Preparation method and application of waterborne polyurethane anti-adhesion coating

By introducing a disulfide bond structure into the aqueous polyurethane and reacting with apropenyl-containing polyfluoride, a fluorinated aqueous polyurethane emulsion was prepared for the preparation of an anti-adhesion coating, which solved the problem of prone to scaling and infection in long-term indwelling medical devices, and achieved excellent biocompatibility and anti-adhesion properties.

CN116375963BActive Publication Date: 2025-05-13WEIGAO HLDG +1
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Patent Information

Application Number
CN202310250585.1
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2023-03-13
Publication Date
2025-05-13
Estimated Expiration
2043-03-13

AI Technical Summary

Technical Problem

Interventional medical devices that are indulged for a long time are prone to scaling, infection and thrombosis, resulting in patient pain and increased medical costs.

Method used

Fluorinated aqueous polyurethane emulsions were prepared by introducing disulfide bond structures into the aqueous polyurethane molecular chain and reacting with the propylene-containing polyfluoride by disulfide bond-ene addition to prepare a fluorinated aqueous polyurethane emulsion for the preparation of an anti-adhesion coating.

Benefits of technology

The prepared fluorinated aqueous polyurethane material has excellent biocompatibility and anti-adhesion properties, which can effectively prevent the adhesion of sediments, bacteria and plasma proteins on the surface of medical devices, and reduce the risk of scaling and infection.

✦ Generated by Eureka AI based on patent content.

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Abstract

The present invention belongs to the field of surface coating material synthesis and application technology of medical devices. The present invention provides a preparation method and application of an aqueous polyurethane anti-adhesion coating, etc. The new fluorinated aqueous polyurethane emulsion is obtained by reacting acryl-containing polyfluoride with an aqueous polyurethane dispersion; the number of fluorine atoms in the acryl-containing polyfluoride is 10 to 14; in the polyurethane molecular chain of the aqueous polyurethane dispersion, aliphatic polycarbonate diol and polyethylene glycol structures are used as soft segments, 4,4'-dicyclohexylmethane diisocyanate structure is used as hard segment, 2,2-dimethylol propionic acid structure is used as internal emulsifier part, and contains disulfide bond structure. The fluorinated aqueous polyurethane material and its coating provided by the present invention have excellent biocompatibility and anti-adhesion, and can be applied to long-term indwelling interventional medical devices.
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Description

Technical Field

[0001] The present invention belongs to the technical field of synthesis and application of surface coating materials for medical devices, and specifically relates to a fluorinated water-based polyurethane emulsion, an anti-adhesion coating, and a preparation method and application thereof, including a preparation method of a water-based polyurethane anti-adhesion coating, etc. Background Art

[0002] Medical devices include interventional devices. For example, ureteral stents are used to support and drain the human ureter, and the retention time in the human body ranges from 30 days to 1 year. Intravascular catheters include central venous catheters, peripheral venous catheters, arterial catheters, balloon dilatation catheters, floating catheters, etc. They are the main reliance for treatment methods such as hemodynamic monitoring, safe infusion, intravenous nutritional support and hemodialysis, and have become an indispensable and important medical device in clinical medical practice. At present, long-term interventional medical devices have scaling (such as the phenomenon that during the retention process of ureteral stents, the surface of the stent has sediment in the urine attached or embedded to form a hard shell), infection, thrombosis and other problems, causing multiple pains to patients and increasing medical expenses. Therefore, in the field of long-term indwelling medical devices, it is of great significance to develop anti-adhesion coatings that effectively prevent sediment adhesion, bacterial adhesion, plasma protein and platelet adhesion.

[0003] Fluorine atoms with low surface energy tend to migrate to the polymer-air interface under thermodynamic driving force to form an anti-adhesion layer. Polyurethane is widely used in the medical industry because of its good compatibility with many polymers. Therefore, fluorine-functionalized waterborne polyurethane can be used as an anti-adhesion coating material for medical devices.

[0004] At present, the methods for preparing fluorine-functionalized waterborne polyurethanes are mainly: 1. Introducing hydroxyl-functionalized fluorides into the polyurethane molecular chain through polyurethane chemistry; 2. Introducing double-bond fluorides into the polyurethane molecular chain through persulfate-catalyzed olefin click chemistry. As for the first method, when the fluorine content is too high, the high hydrophobicity of the polyurethane molecular chain will cause the prepared aqueous polyurethane dispersion to be unstable, and even make the polyurethane molecular chain unable to disperse in water. In the method of introducing fluorides through olefin click chemistry, the emulsion polymerization of double-bond terminated polyurethane prepolymers and double-bond functionalized fluorides requires the addition of a large amount of persulfate catalyst. Summary of the invention

[0005] In view of the above problems, the present invention provides a novel preparation method and application of fluorinated waterborne polyurethane emulsion. The fluorinated waterborne polyurethane material and its coating provided by the present invention have excellent biocompatibility and anti-adhesion properties, and can be applied to long-term indwelling interventional medical devices.

[0006] The present invention provides a fluorinated aqueous polyurethane emulsion, which is obtained by reacting acryl-containing polyfluoride with an aqueous polyurethane dispersion;

[0007] The number of fluorine atoms in the acryl-containing polyfluoride is 10 to 14; in the polyurethane molecular chain of the aqueous polyurethane dispersion, aliphatic polycarbonate diol and polyethylene glycol structures are soft segments, 4,4'-dicyclohexylmethane diisocyanate structure is hard segment, 2,2-dihydroxymethylpropionic acid structure is internal emulsifier part, and contains disulfide bond structure.

[0008] Preferably, the acryl-containing polyfluoride is dodecafluoroheptyl methacrylate.

[0009] The present invention provides a method for preparing the fluorinated aqueous polyurethane emulsion as described above, comprising the following steps:

[0010] S1, reacting an isocyanate-terminated polyurethane prepolymer with 2,2-dimethylol propionic acid in a solvent to obtain a polyurethane solution; the polyurethane prepolymer is formed by polymerization of aliphatic polycarbonate diol, polyethylene glycol and 4,4'-dicyclohexylmethane diisocyanate;

[0011] S2, reacting the polyurethane solution with an amine-functionalized disulfide, dispersing the polyurethane solution in water, and removing the solvent to obtain an aqueous polyurethane dispersion;

[0012] S3, reacting the aqueous polyurethane dispersion with acryl-containing polyfluoride to obtain a fluorinated aqueous polyurethane emulsion.

[0013] Preferably, in step S1, the reaction temperature is 70-90° C., the reaction time is 1-3 h, and the solvent is acetone.

[0014] Preferably, in step S2, the reaction temperature is 70-90° C. and the reaction time is 1-3 h.

[0015] Preferably, in step S2, neutralization is further performed after the reaction, and the mixture is dispersed in water for at least 20 minutes by mechanical stirring, and the solvent is removed to obtain an aqueous polyurethane dispersion.

[0016] Preferably, step S3 specifically comprises: adding acryl-containing polyfluoride to the aqueous polyurethane dispersion, stirring and dispersing, heating to 70-85° C., and reacting for 1-3 hours without using a catalyst to obtain a fluorinated aqueous polyurethane emulsion.

[0017] Preferably, the amine-functionalized disulfide is 4,4-diaminodiphenyl disulfide.

[0018] The present invention provides a method for preparing fluorinated waterborne polyurethane, which is prepared by the above-mentioned disulfide bond-ene addition reaction.

[0019] The present invention provides an anti-adhesion coating, which is formed by coating, drying and curing the above-mentioned fluorinated aqueous polyurethane emulsion.

[0020] The present invention also provides the use of the anti-adhesion coating as described above in interventional medical devices.

[0021] Compared with the prior art, the embodiment of the present invention introduces a disulfide bond into the waterborne polyurethane molecular chain, which reacts with propylene polyfluoride through a disulfide bond-ene addition reaction to obtain a fluorinated waterborne polyurethane emulsion without the use of a persulfate catalyst. The present invention avoids the use of a persulfate catalyst, so that there is no persulfate residue in the fluorinated waterborne polyurethane emulsion, and the obtained anti-adhesion coating has excellent biocompatibility. In addition, the fluorinated waterborne polyurethane material has a low surface energy and can be used for an anti-adhesion coating on the surface of long-term interventional medical devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a schematic diagram of the process of preparing a fluorinated waterborne polyurethane material by a disulfide bond-ene addition reaction in an embodiment of the present invention;

[0023] Figure 2 FTIR spectrum of the fluorinated waterborne polyurethane film in Example 1;

[0024] Figure 3 This is the Raman spectrum of the fluorinated waterborne polyurethane film in Example 1;

[0025] Figure 4 The bacterial counts of the fluorinated waterborne polyurethane and fluorine-free polyurethane films were determined for the plating experiment in Example 2. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments of the present application are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present application.

[0027] The present invention provides a fluorinated aqueous polyurethane emulsion, which is obtained by reacting acryl-containing polyfluoride with an aqueous polyurethane dispersion;

[0028] The number of fluorine atoms in the acryl-containing polyfluoride is 10 to 14; in the polyurethane molecular chain of the aqueous polyurethane dispersion, aliphatic polycarbonate diol and polyethylene glycol structures are soft segments, 4,4'-dicyclohexylmethane diisocyanate structure is hard segment, 2,2-dihydroxymethylpropionic acid structure is internal emulsifier part, and contains disulfide bond structure.

[0029] The present invention provides a method for preparing the fluorinated aqueous polyurethane emulsion as described above, comprising the following steps:

[0030] S1, reacting an isocyanate-terminated polyurethane prepolymer with 2,2-dimethylol propionic acid, and adding an appropriate amount of acetone to adjust the viscosity of the system to obtain a polyurethane solution; the polyurethane prepolymer is formed by polymerization of aliphatic polycarbonate diol, polyethylene glycol and 4,4'-dicyclohexylmethane diisocyanate;

[0031] S2, reacting the polyurethane solution with an amine-functionalized disulfide such as 4,4-diaminodiphenyl disulfide, dispersing the polyurethane solution in water, and removing the solvent to obtain an aqueous polyurethane dispersion;

[0032] S3, reacting the aqueous polyurethane dispersion with acryl-containing polyfluoride to obtain a fluorinated aqueous polyurethane emulsion.

[0033] The embodiment of the present invention provides a new method for preparing a fluorinated waterborne polyurethane material and an anti-adhesion coating thereof, which can prepare a fluorinated functionalized waterborne polyurethane emulsion by a disulfide-ene addition reaction without adding a catalyst. In the embodiment of the present invention, firstly, seed emulsion polymerization does not affect the dispersibility of the polyurethane molecular chain in water. Secondly, due to the high dynamics of aromatic disulfides, they can be broken under mild conditions to generate sulfur free radicals, which then react with double-bonded fluorides, and this process avoids the use of catalysts.

[0034] See also Figure 1 , Figure 1 Schematic diagram of the process for preparing fluorinated waterborne polyurethane material by disulfide bond-ene addition reaction in an embodiment of the present invention.

[0035] In the embodiment of the present invention, a polyurethane prepolymer is first prepared by mixing aliphatic polycarbonate diol (PCD), polyethylene glycol (PEG) and 4,4'-dicyclohexylmethane diisocyanate (HMDI), adding a catalyst dibutyltin dilaurate (DBTDL), reacting at 80°C for 2h, and polymerizing to form the polyurethane prepolymer. The reaction formula is as follows:

[0036]

[0037] The aliphatic carbon chain of the aliphatic polycarbonate diol can be tetramethylene, hexamethylene, etc.; the molecular weight of the aliphatic polycarbonate diol is 300-2000. And the molecular weight of the polyethylene glycol is 600-2000. The catalyst can also be other organic tin, titanium, etc., preferably the catalyst is organic tin, the amount of 0.1wt%-0.5wt%. Preferably, the molar ratio of the diol to the diisocyanate raw material is 1:2; the reaction temperature is preferably 70-90°C, more preferably 80°C, and the reaction time can be 1-3h.

[0038] The structure of the polyurethane prepolymer is briefly shown below, which can also be commercially available;

[0039]

[0040] In the embodiment of the present invention, the obtained polyurethane prepolymer is subjected to chain extension reaction with 2,2-dimethylol propionic acid (DMPA), 2,2-dimethylol propionic acid (DMPA) is also used as an internal emulsifier, and an appropriate amount of acetone or other solvent is added to adjust the viscosity of the system, and a polyurethane solution is obtained after the reaction. 5 H 10 O 4 ) is not only a chain extender in the manufacture of waterborne polyurethane, but also can make polyurethane self-emulsifying, and can be made into self-emulsifying waterborne polyurethane with excellent stability.

[0041] In the above steps of the embodiment of the present invention, there is no special limitation on the amount of the 2,2-dimethylol propionic acid, as long as it can disperse the polyurethane molecular chain in water; the reaction temperature can be 70-90°C, preferably 80°C, and the reaction time can be 1-3h, preferably 1.5-2h. In the obtained polyurethane solution, the waterborne polyurethane structure is briefly represented as follows:

[0042]

[0043] In the embodiment of the present invention, the polyurethane solution is reacted with an aromatic disulfide, such as 4,4-diaminodiphenyl disulfide, wherein the amine-functionalized disulfide is preferably 4,4-diaminodiphenyl disulfide. After the reaction is completed, it can be neutralized with triethylamine, dispersed in water for at least 20 minutes by mechanical stirring, and the solvent acetone is removed by rotary evaporation to obtain an aqueous polyurethane dispersion.

[0044] In the present invention, the 4,4-diaminodiphenyl disulfide used is an aromatic diamine containing a disulfide bond (-SS-), and the structural formula is as follows. The present invention introduces a disulfide bond into the molecular structure of waterborne polyurethane to facilitate the subsequent preparation of a fluorinated waterborne polyurethane material (Fluorinated waterborne polyurethane). The reaction temperature is preferably 70-90°C, more preferably 80°C; the reaction time may be 1-3h. Then, the embodiment of the present invention is neutralized (Neutralizationg) with triethylamine in an equimolar amount to DMPA, and can be emulsified and dispersed (Emulsification) in water at a rotation speed of 5000-6000rpm, and the time is preferably 30 minutes to obtain a disulfide-functionalized waterborne polyurethane.

[0045]

[0046] After removing the acetone, the embodiment of the present invention adds the acryl-containing polyfluoride to the above aqueous polyurethane dispersion, preferably stirring and dispersing for 30 minutes, and then raising the temperature to 70-85° C. and reacting for 1-3 hours without using a catalyst to obtain a fluorinated aqueous polyurethane emulsion.

[0047] The number of fluorine (F) atoms in the acryl-containing polyfluoride is 10 to 14, preferably 11 to 12; the acryl-containing polyfluoride is further preferably dodecafluoroheptyl methacrylate, the structure of which is shown below. The amount of the acryl-containing polyfluoride can be 5.3 wt% to 17.5 wt%; the temperature for the fluorination reaction is preferably 80°C, and no catalyst is required.

[0048]

[0049] The embodiment of the present invention first obtains an aqueous polyurethane dispersion by seed emulsion polymerization, which will not affect the dispersibility of the polyurethane molecular chain in water; in the polyurethane molecular chain of the aqueous polyurethane dispersion, aliphatic polycarbonate diol and polyethylene glycol structures are used as soft segments, 4,4'-dicyclohexylmethane diisocyanate structure is used as hard segment, 2,2-dimethylol propionic acid structure is used as chain extension part, and contains disulfide bond structure. Again, due to the high dynamics of the aromatic disulfide used in the present invention, it can be broken to generate sulfur free radicals under mild conditions without using a catalyst, and then react with fluoride containing double bonds, so that the obtained fluorinated aqueous polyurethane material has good biocompatibility and is conducive to application. In the embodiment of the present invention, the fluorinated aqueous polyurethane emulsion has no catalyst residue, particle size: 180nm-290nm; fluorine content: 3wt%-7wt%; solid content: 2wt%-40wt%.

[0050] The present invention provides an anti-adhesion coating, which is formed by coating, drying and curing the fluorinated aqueous polyurethane emulsion described above. Specifically, the medical device is immersed in the fluorinated aqueous polyurethane, or the fluorinated aqueous polyurethane is sprayed onto the medical device and dried at 80-110°C for 5-30 minutes. Repeat the coating and drying process until the coating thickness is in the range of 0.1-240μm, preferably in the range of 0.5-120μm, and more preferably in the range of 1-25μm. The medical device material is, for example, polyurethane, nylon and nylon elastomer, polysulfone, polyethylene, polyvinyl chloride, silicone, etc.

[0051] In addition, the present invention also provides the use of the anti-adhesion coating as described above in interventional medical devices. Specifically, the fluorinated aqueous polyurethane emulsion is applied to the surface of the medical device, dried and solidified to obtain an anti-adhesion fluorinated aqueous polyurethane coating. In an embodiment of the present invention, the interventional medical device includes but is not limited to: ureteral stents and intravascular catheters.

[0052] Thrombosis refers to catheter-related thrombosis. There are many causes of catheter-related thrombosis, which are mainly divided into four categories: drug factors, patient factors, catheter factors, and iatrogenic factors. Among them, catheter factors are found based on clinical studies that the material of the catheter inserted into the patient's blood vessels will also affect the incidence of catheter-related thrombosis. If the patient's intravascular catheter is made of polyethylene or polyvinyl chloride, the possibility of damaging the blood vessels and stimulating infection is high, thereby causing catheter-related thrombosis in the patient. The present invention preferably uses intravascular catheters made of materials such as polyurethane and silicone rubber for surface coating.

[0053] The embodiment of the present invention prepares the fluorinated waterborne polyurethane material through the addition reaction of disulfide bonds-enes, avoiding the use of persulfate catalysts, so that the obtained anti-adhesion coating has excellent biocompatibility and can be used for long-term indwelling interventional medical devices. The fluorinated waterborne polyurethane emulsion described in the present invention forms a coating on the surface of the substrate, which not only has excellent biocompatibility, but also gives the medical device excellent anti-adhesion properties, thereby effectively preventing ureteral stent scaling and infection, preventing intravascular catheter thrombosis, and allowing the medical device to be indwelling for a long time.

[0054] In order to better understand the technical content of the present invention, specific embodiments are provided below to further illustrate the present invention.

[0055] Example 1

[0056] 16g of aliphatic polycarbonate diol (Mn = 2000g / mol), 4g of polyethylene glycol (Mn = 2000g / mol) and 5.25g of 4,4'-dicyclohexylmethane diisocyanate were mixed, and the catalyst DBTDL was added. The mixture was reacted at 80°C for 2h to polymerize and form a polyurethane prepolymer; then 1.07g of 2,2-dihydroxymethyl propionic acid was added, and an appropriate amount of acetone was added to adjust the viscosity of the system, and the mixture was reacted at 80°C for 2h. The obtained polyurethane solution was reacted with 0.5g of 4,4-diaminodiphenyl disulfide at 80°C. After 2h, the mixture was neutralized with triethylamine in an equal molar amount to DMPA, and dispersed in water at 6000rpm for 30 minutes. After removing the acetone by rotary evaporation, 2.68g of dodecafluoroheptyl methacrylate was added to the obtained aqueous polyurethane dispersion, and the mixture was stirred and dispersed for 30 minutes. Then the temperature was raised to 80°C and the mixture was reacted for 2 hours to obtain a fluorinated aqueous polyurethane emulsion.

[0057] For product structural characterization, see Figure 2 and Figure 3 .like Figure 2 As shown, no 2270 cm -1 The peak of isocyanate group (-NCO) at 1704.9 cm-1 indicates that the isocyanate group has completely reacted to form urethane group and urea group. The C=O stretching vibration peaks attributable to urethane group and urea group appear at 1704.9 cm-1. -1 The CF (1220.8cm -1 ) and CH(972.1cm -1 ) peak, indicating that dodecafluoroheptyl methacrylate was introduced into the polyurethane molecular chain through disulfide bond-ene addition reaction. Figure 3 The Raman spectrum of the fluorinated waterborne polyurethane film also shows the characteristic peak of the disulfide bond, indicating that 4,4-diaminodiphenyl disulfide is successfully introduced into the polyurethane molecular chain. In summary, through FTIR and Raman testing, it is proved that the present application successfully synthesized the fluorinated waterborne polyurethane through the disulfide bond-ene addition reaction.

[0058] Example 2

[0059] The fluorinated aqueous polyurethane emulsion obtained in Example 1 is applied to the surface of the medical device and dried at 100-110° C. for 15-20 minutes. The coating and drying process are repeated until the coating thickness is within the range of 5-20 μm. The material of the medical device: conventional medical polyurethane.

[0060] Anti-adhesion performance test

[0061] The anti-bacterial adhesion performance of the coating was evaluated by using the colony counting method. The packaged Staphylococcus aureus strains were placed in a -80°C refrigerator. 100 μL of the above strains and 10 mL of LB liquid culture medium were placed in a shaking tube, placed on a bacterial shaker, and shaken for 24 hours at 37°C and 120 r / min. 8 mL of the above bacterial solution was placed in a centrifuge tube, centrifuged at 3000 r / min for 10 minutes, the bacterial precipitate in the lower layer was retained, and the bacterial concentration was dispersed with PBS solution to a bacterial concentration of 108 CFU / mL (determined by an enzyme marker, the OD value was 0.1). Place 1cm×1cm fluorinated polyurethane membrane (Fluorinated PU) and fluorine-free polyurethane membrane (Fluorine-free PU) in 24-well plates, take 10μL of 108CFU / mL bacterial solution, drop it on the surface of the silicon wafer, cover it with PE film (0.7cm×0.7cm), and culture it in a biological incubator at 37℃ for 4h, then rinse the polyurethane membrane with 1mL PBS solution 3 times. Put the polyurethane membrane in a centrifuge tube, add 2mL PBS, ultrasonicate for 2 minutes, take 200μL of the liquid in the centrifuge tube to the culture dish containing LB solid culture medium, shake it on the surface of LB solid culture medium with 10 sterile beads, culture it in a biological incubator at 37℃ for 24h, take out the culture dish, and count the number of bacteria (BacterialCount) according to the plate experiment photos.

[0062] like Figure 4 As shown in the plate test, 2.0×10 2 CFU / cm 2 The number of live bacteria detected on the surface of fluorine-free polyurethane membrane was 6.1×10 6 CFU / cm 2 live bacteria, indicating that the fluorinated waterborne polyurethane film prepared in this scheme has excellent anti-adhesion properties.

[0063] Biocompatibility testing (cytotoxicity)

[0064] The cytotoxicity experiment was tested by CCK-8 method. The fluorinated polyurethane membrane and the fluorinated polyurethane membrane were immersed in 0.9% saline at 37°C for 24 h, L929 cells were cultured in vitro, and cell suspension was prepared. 1×10 4 Cells / 100 μL were inoculated into 96-well plates, with 3 replicates per group, and incubated in a 37°C incubator for 24 hours. The extract was added to the surface of L929 mouse fibroblasts grown on the wall, and the cell culture medium was removed after 24 hours of culture. Then 10 μL of CCK-8 solution and 90 μL of culture medium were added to the cells, and the OD value at 450 nm was measured after 2 hours of culture in a biological incubator. The blank group had culture medium and CCK-8 solution but no cells, and the positive control group did not add samples but only cell culture medium, and the cell activity was calculated using the following formula.

[0065]

[0066] After testing, the cell survival rate of the fluorinated waterborne polyurethane membrane was 91.2%, and the membrane's in vitro cytotoxicity level was level one.

[0067] As can be seen from the above examples, the embodiments of the present invention introduce disulfide bonds into the waterborne polyurethane molecular chain, which reacts with propylene polyfluoride through a disulfide-ene addition reaction to obtain a fluorinated waterborne polyurethane emulsion without the use of a persulfate catalyst. The present invention avoids the use of a persulfate catalyst, so that there is no persulfate residue in the fluorinated waterborne polyurethane emulsion, and the obtained anti-adhesion coating has excellent biocompatibility. In addition, the fluorinated waterborne polyurethane material has a low surface energy and can be used for an anti-adhesion coating on the surface of long-term interventional medical devices.

[0068] This article uses specific examples to illustrate the principles and implementation methods of the present invention. The above examples are only used to help understand the method and core ideas of the present invention. The above is only a preferred implementation of the present invention. It should be pointed out that due to the limitations of textual expression and the objective existence of infinite specific structures, ordinary technicians in this technical field can make several improvements, modifications or changes without departing from the principles of the present invention, and can also combine the above technical features in an appropriate manner; these improvements, modifications, changes or combinations, or the direct application of the inventive concept and technical solution to other occasions without improvement, should be regarded as the protection scope of the present invention.

Claims

1. A fluorinated aqueous polyurethane emulsion, characterized in that: It is obtained by reacting acryl-containing polyfluoride with an aqueous polyurethane dispersion; The acryl-containing polyfluoride is dodecafluoroheptyl methacrylate; in the polyurethane molecular chain of the aqueous polyurethane dispersion, aliphatic polycarbonate diol and polyethylene glycol structures are used as soft segments, 4,4'-dicyclohexylmethane diisocyanate structure is used as hard segment, 2,2-dimethylol propionic acid structure is used as internal emulsifier part, and contains disulfide bond structure; The disulfide bond structure is introduced into the polyurethane molecular chain through 4,4-diaminodiphenyl disulfide.

2. The method for preparing the fluorinated aqueous polyurethane emulsion according to claim 1, comprising the following steps: S1, reacting an isocyanate-terminated polyurethane prepolymer with 2,2-dimethylol propionic acid in a solvent to obtain a polyurethane solution; the polyurethane prepolymer is formed by polymerization of aliphatic polycarbonate diol, polyethylene glycol and 4,4'-dicyclohexylmethane diisocyanate; S2, reacting the polyurethane solution with an amine-functionalized disulfide, dispersing the reactants in water, and removing the solvent to obtain an aqueous polyurethane dispersion; the amine-functionalized disulfide is 4,4-diaminodiphenyl disulfide; S3, reacting the aqueous polyurethane dispersion with acryl-containing polyfluoride to obtain a fluorinated aqueous polyurethane emulsion.

3. The method for preparing the fluorinated aqueous polyurethane emulsion according to claim 2, characterized in that: In step S1, the reaction temperature is 70-90° C., the reaction time is 1-3 h, and the solvent is acetone.

4. The method for preparing the fluorinated aqueous polyurethane emulsion according to claim 2, characterized in that: In step S2, the reaction temperature is 70-90°C and the reaction time is 1-3h.

5. The method for preparing the fluorinated aqueous polyurethane emulsion according to claim 4, characterized in that: In step S2, the reaction is followed by neutralization, and the mixture is dispersed in water for at least 20 minutes by mechanical stirring, and the solvent is removed to obtain an aqueous polyurethane dispersion.

6. The method for preparing the fluorinated aqueous polyurethane emulsion according to any one of claims 2 to 5, characterized in that: Step S3 specifically includes: adding acryl-containing polyfluoride to the aqueous polyurethane dispersion, stirring and dispersing, heating to 70-85° C., and reacting for 1-3 hours without using a catalyst to obtain a fluorinated aqueous polyurethane emulsion.

7. An anti-adhesion coating formed by coating, drying and curing the fluorinated aqueous polyurethane emulsion according to claim 1.

8. Use of the anti-adhesion coating as claimed in claim 7 in interventional medical devices.

Citation Information

Patent Citations

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