Modified polycarbonate type polyurethane material and preparation method thereof

Abstract

The invention discloses a modified polycarbonate type polyurethane material and a preparation method thereof. The modified polycarbonate type polyurethane material comprises reaction products generated by reaction of the following raw materials: (a) polycarbonate polyol; (b) a polyisocyanate; (c) a silane modifier, wherein the silane modifier is silane containing at least two isocyanate group reactive groups; and (d) a chain extender selected from polyhydric alcohols, polyhydric alcohol amines or a mixture of the polyhydric alcohols and the polyhydric alcohol amines. The modified polycarbonate type polyurethane material disclosed by the invention has good biocompatibility, hardness, stretchability, oxidation resistance, water immersion resistance and pollution resistance.

Description

Technical Field

[0001] This application relates to the technical field of polymer materials, and particularly relates to a modified polycarbonate-based polyurethane material and a preparation method thereof. Background Art

[0002] Polyurethane (PU) is a polymer formed by the reaction of isocyanate with polyol. Polyurethane materials are widely used in the medical device field due to their excellent mechanical properties, processability, biocompatibility, etc. For example, a polyurethane film is used to wrap a metal stent to prevent the exposed metal of the stent from directly contacting the mucosa or inner wall in the human body cavity. However, conventional polyurethane materials cannot well meet the actual requirements, such as poor hydrophobicity, antioxidant property, water immersion resistance, stain resistance, etc., and cannot meet the application requirements of implantable medical devices. Therefore, it is necessary to develop polyurethane materials with better comprehensive properties. Summary of the Invention

[0003] This application provides a modified polycarbonate-based polyurethane material and a preparation method thereof, which are used to solve the problem that the existing polyurethane materials have poor comprehensive properties and cannot well meet the actual requirements.

[0004] One aspect of the present application discloses a modified polycarbonate-based polyurethane material, which is a reaction product formed by reacting the following raw materials: (a) a polycarbonate polyol; (b) a polyisocyanate; (c) a silane modifier, where the silane modifier is a silane containing at least two isocyanate-reactive groups; (d) a chain extender, and the chain extender is selected from polyols, polyol amines or mixtures thereof. It should be noted that the polyisocyanate can react with the polycarbonate polyol to form a polycarbonate-based polyurethane prepolymer. The isocyanate groups of the hard segments are retained in the polyurethane prepolymer, which has the active ability to carry out further synthesis and can react with hydroxyl groups, amino groups, etc. containing soft segments to synthesize a polyurethane with "memory ability"; the synthesized polyurethane has better tensile strength, elongation at break, and tear strength performance. The silicon element contained in the silane modifier can improve the hydrophobicity and oxidation resistance stability of the synthesized material, making the synthesized material have better antioxidant and water immersion resistance; in the present application, through the isocyanate-reactive groups (such as hydroxyl groups) in the silane modifier, cross-linking is carried out with the isocyanate groups on the synthesized polycarbonate-based polyurethane prepolymer to obtain a silane-polycarbonate-based polyurethane structure. By introducing the silicon element contained in the silane modifier into the synthesized polyurethane and completing the modification, the modified polyurethane has the above-mentioned excellent properties while reducing the adhesion of dirt and impurities. In addition to being a component of the hard segment of the modified polycarbonate-based polyurethane material, the chain extender can also connect the synthesized silane-polycarbonate-based polyurethane structures to form a cross-linked three-dimensional polyurethane. In summary, the modified polycarbonate-based polyurethane material composed of the soft segment polycarbonate polyol, the hard segment polyisocyanate, the silane modifier, and the chain extender has good oxidation resistance stability, elongation, hydrophobicity and other properties.

[0005] In one implementation of the present application, the polycarbonate polyol includes at least one of polycarbonate diols with different molecular weights.

[0006] In one implementation of the present application, the polycarbonate polyol includes at least two polycarbonate diols with different molecular weights. It should be noted that the material formed by the interweaving of different soft segment polycarbonate parts and hard segment isocyanate parts has better flexibility, more excellent strength and elongation than the material formed by the interweaving of a single soft segment polycarbonate part and hard segment isocyanate part.

[0007] In one implementation of the present application, the polyisocyanate includes at least one of dimethylmethylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, 1,4-cyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, trimethyl-1,6-hexamethylene diisocyanate, norbornane diisocyanate, and methylcyclohexyl diisocyanate.

[0008] In one implementation of the present application, the silane modifier includes at least one of diphenyldihydroxy silane, epoxy silane, 3-piperazinylpropylmethyldimethoxysilane, KH-560, MPEG-SS-Silane, 3-aminopropyltriethoxysilane, and carboxyl silane.

[0009] In one implementation of the present application, the chain extender includes at least one of 1,1,1-trimethylolpropane, 1,4-butanediol, ethylene glycol, 1,6-hexanediol, glycerol, pentaerythritol, diethanolamine, triethanolamine, and ethanolamine.

[0010] In one implementation of the present application, the compositional structural formula of the modified polycarbonate-based polyurethane material is as shown in Formula (I):

[0011]

[0012] Among them, the structure of R1 is as shown in the following Formula (II):

[0013]

[0014] In one implementation of the present application, by mass parts, the raw materials of the modified polycarbonate-based polyurethane material include: 10 parts to 30 parts of the polycarbonate polyol, 5 parts to 15 parts of the polyisocyanate, 0.1 part to 1 part of the silane modifier, and 0.5 part to 1.5 parts of the chain extender. It should be noted that in the modified polycarbonate-based polyurethane material, each component affects or is related to and synergizes with each other for the comprehensive properties of the material (such as mechanical properties (strength, toughness, etc.), surface properties (hydrophobicity, low friction and adhesion, etc.), chemical resistance, thermal stability, processing properties, etc.). Through a suitable ratio, it is beneficial to further obtain a modified polycarbonate-based polyurethane material with good comprehensive properties.

[0015] In one implementation of the present application, by mass parts, the raw materials of the modified polycarbonate-based polyurethane material include: 10 parts to 20 parts of the polycarbonate polyol, 5 parts to 10 parts of the polyisocyanate, 0.2 part to 0.8 part of the silane modifier, and 0.6 part to 1.2 parts of the chain extender.

[0016] In one implementation of the present application, by mass parts, the raw materials of the modified polycarbonate-based polyurethane material include: 15 parts of the polycarbonate polyol, 7.3 parts of the polyisocyanate, 0.5 part of the silane modifier, and 0.9 part of the chain extender.

[0017] Another aspect of the present application discloses a method for preparing a modified polycarbonate-based polyurethane material, comprising: mixing a polycarbonate polyol, a polyisocyanate, a solvent and a catalyst, and carrying out a first reaction at 50°C to 80°C; adding a silane modifier and a chain extender, and carrying out a second reaction under the condition of 60°C to 90°C to obtain the modified polycarbonate-based polyurethane material.

[0018] In one implementation of the present application, the polycarbonate polyol includes at least one of polycarbonate diols with different molecular weights.

[0019] In one implementation of the present application, the polycarbonate polyol includes at least two polycarbonate diols with different molecular weights.

[0020] In one implementation of the present application, the polyisocyanate includes at least one of dimethylmethylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, 1,4-cyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, trimethyl-1,6-hexamethylene diisocyanate, norbornane diisocyanate, methylcyclohexyl diisocyanate.

[0021] In one implementation of the present application, the silane modifier includes at least one of diphenyl dihydroxy silane, epoxy silane, 3-piperazinylpropyl methyl dimethoxy silane, KH-560, MPEG-SS-Silane, 3-aminopropyltriethoxysilane, carboxyl silane.

[0022] In one implementation of the present application, the chain extender includes at least one of 1,1,1-trimethylolpropane, 1,4-butanediol, ethylene glycol, 1,6-hexanediol, glycerol, pentaerythritol, diethanolamine, triethanolamine, ethanolamine.

[0023] In one implementation of the present application, the catalyst includes at least one of triethylenediamine, bis(dimethylaminoethyl) ether, dimethylcyclohexylamine, tetramethylethylenediamine, dimethylethanolamine, dibutyltin dilaurate, dibutyltin diacetate, zinc isooctanoate.

[0024] In one implementation of the present application, by mass, in the reaction system of the preparation method, it includes: 10 parts to 30 parts of the polycarbonate polyol, 5 parts to 15 parts of the polyisocyanate, 0.1 part to 0.5 part of the catalyst, 0.1 part to 1 part of the silane modifier, 0.5 part to 1.5 parts of the chain extender, 50 parts to 80 parts of the solvent.

[0025] In one implementation of the present application, in the reaction system of the preparation method, by mass parts, it includes: 10 parts to 20 parts of the polycarbonate polyol, 5 parts to 10 parts of the polyisocyanate, 0.2 parts to 0.4 parts of the catalyst, 0.2 parts to 0.8 parts of the silane modifier, 0.6 parts to 1.2 parts of the chain extender, and 60 parts to 80 parts of the solvent.

[0026] In one implementation of the present application, in the reaction system of the preparation method, by mass parts, it includes: 15 parts of the polycarbonate polyol, 7.3 parts of the polyisocyanate, 0.3 parts of the catalyst, 0.5 parts of the silane modifier, 0.9 parts of the chain extender, and 67 parts of the solvent.

[0027] The beneficial effects of the present application are as follows:

[0028] The modified polycarbonate-based polyurethane material of the present application has good biocompatibility, hardness, stretchability, antioxidant property, water immersion resistance, and stain resistance. Description of the Drawings

[0029] Figure 1 It is a synthesis route diagram of the modified polycarbonate-based polyurethane material in a specific implementation manner related to the present application.

[0030] Figure 2 It is the anti-fouling performance test results of the polyurethane films of Example 1 and Comparative Example 1 related to the present application. Detailed Embodiments

[0031] The present invention will be further described in detail below through specific embodiments in conjunction with the drawings. In the following embodiments, many detailed descriptions are provided to enable a better understanding of the present application. However, those skilled in the art can easily recognize that some of these features can be omitted in different situations, or can be replaced by other materials or methods. In some cases, some operations related to the present application are not shown or described in the specification, which is to avoid the core part of the present application being overwhelmed by excessive descriptions. For those skilled in the art, it is not necessary to describe these related operations in detail, and they can fully understand the related operations based on the description in the specification and the general technical knowledge in the field.

[0032] In addition, the features, operations, or characteristics described in the specification can be combined in any appropriate manner to form various embodiments. At the same time, the steps or actions in the method description can also be reordered or adjusted in an obvious manner by those skilled in the art. Therefore, the various sequences in the specification and drawings are only for clearly describing a certain embodiment, and do not mean that they are the necessary sequences, unless it is stated that a certain sequence must be followed.

[0033] The serial numbers assigned to the components in this text itself, such as "first", "second", etc., are only used to distinguish the described objects and do not have any sequential or technical meaning.

[0034] In the field of medical devices, a stent with a metal mesh and a coating is used in natural lumen channels inside the human body, such as the ureter, blood vessels, bile duct, esophagus, etc. The outer layer of this metal-coated stent is usually covered by a polymer film to prevent the exposed metal of the stent from directly contacting the mucosa or inner wall in the human body cavity. Currently, the common materials used for the polymer film on metal stents are polyvinyl chloride (PVC), polyurethane (PU), polytetrafluoroethylene (PTFE), etc. Since PVC film contains chlorine elements, it may cause harm to human health during long-term contact with the human body, and PVC has poor temperature adaptability. Currently, its application on long-term implanted medical devices is gradually decreasing until it is phased out. The poor processability and weak anti-pollution ability of PTFE film make the application of PTFE more inclined to the coating aspect. The excellent ductility, processability, resilience, biocompatibility, etc. of PU film make the application of PU film on metal stents more favored. On this basis, modifying PU film to endow it with more properties such as hydrophobicity, antioxidant property, water immersion resistance, etc. is becoming a hot research direction for PU modification. In addition, the strict usage conditions of long-term implanted medical devices also further require that PU film needs to have strong anti-pollution ability and anti-scaling ability. Therefore, developing a PU film suitable for application in long-term implanted medical devices and being able to effectively combine the PU film with the metal stent is of great significance.

[0035] In view of this, the present application provides a silane-modified polycarbonate-based polyurethane material and its preparation method. The polyurethane film is a polymer composed of alternating flexible hard and soft segments, mainly composed of soft segment polycarbonate polyol, hard segment polyisocyanate, and chain extender. The modified polycarbonate-based polyurethane material composed of hard and soft segments has good oxidation resistance stability, elongation, hydrophobicity and other properties, with a moderate hardness. Silane modification can improve the resilience, hydrophobicity, water immersion resistance, oxidation resistance stability and anti-pollution property of the polymer. The preparation process of the present application is simple and easy to operate, and the raw materials are inexpensive, effectively reducing the production cost and ensuring the coherence and stability of the entire production process.

[0036] In a specific embodiment, the silane-modified polycarbonate-based polyurethane material includes a reaction product formed by the reaction of the following raw materials: (a) polycarbonate polyol; (b) polyisocyanate; (c) silane modifier; (d) chain extender.

[0037] In a specific embodiment, the polycarbonate polyol may be a polycarbonate diol. It should be noted that the polycarbonate diol has good mechanical properties, hydrolysis resistance and biocompatibility, and is suitable for applications in medical devices in humid environments.

[0038] In a specific embodiment, the polycarbonate diol may include at least one of polycarbonate diols with various different molecular weights. For example, the polycarbonate diol may include at least one of polycarbonate diol (PH-100), polycarbonate diol (PH-200), polycarbonate diol (PH-300), polycarbonate diol (PH-500), polycarbonate diol (PH-1000). Further, the polycarbonate diol may include at least two polycarbonate diols with different molecular weights. Further, the polycarbonate diol may include polycarbonate diol (PH-100) and polycarbonate diol (PH-200). It should be noted that the material formed by the interweaving of different soft segment polycarbonate parts and hard segment isocyanate parts has better flexibility, more excellent strength and elongation compared to the material formed by the interweaving of a single soft segment polycarbonate part and hard segment isocyanate part.

[0039] In a specific embodiment, by mass parts, the raw materials of the silane-modified polycarbonate-based polyurethane material may include 10 parts to 30 parts of polycarbonate polyol. For example, by mass parts, the raw materials of the modified polycarbonate-based polyurethane material may include 10 parts, 15 parts, 20 parts, 25 parts or 30 parts of polycarbonate polyol. Further, by mass parts, the raw materials of the modified polycarbonate-based polyurethane material may include 10 parts to 20 parts of polycarbonate polyol. Further, by mass parts, the raw materials of the modified polycarbonate-based polyurethane material may include 15 parts of polycarbonate polyol.

[0040] In a specific embodiment, the polyisocyanate may include a diisocyanate. It should be noted that the polyisocyanate can react with the polycarbonate polyol to form a polycarbonate-based polyurethane prepolymer. The polyurethane prepolymer retains the isocyanate groups of the hard segments and has the active ability to carry out further synthesis. It can react with hydroxyl groups, amino groups, etc. containing soft segments to synthesize polyurethanes with "memory ability"; the synthesized polyurethanes have better tensile strength, elongation at break and tear strength performance.

[0041] In a specific embodiment, the polyisocyanate may include at least one of dimethylmethylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, 1,4-cyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, trimethyl-1,6-hexamethylene diisocyanate, norbornane diisocyanate, methylcyclohexyl diisocyanate.

[0042] In a specific embodiment, by mass parts, the raw materials of the modified polycarbonate-based polyurethane material may include 5 to 15 parts of polyisocyanate. For example, by mass parts, the raw materials of the modified polycarbonate-based polyurethane material may include 5 parts, 8 parts, 10 parts, 12 parts or 15 parts of polyisocyanate. Further, by mass parts, the raw materials of the modified polycarbonate-based polyurethane material may include 5 to 10 parts of polyisocyanate. Further, by mass parts, the raw materials of the modified polycarbonate-based polyurethane material may include 7.3 parts of polyisocyanate. It should be noted that appropriate ratios of polycarbonate polyol and polyisocyanate can endow the modified polycarbonate-based polyurethane material with good comprehensive properties. The ratio of polycarbonate polyol and polyisocyanate affects many properties, such as hardness, flexibility, tensile strength (for example, a lower NCO / OH ratio helps improve the tear resistance of the material), weather resistance (for example, a higher NCO / OH ratio helps improve the UV resistance and antioxidant properties of the material), thermal stability (for example, a higher NCO / OH ratio helps improve the thermal stability of the material), processability (a higher NCO / OH ratio will increase the viscosity of the system, which may affect the fluidity during processing); the more the amount of isocyanate used, the faster the reaction rate and the shorter the curing time. However, too fast a curing speed may lead to bubble formation or other defects, so precise control is required), etc. Therefore, an appropriate ratio is needed to balance various properties and obtain a modified polycarbonate-based polyurethane material with good comprehensive properties.

[0043] In a specific embodiment, the silane modifier is a silane containing at least two isocyanate-reactive groups. The isocyanate-reactive groups may include hydroxyl, mercapto, and carboxyl groups. It should be noted that the silicon element contained in the silane modifier can improve the hydrophobicity and oxidation resistance stability of the synthetic material, making the synthesized material have better antioxidant and water immersion resistance; in this application, through the isocyanate-reactive groups (such as hydroxyl groups) in the silane modifier, cross-linking with the isocyanate groups on the synthesized polycarbonate-based polyurethane prepolymer to obtain a silane-polycarbonate-based polyurethane structure. By introducing the silicon element contained in the silane modifier into the synthesized polyurethane and completing the modification, the modified polyurethane has the above-mentioned excellent properties while reducing the adhesion of dirt and impurities.

[0044] In a specific embodiment, the silane modifier may include at least one of diphenyldihydroxy silane, epoxy silane, 3-piperazinylpropylmethyldimethoxysilane, KH-560, MPEG-SS-Silane, 3-aminopropyltriethoxysilane, and carboxyl silane.

[0045] In a specific embodiment, by mass parts, the raw materials of the modified polycarbonate-based polyurethane material may include 0.1 part to 1 part of a silane modifier. For example, by mass parts, the raw materials of the modified polycarbonate-based polyurethane material may include 0.1 part, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts or 1 part of a silane modifier. Further, by mass parts, the raw materials of the modified polycarbonate-based polyurethane material may include 0.2 parts to 0.8 parts of a silane modifier. Further, by mass parts, the raw materials of the modified polycarbonate-based polyurethane material may include 0.5 part of a silane modifier. It should be noted that the content of the silane modifier has an impact on the mechanical properties (strength, toughness, etc.), surface properties (hydrophobicity, low friction and adhesion, etc.), chemical resistance, thermal stability, etc. of the modified polycarbonate-based polyurethane material. An appropriate ratio is required to balance the properties in various aspects. An appropriate content of the silane modifier is beneficial to obtaining a modified polycarbonate-based polyurethane material with good comprehensive properties in this application.

[0046] In a specific embodiment, the chain extender is selected from polyols, polyolamines or mixtures thereof. Further, the chain extender is a polyol with at least three hydroxyl groups. It should be noted that in addition to being a component of the hard segment of the modified polycarbonate-based polyurethane material, the chain extender can also connect the synthesized silane-polycarbonate-based polyurethane structures to form a crosslinked three-dimensional polyurethane (also known as crosslinked polyurethane or network polyurethane, which is a polyurethane material formed by chemical crosslinking to form a three-dimensional network structure).

[0047] In a specific embodiment, the chain extender includes at least one of 1,1,1-trimethylolpropane, 1,4-butanediol, ethylene glycol, 1,6-hexanediol, glycerol, pentaerythritol, diethanolamine, triethanolamine, ethanolamine.

[0048] In a specific embodiment, based on parts by mass, the raw materials of the modified polycarbonate-based polyurethane material may include 0.5 to 1.5 parts of a chain extender. For example, based on parts by mass, the raw materials of the modified polycarbonate-based polyurethane material may include 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts or 1.5 parts of a chain extender. Further, based on parts by mass, the raw materials of the modified polycarbonate-based polyurethane material may include 0.6 to 1.2 parts of a chain extender. Further, based on parts by mass, the raw materials of the modified polycarbonate-based polyurethane material may include 0.9 part of a chain extender. It should be noted that the content of the chain extender has an impact on the molecular chain structure (chain segment length, crosslinking density, ratio of hard segment to soft segment), mechanical properties (hardness, tensile strength, elongation at break, tear strength, elastic modulus), processing properties (curing time, viscosity, fluidity), heat resistance, chemical corrosion resistance, surface properties (friction force), etc. of the modified polycarbonate-based polyurethane material. Using an appropriate and balanced amount of the chain extender helps to obtain a modified polycarbonate-based polyurethane material with good comprehensive properties in this application.

[0049] It should also be noted that in the modified polycarbonate-based polyurethane material, the components affect, are related to, and cooperate with each other regarding the comprehensive properties of the material. Through appropriate ratios, it is beneficial to further obtain a modified polycarbonate-based polyurethane material with good comprehensive properties.

[0050] Figure 1 It is a synthesis route diagram of the modified polycarbonate-based polyurethane material in a specific embodiment involved in this application.

[0051] Such as Figure 1 shown, in a specific embodiment, the modified polycarbonate-based polyurethane material can be obtained by the reaction of the route shown in Figure 1 shown.

[0052] In a specific embodiment, the compositional structural formula of the modified polycarbonate-based polyurethane material may be as shown in formula (I):

[0053]

[0054] Among them, the structure of R1 is as shown in the following formula (II):

[0055]

[0056] This application also provides a preparation method of a modified polycarbonate-based polyurethane material. It should be noted that the raw materials, ratios, etc. involved in the preparation method can refer to the foregoing content and will not be elaborated here.

[0057] In a specific embodiment, the preparation method may include: mixing a polycarbonate polyol, a polyisocyanate, a solvent, and a catalyst, and performing a first reaction at 50°C to 80°C; adding a silane modifier and a chain extender, and performing a second reaction at 60°C to 90°C to obtain the modified polycarbonate-based polyurethane material.

[0058] In a specific embodiment, the catalyst may include at least one of triethylenediamine, bis(dimethylaminoethyl) ether, dimethylcyclohexylamine, tetramethylethylenediamine, dimethylethanolamine, dibutyltin dilaurate, dibutyltin diacetate, and zinc isooctanoate.

[0059] In a specific embodiment, the solvent may include N,N-dimethylformamide.

[0060] In a specific embodiment, by mass, in the reaction system of the preparation method, it includes: 10 parts to 30 parts of polycarbonate polyol, 5 parts to 15 parts of polyisocyanate, 0.1 part to 0.5 part of catalyst, 0.1 part to 1 part of silane modifier, 0.5 part to 1.5 parts of chain extender, and 50 parts to 80 parts of solvent.

[0061] In a specific embodiment, by mass, in the reaction system of the preparation method, it includes: 10 parts to 20 parts of polycarbonate polyol, 5 parts to 10 parts of polyisocyanate, 0.2 part to 0.4 part of catalyst, 0.2 part to 0.8 part of silane modifier, 0.6 part to 1.2 parts of chain extender, and 60 parts to 80 parts of solvent;

[0062] In a specific embodiment, by mass, in the reaction system of the preparation method, it includes: 15 parts of polycarbonate polyol, 7.3 parts of polyisocyanate, 0.3 part of catalyst, 0.5 part of silane modifier, 0.9 part of chain extender, and 67 parts of solvent.

[0063] In a specific embodiment, the preparation method further includes: coating or spreading the reaction product of the first reaction on a plane to obtain a wet film, and drying the wet film to obtain a modified polycarbonate-based polyurethane film.

[0064] The present application also provides an application of the modified polycarbonate-based polyurethane material in implantable medical devices. The implantable medical device may include a ureteral stent, a biliary stent, a vascular stent, an esophageal stent, an implantable sensor, a cardiac pacemaker, etc. It should be noted that the modified polycarbonate-based polyurethane material of the present application can be in the form of a thin film to wrap the internal device to form an implantable medical device. The thickness of the thin film can be 0.03 mm to 0.1 mm. The modified polycarbonate-based polyurethane material of the present application has good biocompatibility, elasticity, stretchability, waterproof and moisture-permeable function, and anti-fouling property, and is particularly suitable for the application of implantable medical devices.

[0065] The present application will be further described in detail below through specific embodiments. The following embodiments are only for further illustration of the present application and should not be construed as limitations on the present application. In this embodiment, unless otherwise specified, the reagents and instruments used are all commercially available, and the experimental operations are carried out in accordance with the product instructions and conventional experimental specifications.

[0066] Example 1:

[0067] (1) Accurately weigh 5 parts of polycarbonate diol (PH-100) and 10 parts of polycarbonate diol (PH-200) respectively with an electronic balance, add them to a reaction flask, and mix and stir evenly;

[0068] (2) Add 7.3 parts of isophorone diisocyanate to the reaction flask; then sequentially add 0.3 parts of dibutyltin dilaurate as a catalyst and 66.9 parts of N,N-dimethylformamide as a reaction solvent to the reaction flask, and mix and stir evenly;

[0069] (3) Place the reaction flask containing the above mixture in a water bath, and set the conditions for the prepolymerization reaction as follows: temperature 60 °C, rotation speed 3000 r / min, reaction time 120 min;

[0070] (4) After the reaction is completed, raise the temperature to 70 °C, sequentially add 0.5 part of diphenyldihydroxysilane as a modifier and 0.9 part of trimethylolpropane as a chain extender, and continue the reaction for 120 min under water bath conditions;

[0071] (5) After the reaction is completed, raise the temperature to 80 °C, and the reaction time ranges from 30 min to 60 min. Stop the reaction after the time ends;

[0072] (6) After the above reaction is completed, evenly spread the product in the reaction flask on a clean and smooth mold to obtain a wet film; then place the wet film in a vacuum drying oven for vacuum drying, set the drying temperature to 75 °C, and the drying time to 8 h;

[0073] (7) After drying, obtain the silane-modified polycarbonate-based polyurethane film of Example 1, with a thickness of 0.04 mm.

[0074] Comparative Example 1:

[0075] Compared with Example 1, in step (4) of Comparative Example 1, 0.5 part of diphenyldihydroxysilane as a modifier was not added, and the rest was the same as in Example 1.

[0076] Example 2:

[0077] (1) Accurately weigh 10 parts of polycarbonate diol (PH-100) with an electronic balance, add it to a reaction flask, and mix and stir evenly;

[0078] (2) Add 7.3 parts of isophorone diisocyanate to the reaction flask; subsequently, add 0.3 parts of dibutyltin dilaurate as the catalyst and 66.9 parts of N,N-dimethylformamide as the reaction solvent to the reaction flask in sequence, and mix and stir evenly;

[0079] (3) Place the reaction flask containing the above mixture in a water bath, and set the conditions for the prepolymerization reaction as follows: temperature 60°C, rotation speed 3000 r / min, reaction time 120 min;

[0080] (4) After the reaction is completed, raise the temperature to 70°C, add 0.5 parts of diphenyldihydroxysilane as the modifier and 0.9 parts of trimethylolpropane as the chain extender in sequence, and continue the reaction for 120 min under the water bath conditions;

[0081] (5) After the reaction is completed, raise the temperature to 80°C, and the reaction time ranges from 30 min to 60 min. Stop the reaction after the time ends;

[0082] (6) After the reaction is completed, evenly spread the product in the reaction flask on a clean and smooth mold to obtain a wet film; then place the wet film in a vacuum drying oven for vacuum drying, set the drying temperature to 75°C, and the drying time to 8 h;

[0083] (7) After drying, obtain the silane-modified polycarbonate-based polyurethane film of Example 2, with a thickness of 0.04 mm.

[0084] Comparative Example 2:

[0085] Compared with Example 2, in step (4) of Comparative Example 2, 0.5 parts of diphenyldihydroxysilane as the modifier was not added, and the rest was the same as in Example 2.

[0086] Example 3:

[0087] (1) Accurately weigh 20 parts of polycarbonate diol (PH-200) with an electronic balance, add it to the reaction flask, and mix and stir evenly;

[0088] (2) Add 7.3 parts of isophorone diisocyanate to the reaction flask; subsequently, add 0.3 parts of dibutyltin dilaurate as the catalyst and 66.9 parts of N,N-dimethylformamide as the reaction solvent to the reaction flask in sequence, and mix and stir evenly;

[0089] (3) Place the reaction flask containing the above mixture in a water bath, and set the conditions for the prepolymerization reaction as follows: temperature 60°C, rotation speed 3000 r / min, reaction time 120 min;

[0090] (4) After the reaction is completed, the temperature is raised to 70 °C, and 0.5 part of the modifier diphenyldihydroxysilane and 0.9 part of the chain extender trimethylolpropane are added in sequence, and the reaction is continued for 120 min under the condition of a water bath;

[0091] (5) After the reaction is completed, the temperature is raised to 80 °C, and the reaction time ranges from 30 min to 60 min. After the time ends, the reaction is stopped;

[0092] (6) After the reaction is completed, the product in the reaction flask is evenly spread out in a clean and smooth mold to obtain a wet film; then the wet film is placed in a vacuum drying oven for vacuum drying, the drying temperature is set at 75 °C, and the drying time is 8 h;

[0093] (7) After drying, the silane-modified polycarbonate-based polyurethane film of Example 3 is obtained, with a thickness of 0.04 mm.

[0094] Comparative Example 3:

[0095] Compared with Example 3, in step (4) of Comparative Example 3, 0.5 part of the modifier diphenyldihydroxysilane was not added, and the rest was the same as in Example 3.

[0096] Performance test:

[0097] (1) Physical property test: The polycarbonate-based polyurethane films prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were subjected to performance tests, and the results are shown in Table 1 below:

[0098]

[0099] As can be seen from the above table, the silane-modified polycarbonate-based polyurethane films of Examples 1 to 3 of the present application all have high elasticity, stretchability, and good waterproof and moisture-permeable functions. Among them, in each example, Example 1 performed better in various test items, and the silane-modified polycarbonate-based polyurethane film prepared in Example 1 had the best effects in mechanical properties, hydrophobicity, and durability, and the performance was the most excellent. Since Example 1 used two different soft-segment polycarbonate diols, the polyurethane film formed by the interweaving of the two different soft-segment parts and the hard-segment part has better flexibility, more excellent strength and elongation.

[0100] Compared with the comparative examples, by adding the modifier diphenyldihydroxysilane in the examples, the polyurethane material has significantly improved strength and waterproof and moisture-permeable properties. This improvement in performance makes the silane-modified polycarbonate-based polyurethane film more versatile and practical in applications.

[0101] (2) Antifouling performance test: The polyurethane films prepared in Example 1 and Comparative Example 1 were immersed in an Escherichia coli culture solution in an environment of 37°C ± 0.5°C, and a microbial protein adhesion test was carried out. The situation of the microbial protein adhered to the surface of the polyurethane film on the first day, the third day, the seventh day, and the fourteenth day was recorded respectively, and Figure 2 was obtained. Figure 2 , Figure 2 which are the antifouling performance test results of the polyurethane films of Example 1 and Comparative Example 1 involved in this application.

[0102] It can be seen from Figure 2 that in the detections on the first day, the third day, the seventh day, and the fourteenth day, the adhesion amount of surface microorganisms of the silane-modified polyurethane film in Example 1 was less than that of the unmodified polyurethane film in Comparative Example 1, indicating that the silane-modified polycarbonate-based polyurethane film prepared in Example 1 can, to a certain extent, isolate or block the adhesion of pollutant flora, thereby improving or avoiding the pollution of the silane-modified polyurethane film or medical device products coated with the silane-modified polyurethane film by pollutants during use.

[0103] The above content is a further detailed description of this application in combination with specific embodiments, and it cannot be determined that the specific implementation of this application is only limited to these descriptions. For those of ordinary skill in the technical field to which this application belongs, without departing from the concept of this application, several simple deductions or substitutions can also be made.

Claims

1. A modified polycarbonate-based polyurethane material, characterized in that, The reaction product formed from the following raw materials: (a) Polycarbonate polyol; (b) Polyisocyanate; (c) Silane modifier, and the silane modifier is a silane containing at least two isocyanate-reactive groups; (d) Chain extender, and the chain extender is selected from polyols, polyol amines or mixtures thereof.

2. The modified polycarbonate-based polyurethane material according to claim 1, wherein The polycarbonate polyol includes at least one of polycarbonate diols with different molecular weights; Preferably, the polycarbonate polyol includes at least two polycarbonate diols with different molecular weights.

3. The modified polycarbonate-based polyurethane material according to claim 1, characterized in that, The polyisocyanate includes at least one of dimethylmethylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, 1,4-cyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, trimethyl-1,6-hexamethylene diisocyanate, norbornane diisocyanate, methylcyclohexyl diisocyanate.

4. The modified polycarbonate-based polyurethane material according to claim 1, wherein The silane modifier includes at least one of diphenyldihydroxy silane, epoxy silane, 3-piperazinylpropylmethyldimethoxysilane, KH-560, MPEG-SS-Silane, 3-aminopropyltriethoxysilane, carboxyl silane.

5. The modified polycarbonate-based polyurethane material according to claim 1, wherein The chain extender includes at least one of 1,1,1-trimethylolpropane, 1,4-butanediol, ethylene glycol, 1,6-hexanediol, glycerol, pentaerythritol, diethanolamine, triethanolamine, ethanolamine.

6. The modified polycarbonate-based polyurethane material according to claim 1, characterized in that, The compositional structural formula of the modified polycarbonate-based polyurethane material is shown in Formula (I): Among them, the structure of R1 is shown in the following formula (II):

7. The modified polycarbonate-based polyurethane material according to any one of claims 1 to 6, characterized in that By mass, the raw materials of the modified polycarbonate-based polyurethane material include: 10 parts to 30 parts of the polycarbonate polyol, 5 parts to 15 parts of the polyisocyanate, 0.1 part to 1 part of the silane modifier, 0.5 part to 1.5 parts of the chain extender; Preferably, by mass, the raw materials of the modified polycarbonate-based polyurethane material include: 10 parts to 20 parts of the polycarbonate polyol, 5 parts to 10 parts of the polyisocyanate, 0.2 part to 0.8 part of the silane modifier, 0.6 part to 1.2 parts of the chain extender; Preferably, by mass, the raw materials of the modified polycarbonate-based polyurethane material include: 15 parts of the polycarbonate polyol, 7.3 parts of the polyisocyanate, 0.5 part of the silane modifier, 0.9 part of the chain extender.

8. A preparation method of a modified polycarbonate-based polyurethane material, characterized in that, Include: Mix the polycarbonate polyol, polyisocyanate, solvent and catalyst, and carry out the first reaction at 50°C to 80°C; Add the silane modifier and the chain extender, and carry out the second reaction under the condition of 60°C to 90°C to obtain the modified polycarbonate-based polyurethane material.

9. The preparation method according to claim 8, characterized in that, The polycarbonate polyol includes at least one of polycarbonate diols with different molecular weights; Preferably, the polycarbonate polyol includes at least two polycarbonate diols with different molecular weights; Preferably, the polyisocyanate includes at least one of dimethylmethylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, 1,4-cyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, trimethyl-1,6-hexamethylene diisocyanate, norbornane diisocyanate, and methylcyclohexyl diisocyanate; Preferably, the silane modifier includes at least one of diphenyl dihydroxy silane, epoxy silane, 3-piperazinylpropyl methyl dimethoxy silane, KH-560, MPEG-SS-Silane, 3-aminopropyltriethoxy silane, and carboxyl silane; Preferably, the chain extender includes at least one of 1,1,1-trimethylolpropane, 1,4-butanediol, ethylene glycol, 1,6-hexanediol, glycerol, pentaerythritol, diethanolamine, triethanolamine, and ethanolamine; Preferably, the catalyst includes at least one of triethylenediamine, bis(dimethylaminoethyl) ether, dimethylcyclohexylamine, tetramethylethylenediamine, dimethylethanolamine, dibutyltin dilaurate, dibutyltin diacetate, and zinc isooctanoate.

10. The preparation method according to claim 8 or 9, characterized in that, By mass, in the reaction system of the preparation method, it includes: 10 parts to 30 parts of the polycarbonate polyol, 5 parts to 15 parts of the polyisocyanate, 0.1 part to 0.5 part of the catalyst, 0.1 part to 1 part of the silane modifier, 0.5 part to 1.5 parts of the chain extender, and 50 parts to 80 parts of the solvent; Preferably, by mass, in the reaction system of the preparation method, it includes: 10 parts to 20 parts of the polycarbonate polyol, 5 parts to 10 parts of the polyisocyanate, 0.2 part to 0.4 part of the catalyst, 0.2 part to 0.8 part of the silane modifier, 0.6 part to 1.2 parts of the chain extender, and 60 parts to 80 parts of the solvent; Preferably, by mass, in the reaction system of the preparation method, it includes: 15 parts of the polycarbonate polyol, 7.3 parts of the polyisocyanate, 0.3 part of the catalyst, 0.5 part of the silane modifier, 0.9 part of the chain extender, and 67 parts of the solvent.

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