the material, facilitate the use of medical catheter products, and avoid problems such as poor flexibility or even rupture during use or transportation. At the same time, the water contact angle of the prepared material increases from 85° to 140°, greatly enhancing the hydrophobicity of the material, thereby improving the anti-fouling and anti-adhesion effects of the product. In the present invention, due to fluorinated POSS, the surface energy of the material is greatly reduced, reducing the adhesion of biological cells on the surface. At the same time, since fluorinated POSS is a microscopic cage structure containing a large number of silicon-oxygen bonds, it not only has good biocompatibility but also can act as a nucleating agent, being beneficial to the orderly arrangement of PVC molecular chains, making the microscopic molecular chain arrangement on the material surface more compact and the macroscopic and microscopic structures more flat, and not easily adsorbing proteins, biological tissues, and cells.

[0162] In addition, the low-temperature resistant and anti-adhesion modification of the present invention is for the modification of PVC pellets, that is, modification from the source, which means that the anti-adhesion material is directly used to prepare products, with a wider range of applicable products and more convenient processing; the preparation process is simple and easy to operate, the material selection is safe, only simple reaction, blending, and extrusion devices are required, without using more complex production equipment, and the preparation process is safe and controllable, and it can also be applied to large-scale production. The anti-adhesion stability of the present invention is good. The products prepared by the present invention still have a significant anti-adhesion effect after being oscillated at 60 rpm in a 37°C constant temperature water bath for 7 days, and very little precipitates (the ultraviolet absorbance of the oscillation treatment solution < 0.1 Abs), and its anti-adhesion efficacy time is longer.

[0163] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them; although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that: it is still possible to modify the specific implementation manners of the present invention or perform equivalent replacements on some technical features; without departing from the spirit of the technical solutions of the present invention, they should all be covered within the scope of the technical solutions claimed by the present invention.

Claims

1. An anti-adhesion and low-temperature resistant material, wherein the raw materials include, by weight, 100 parts of polyvinyl chloride resin, 1-5 parts of fluorinated octavinyl cage polysilsesquioxane, 3-8 parts of polysiloxane, 5-10 parts of composite heat stabilizer, 5-10 parts of epoxy soybean oil, 30-70 parts of plasticizer, 1-5 parts of crosslinking aid MBS, 0.5-1.5 parts of polyethylene oxide, 0.5-5 parts of wax powder and 0.1-0.5 parts of anionic surfactant; The raw materials of fluorine-containing octavinyl cage-type polysilsesquioxane include, by weight, 10 parts of cage-type polysilsesquioxane, 2-15 parts of 1H,1H,2H,2H-perfluorodecanethiol, 0.1-1 parts of 2,2-dimethoxyphenylacetophenone and 100-150 parts of dichloromethane; The preparation method of fluorine-containing octavinyl cage-type polysilsesquioxane comprises the following steps: The cage-type polysilsesquioxane, 1H,1H,2H,2H-perfluorodecanethiol and 2,2-dimethoxyphenylacetophenone are dissolved in a dichloromethane solution; the mixture is reacted under 300-500 W ultraviolet light for 10-20 min, and a white precipitate is obtained by centrifugation; the fluorinated octavinyl cage-type polysilsesquioxane is obtained after washing and drying; The composite heat stabilizer includes a main stabilizer and an auxiliary stabilizer in a mass ratio of (2-4):1, wherein the main stabilizer is stabilizer 1010 and stabilizer 168 in a mass ratio of 2:1; the auxiliary stabilizer is phosphite; The wax powder is polyamide wax and maleic anhydride grafted PE wax in a mass ratio of 1: (1-2); the anionic surfactant is one of sodium secondary alkyl sulfonate, sodium dodecylbenzene sulfonate, and sodium dodecyl sulfate, which are compounded with polystyrene sulfonic acid in a mass ratio of 1: (2-3).

2. The anti-adhesion and low-temperature resistant material according to claim 1, characterized in that: The average degree of polymerization of polyvinyl chloride resin is 1000-1800; the number average molecular weight of polysiloxane is 1000-15000; the number average molecular weight of polyethylene oxide is 1×10 5 ~1×10 6 .

3. The anti-adhesion and low-temperature resistant material according to claim 1, characterized in that: The plasticizer is one of diisooctyl cyclohexane 1,2-dicarboxylate, diisononyl cyclohexane 1,2-dicarboxylate, and tributyl acetyl citrate, or a combination of at least two of them.

4. A method for preparing the anti-adhesion and low-temperature resistant material according to any one of claims 1 to 3, comprising the following steps: Add polyvinyl chloride resin, fluorinated octavinyl cage polysilsesquioxane, polysiloxane, composite heat stabilizer, epoxy soybean oil, crosslinking aid MBS, wax powder, polyethylene oxide, and anionic surfactant into a high-speed mixer, and stir evenly at 500-800 rpm to obtain a mixture a; Raise the temperature to 40-50°C, add plasticizer to mixture a, continue stirring at 800-1100 rpm and raise the temperature to 80-100°C to obtain mixture b; The mixture is cooled to 20-30°C, melt-kneaded at 80-170°C, plasticized, extruded, and finally granulated to obtain an anti-adhesion and low-temperature resistant material.

5. The preparation method according to claim 4, characterized in that: A single-screw or twin-screw extruder is used for melt kneading at 80-170°C, a screw speed of 40-100 rpm, a screw feed section temperature of 80-120°C, a plasticizing and melting section temperature of 130-150°C, and a die discharge section temperature of 150-170°C.

6. A method for applying the anti-adhesion and low-temperature resistant material according to any one of claims 1 to 3, characterized in that: Anti-adhesion and low-temperature resistant materials are used to prepare tubing for continuous renal replacement therapy, extracorporeal membrane oxygenation tubing, extracorporeal circulation tubing, vascular access for dialysis catheters, and vascular access for disposable arteriovenous puncture devices.

7. The application method according to claim 6, characterized in that: The anti-adhesion and low-temperature resistant material is extruded and formed by a pipe extruder; the temperature of the heating area of ​​the pipe extruder is 145°C to 175°C, the temperature of the mold is 130°C to 150°C, and the temperature of the cooling water tank is 40°C to 60°C.

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