Composite material for anesthetic laryngoscope and preparation method thereof

Abstract

The invention belongs to the technical field of medical instruments, and particularly relates to a composite material for an anaesthetic laryngoscope and a preparation method thereof. The composite material for the anaesthetic laryngoscope comprises the following raw materials in parts by weight: 50-80 parts of polyvinyl chloride, 45-65 parts of a plasticizer, 0.5-1 part of a lubricant, 0.5-1 part of a stabilizer, 0.5-1 part of a chitosan derivative and 3-8 parts of modified hydroxyapatite. The chitosan derivative, the modified hydroxyapatite and other components are added into the polyvinyl chloride (PVC), so that the composite material is endowed with stable lubricity and antibacterial property, and meanwhile, the mechanical property of the composite material is also improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of medical devices, and in particular relates to a composite material for an anesthesia laryngoscope and a preparation method thereof. Background Art

[0002] With advancements in medical technology, the application of medical devices continues to improve. As a crucial medical device for laryngeal examination, laryngoscopes are increasingly used clinically. Anesthesia laryngoscopes are a common type of device, primarily used for intubation, anesthesia, or emergency treatment of asphyxiated patients. They are essential medical equipment in hospital operating rooms. Anesthesia laryngoscopes primarily consist of a handle, a lens, and a sheath. Medical PVC, due to its excellent physical and mechanical properties and chemical stability, is an ideal material for the sheath.

[0003] In the selection of materials for anesthesia laryngoscope covers, lubricity and antibacterial properties are key characteristics that need to be examined in detail. Good surface lubricity can not only effectively reduce friction damage between the organ and the contact surface of the anesthesia laryngoscope, significantly reducing the patient's pain, but also inhibit cell adhesion and bacterial adsorption. Good antibacterial properties can fundamentally reduce the risk of infection and reduce the occurrence of postoperative complications, which is crucial to improving surgical safety and patient recovery quality. Currently, antibacterial and lubricity are mainly achieved by coating the surface of the cover material, but this method has obvious limitations: the coating effect will rapidly decay as the film layer ruptures. Therefore, it is very important to develop anesthesia laryngoscope materials with stable lubricity and antibacterial properties. Summary of the Invention

[0004] In order to overcome the deficiencies of the prior art, the primary purpose of the present invention is to provide a composite material for anesthesia laryngoscope, which has excellent lubricity, antibacterial properties and mechanical properties.

[0005] Another object of the present invention is to provide a method for preparing the composite material for anesthesia laryngoscope.

[0006] The purpose of the present invention is achieved through the following technical solutions:

[0007] A composite material for anesthesia laryngoscope, comprising the following raw materials in parts by weight: 50-80 parts of polyvinyl chloride, 45-65 parts of a plasticizer, 0.5-1 part of a lubricant, 0.5-1 part of a stabilizer, 0.5-1 part of a chitosan derivative, and 3-8 parts of modified hydroxyapatite;

[0008] The structural formula of the chitosan derivative is:

[0009]

[0010] According to the composite material for anesthesia laryngoscope, further, the chitosan derivative is prepared by the following preparation process:

[0011] (1) 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide were added to an ethanol solution of 4-mercaptobutyric acid for activation, and then an acetic acid solution of chitosan was added and reacted in a light-proof and inert gas atmosphere; after the reaction was completed, the intermediate 1 was obtained by dialysis and drying;

[0012] The structural formula of the intermediate 1 is:

[0013]

[0014] (2) adding the intermediate 1, methacryloylethyl sulfobetaine and a photoinitiator into dimethyl sulfoxide, reacting them in an inert gas atmosphere under ultraviolet light irradiation, and post-processing after the reaction to obtain the chitosan derivative.

[0015] According to the composite material for anesthesia laryngoscope, further, the mass ratio of chitosan, 4-mercaptobutyric acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide in step (1) is 1:(1.8-2.0):(1-1.2):(1-1.2); the concentration of 4-mercaptobutyric acid in the ethanol solution of 4-mercaptobutyric acid is 0.02-0.025 g / mL; the concentration of chitosan in the acetic acid solution of chitosan is 0.005-0.01 g / mL; the activation time is 2-3 hours; and the reaction time is 24-36 hours.

[0016] According to the composite material for anesthesia laryngoscope, further, in step (2), the amount ratio of the intermediate 1, methacryloylethyl sulfobetaine, photoinitiator and dimethyl sulfoxide is 1g: (1.5-3)g: (0.015-0.03)g: (50-75)mL; the photoinitiator is benzoin dimethyl ether; and the reaction time is 5-10h.

[0017] According to the composite material for anesthesia laryngoscope, further, the modified hydroxyapatite is prepared by the following preparation process:

[0018] Dopamine hydrochloride is added to a Tris-HCl buffer solution, and then [2-(5-imidazolyl)ethyl]acrylamide, sodium lauryl sulfate and an emulsifier are added for emulsification. After the emulsification is completed, CuSO4·5H2O and H2O2 solutions are added in sequence. The mixture is then heated to 65-80°C and hydroxyapatite is added for soaking. The mixture is filtered, washed and dried to obtain modified hydroxyapatite.

[0019] According to the above-mentioned composite material for anesthesia laryngoscope, further, the dosage ratio of dopamine hydrochloride, Tris-HCl buffer, [2-(5-imidazolyl)ethyl]acrylamide, sodium lauryl sulfate, emulsifier, CuSO4·5H2O, H2O2 solution and hydroxyapatite is (0.04-0.1) g: (20-50) mL: (0.36-0.90) g: (0.13-0.33) g: (0.26-0.66) g: (0.016-0.04) g: (40-100) μL: (0.08-0.2) g; the emulsifier is octylphenol polyoxyethylene ether; and the concentration of the H2O2 solution is 30 wt%.

[0020] According to the composite material for anesthesia laryngoscope, further, the soaking time is 3-5 hours.

[0021] According to the above-mentioned composite material for anesthesia laryngoscope, further, the average degree of polymerization of the polyvinyl chloride is 1200-2400; the plasticizer is at least one of dioctyl phthalate, diisononyl phthalate, butyl benzyl phthalate, and dicyclohexyl phthalate; the lubricant is at least one of silicone oil and stearic acid; and the stabilizer is a calcium zinc stabilizer.

[0022] The method for preparing the composite material for anesthesia laryngoscope comprises the following steps:

[0023] According to the aforementioned weight proportions, polyvinyl chloride, plasticizer, lubricant, stabilizer, chitosan derivative and modified hydroxyapatite are added into a twin-screw extruder, melt-extruded and granulated to obtain a composite material for anesthesia laryngoscope.

[0024] According to the above-mentioned method for preparing the composite material for anesthesia laryngoscope, further, the temperature range of each zone of the twin-screw extruder is 110-180° C., and the screw speed is 80-100 rpm.

[0025] The present invention has the following effects compared to the prior art:

[0026] 1. The present invention provides a composite material for anesthesia laryngoscope. By adding components such as chitosan derivatives and modified hydroxyapatite to polyvinyl chloride (PVC), the composite material is endowed with stable lubricity and antibacterial properties, while also improving its mechanical properties.

[0027] 2. This invention uses a two-step process to graft the zwitterionic compound methacryloylethyl sulfobetaine (SBMA) onto chitosan to produce a chitosan derivative. The introduced zwitterionic groups, with their excellent hydration capacity, can form a lubricating layer on the surface of the PVC matrix, effectively reducing the coefficient of friction and thus improving the lubricity of the composite material. Furthermore, the introduction of SBMA significantly enhances the flexibility and mobility of the chitosan molecular chains, which not only makes them more compatible with the PVC molecular chain structure and reduces interchain entanglement, but also weakens intermolecular forces by reducing the surface energy of PVC, thereby increasing the toughness of the composite material and improving its processing properties.

[0028] 3. The present invention uses a CuSO4 / H2O2 redox system to initiate the polymerization of dopamine on the surface of hydroxyapatite, and then initiates the graft copolymerization of [2-(5-imidazolyl)ethyl]acrylamide on its surface, and successfully prepares modified hydroxyapatite. Modified hydroxyapatite can not only be used as a reinforcing agent to improve the tensile strength of the composite material, but also improve the antibacterial properties of the composite material. Specifically, the poly[2-(5-imidazolyl)ethyl]acrylamide introduced on the surface of hydroxyapatite contains imidazole groups with excellent antibacterial properties, which can cooperate with the quaternary ammonium ions in the chitosan derivatives to significantly improve the antibacterial properties of the composite material. In addition, the polydopamine on the surface of the modified hydroxyapatite can not only improve its dispersibility, but also further improve the antibacterial properties of the composite material. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 FT-IR images of chitosan and chitosan derivatives in Example 1;

[0030] Figure 2 FT-IR images of hydroxyapatite and modified hydroxyapatite in Example 1. DETAILED DESCRIPTION

[0031] The technical solution of the present invention will be further described below in conjunction with specific embodiments. However, it should be understood by those skilled in the art that the following examples are only intended to illustrate the present invention and should not be construed as limiting the present invention. Specific conditions not specified in the examples are to be followed according to conventional conditions or the conditions recommended by the manufacturer. All reagents or instruments used, unless otherwise specified, are conventional products obtained from commercial channels.

[0032] The average degree of polymerization of polyvinyl chloride in the following examples and comparative examples is 1200-2400.

[0033] Example 1

[0034] A composite material for anesthesia laryngoscope comprises the following raw materials in parts by weight: 65 parts of polyvinyl chloride, 55 parts of dioctyl phthalate, 0.8 parts of silicone oil, 0.8 parts of calcium zinc stabilizer, 0.8 parts of chitosan derivative, and 5 parts of modified hydroxyapatite.

[0035] The chitosan derivatives are prepared by the following preparation process:

[0036]

[0037] (1) Chitosan was dissolved in 2 wt% acetic acid solution to prepare a chitosan solution with a concentration of 0.008 g / mL; 4-mercaptobutyric acid was dissolved in 50% (v / v) ethanol aqueous solution to prepare a 4-mercaptobutyric acid solution with a concentration of 0.02 g / mL; then, EDC hydrochloride and N-hydroxysuccinimide (NHS) were added to the 4-mercaptobutyric acid solution according to the mass ratio of chitosan, 4-mercaptobutyric acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC hydrochloride) and N-hydroxysuccinimide (NHS) of 1:1.9:1.1:1.1, and activated for 2.5 h, and then the chitosan solution was added, and the reaction was carried out in a dark and nitrogen atmosphere for 30 h to obtain a crude product, which was dialyzed in deionized water for 3 days and dried in vacuo at 50°C to obtain intermediate 1;

[0038] (2) According to the amount ratio of intermediate 1, methacryloylethyl sulfobetaine, benzoin dimethyl ether and dimethyl sulfoxide (DMSO) of 1 g: 2.2 g: 0.02 g: 65 mL, intermediate 1, methacryloylethyl sulfobetaine and benzoin dimethyl ether were added to DMSO, and the mixture was reacted for 8 h under nitrogen atmosphere and irradiation with an ultraviolet lamp (15 W, 365 nm). After the reaction, the product was precipitated with acetone, and the precipitate was washed with acetone / DMSO (95:5, v / v) solution and pure acetone in sequence. The collected crude product was dialyzed against deionized water for 3 days and dried in vacuo at 50°C to obtain the above-mentioned chitosan derivative.

[0039] The FT-IR images of the above chitosan and chitosan derivatives are as follows: Figure 1 As shown in the figure, curve 1 corresponds to chitosan and curve 2 corresponds to chitosan derivatives. As can be seen from the figure, chitosan has a high -1 There is a stretching vibration peak of -NH2 at 1728cm, but it disappears in chitosan derivatives, indicating that the -NH2 on chitosan is destroyed. In addition, the chitosan derivative has a stretching vibration peak at 1728cm -1 、1077cm -1 、857cm -1 Amide bonds, sulfonic acid groups and CN + The characteristic peaks of chitosan derivatives were detected, indicating the successful synthesis of chitosan derivatives.

[0040] The modified hydroxyapatite is prepared by the following preparation process:

[0041] According to the amount ratio of dopamine hydrochloride, Tris-HCl buffer, [2-(5-imidazolyl)ethyl]acrylamide, sodium dodecyl sulfate, emulsifier, CuSO4·5H2O, H2O2 solution and hydroxyapatite of 0.07g:35mL:0.5g:0.23g:0.46g:0.03g:70μL:0.15g, dopamine hydrochloride was added to Tris-HCl buffer (50mM, pH=8.5), and then [2-(5-imidazolyl)ethyl]acrylamide, sodium dodecyl sulfate and emulsifier were added to fully emulsify, and then CuSO4·5H2O and 30wt% H2O2 solution were added in sequence. Then, the temperature was raised to 70℃ and hydroxyapatite was added and soaked for 4h. The mixture was filtered and washed with deionized water, and dried in a vacuum oven at 50℃ for 7h to obtain modified hydroxyapatite.

[0042] The FT-IR images of the above hydroxyapatite and modified hydroxyapatite are as follows: Figure 2 As shown, curve 1 corresponds to hydroxyapatite and curve 2 corresponds to modified hydroxyapatite. As can be seen from the figure, compared with hydroxyapatite, modified hydroxyapatite has a higher δ-value at 1650 cm -1 and 1495cm -1 The characteristic peaks of -NH- and -CH2- appear at , indicating that the hydroxyapatite modification is successful.

[0043] Example 1 also provides a method for preparing the composite material for anesthesia laryngoscope, comprising the following steps:

[0044] Polyvinyl chloride, dioctyl phthalate, medical-grade methyl silicone oil, calcium zinc stabilizer, chitosan derivative, and modified hydroxyapatite were added to a twin-screw extruder according to the above-mentioned parts by weight, melt-extruded, and granulated to obtain a composite material for anesthesia laryngoscope; the processing temperatures of each zone of the twin-screw extruder were as follows: section 1: 110°C; section 2: 130°C; section 3: 150°C; section 4: 180°C; section 5: 145°C, and the screw speed was 80 rpm.

[0045] Example 2

[0046] A composite material for an anesthesia laryngoscope comprises the following raw materials in parts by weight: 50 parts of polyvinyl chloride, 45 parts of diisononyl phthalate, 0.5 parts of stearic acid, 0.5 parts of a calcium zinc stabilizer, 0.5 parts of a chitosan derivative, and 3 parts of modified hydroxyapatite.

[0047] The reaction formula of the chitosan derivative is the same as that of Example 1, and is prepared by the following preparation process:

[0048] (1) Chitosan was dissolved in 2 wt% acetic acid solution to prepare a chitosan solution with a concentration of 0.005 g / mL; 4-mercaptobutyric acid was dissolved in 50% (v / v) ethanol aqueous solution to prepare a 4-mercaptobutyric acid solution with a concentration of 0.025 g / mL; then, according to the mass ratio of chitosan, 4-mercaptobutyric acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC hydrochloride) and N-hydroxysuccinimide (NHS) of 1:1.8:1:1, EDC hydrochloride and NHS were added to the 4-mercaptobutyric acid solution for activation for 2 h, and then the chitosan solution was added and the reaction was carried out in a dark and nitrogen atmosphere for 24 h to obtain a crude product, which was dialyzed in deionized water for 3 days and dried in vacuo at 50°C to obtain intermediate 1;

[0049] (2) According to the amount ratio of intermediate 1, methacryloylethyl sulfobetaine, benzoin dimethyl ether and dimethyl sulfoxide (DMSO) of 1 g:1.5 g:0.015 g:50 mL, intermediate 1, methacryloylethyl sulfobetaine and benzoin dimethyl ether were added to DMSO, and the mixture was reacted for 5 h under nitrogen atmosphere and irradiation with an ultraviolet lamp (15 W, 365 nm). After the reaction, the product was precipitated with acetone, and the precipitate was washed with acetone / DMSO (95:5, v / v) solution and pure acetone in sequence. The collected crude product was dialyzed against deionized water for 3 days and dried in vacuo at 50°C to obtain the above-mentioned chitosan derivative.

[0050] The modified hydroxyapatite is prepared by the following preparation process:

[0051] According to the amount ratio of dopamine hydrochloride, Tris-HCl buffer, [2-(5-imidazolyl)ethyl]acrylamide, sodium dodecyl sulfate, emulsifier, CuSO4·5H2O, H2O2 solution and hydroxyapatite of 0.04g:20mL:0.36g:0.13g:0.26g:0.016g:40μL:0.08g, dopamine hydrochloride was added to Tris-HCl buffer (50mM, pH=8.5), and then [2-(5-imidazolyl)ethyl]acrylamide, sodium dodecyl sulfate and emulsifier were added to fully emulsify, and then CuSO4·5H2O and 30wt% H2O2 solution were added in sequence. Then, the temperature was raised to 65°C and hydroxyapatite was added and soaked for 5h. The mixture was filtered and washed with deionized water, and dried in a vacuum oven at 50°C for 5h to obtain modified hydroxyapatite.

[0052] Example 2 also provides a method for preparing the composite material for anesthesia laryngoscope, comprising the following steps:

[0053] Polyvinyl chloride, diisononyl phthalate, stearic acid, calcium zinc stabilizer, chitosan derivative and modified hydroxyapatite were added to a twin-screw extruder according to the above weight proportions, melt-extruded and granulated to obtain a composite material for anesthesia laryngoscope; the processing temperatures of each zone of the twin-screw extruder were as follows: section 1: 110°C; section 2: 130°C; section 3: 150°C; section 4: 180°C; section 5: 145°C, and the screw speed was 60 rpm.

[0054] Example 3

[0055] A composite material for anesthesia laryngoscope comprises the following raw materials in parts by weight: 80 parts of polyvinyl chloride, 35 parts of butyl benzyl phthalate, 30 parts of dicyclohexyl phthalate, 0.5 parts of silicone oil, 0.5 parts of stearic acid, 1 part of calcium zinc stabilizer, 1 part of chitosan derivative, and 8 parts of modified hydroxyapatite.

[0056] The reaction formula of the chitosan derivative is the same as that of Example 1, and is prepared by the following preparation process:

[0057] (1) Chitosan was dissolved in 2 wt% acetic acid solution to prepare a chitosan solution with a concentration of 0.01 g / mL; 4-mercaptobutyric acid was dissolved in 50% (v / v) ethanol aqueous solution to prepare a 4-mercaptobutyric acid solution with a concentration of 0.025 g / mL; then, EDC hydrochloride and N-hydroxysuccinimide (NHS) were added to the 4-mercaptobutyric acid solution in a mass ratio of 1:2.0:1.2:1.2 to activate the chitosan, 4-mercaptobutyric acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC hydrochloride) and NHS for 3 h, and then the chitosan solution was added and the reaction was carried out in a dark and nitrogen atmosphere for 36 h to obtain a crude product, which was dialyzed in deionized water for 3 days and dried in vacuo at 50°C to obtain intermediate 1;

[0058] (2) According to the amount ratio of intermediate 1, methacryloylethyl sulfobetaine, benzoin dimethyl ether and dimethyl sulfoxide (DMSO) of 1 g:3 g:0.03 g:75 mL, intermediate 1, methacryloylethyl sulfobetaine and benzoin dimethyl ether were added to DMSO, and the mixture was reacted for 10 h under nitrogen atmosphere and irradiation with an ultraviolet lamp (15 W, 365 nm). After the reaction, the product was precipitated with acetone, and the precipitate was washed with acetone / DMSO (95:5, v / v) solution and pure acetone in sequence. The collected crude product was dialyzed against deionized water for 3 days and dried in vacuo at 50°C to obtain the above-mentioned chitosan derivative.

[0059] The modified hydroxyapatite is prepared by the following preparation process:

[0060] According to the amount ratio of dopamine hydrochloride, Tris-HCl buffer, [2-(5-imidazolyl)ethyl]acrylamide, sodium dodecyl sulfate, emulsifier, CuSO4·5H2O, H2O2 solution and hydroxyapatite of 0.1g:50mL:0.9g:0.33g:0.66g:0.04g:100μL:0.2g, dopamine hydrochloride was added to Tris-HCl buffer (50mM, pH=8.5), and then [2-(5-imidazolyl)ethyl]acrylamide, sodium dodecyl sulfate and emulsifier were added to fully emulsify, and then CuSO4·5H2O and 30wt% H2O2 solution were added in sequence. Then, the temperature was raised to 80℃ and hydroxyapatite was added and soaked for 3h. The mixture was filtered and washed with deionized water, and dried in a vacuum oven at 50℃ for 8h to obtain modified hydroxyapatite.

[0061] Example 3 also provides a method for preparing the composite material for anesthesia laryngoscope, comprising the following steps:

[0062] Polyvinyl chloride, butyl benzyl phthalate, dicyclohexyl phthalate, silicone oil, stearic acid, a calcium zinc stabilizer, a chitosan derivative, and modified hydroxyapatite were added to a twin-screw extruder according to the above-mentioned parts by weight, melt-extruded, and granulated to obtain a composite material for an anesthetic laryngoscope; the processing temperatures of each zone of the twin-screw extruder were as follows: section 1: 110°C; section 2: 130°C; section 3: 150°C; section 4: 180°C; section 5: 145°C, and the screw speed was 100 rpm.

[0063] Comparative Example 1

[0064] Comparative Example 1 is substantially the same as Example 1, except that the chitosan derivative in Example 1 is replaced by chitosan.

[0065] Comparative Example 2

[0066] Comparative Example 2 is substantially the same as Example 1, except that the modified hydroxyapatite in Example 1 is replaced by hydroxyapatite.

[0067] Test example

[0068] The composite materials obtained in Examples 1-3 and Comparative Examples 1-2 were made into standard test specimens or samples, and the following performance tests were performed:

[0069] (1) Biological performance: Intradermal irritation and skin sensitization biological performance tests were conducted in accordance with GB / T 16886.10-2017 “Biological evaluation of medical devices Part 10: Irritation and skin sensitization tests”. The results are shown in Table 1.

[0070] (2) Mechanical properties: The tensile strength and elongation at break were tested in accordance with GB / T1040.1-2018 “Tensile Properties of Plastics”. The results are shown in Table 1.

[0071] (3) Lubricity: The water contact angle was tested using an optical contact angle meter. Three different smooth locations on each sample surface were randomly selected for measurement, and the average value was taken. The friction coefficient was measured using a friction and wear tester. The sample was subjected to linear reciprocating friction under the conditions of an applied load and a sliding rate of 1 N and 1 Hz, and the friction coefficient COF was statistically analyzed. The above test results are shown in Table 1.

[0072] (4) Antibacterial activity: The test was conducted according to the method of GB / T 31402-2023 “Determination of antibacterial activity on the surfaces of plastics and other non-porous materials”. The test bacteria were Staphylococcus aureus and Escherichia coli. The results are shown in Table 2.

[0073] Table 1

[0074]

[0075] Table 2

[0076]

[0077]

[0078] From the results in Table 1 and Table 2, it can be seen that the composite materials for anesthesia laryngoscopes prepared in Examples 1-3 of the present invention have excellent lubricity, antibacterial properties and mechanical properties.

[0079] Compared with Example 1, Comparative Example 1 replaces the chitosan derivative with chitosan, and the lubricity is significantly deteriorated, while the antibacterial property and mechanical properties are also reduced. This shows that the addition of the chitosan derivative gives the composite material lubricity and improves its mechanical properties. The chitosan derivative of the present invention is prepared by grafting the zwitterionic compound methacryloylethyl sulfobetaine (SBMA) onto chitosan in a two-step process. The introduced zwitterionic group can construct a lubricating layer on the surface of the PVC matrix by virtue of its excellent hydration ability, effectively reducing the friction coefficient and thus improving the lubrication performance of the composite material. At the same time, the introduction of SBMA significantly enhances the flexibility and mobility of the chitosan molecular chain, which on the one hand makes it more compatible with the PVC molecular chain structure and reduces interchain entanglement, and on the other hand weakens the intermolecular force by reducing the surface energy of PVC, thereby improving the toughness of the composite material and improving the processing performance of the composite material.

[0080] In Comparative Example 2, the modified hydroxyapatite was replaced with hydroxyapatite. The antibacterial properties and mechanical strength were significantly reduced compared with those in Example 1, while the lubricity was basically the same as that in Example 1, indicating that the modification of hydroxyapatite can improve the antibacterial effect and mechanical strength of the composite material. Analysis of the reasons shows that the poly[2-(5-imidazolyl)ethyl]acrylamide introduced on the surface of hydroxyapatite contains imidazole groups with excellent antibacterial properties, which can cooperate with the quaternary ammonium ions in the chitosan derivatives to significantly improve the antibacterial properties of the composite material. In addition, the polydopamine on the surface of the modified hydroxyapatite can not only improve its dispersibility, but also further improve the antibacterial properties of the composite material.

[0081] Finally, it should be noted that the above embodiments are intended only to illustrate the technical solutions of the present invention and are not intended to limit the same. The basic principles and main features of the present invention have been described above using specific implementation schemes. Modifications or substitutions may be made based on the present invention, but such modifications or substitutions do not detract from the essence of the corresponding technical solutions from the scope of protection claimed by the present invention.

Claims

1. A composite material for anesthesia laryngoscope, characterized in that: The invention comprises the following raw materials in parts by weight: 50-80 parts of polyvinyl chloride, 45-65 parts of plasticizer, 0.5-1 part of lubricant, 0.5-1 part of stabilizer, 0.5-1 part of chitosan derivative, and 3-8 parts of modified hydroxyapatite; The structural formula of the chitosan derivative is:

2. The composite material for anesthesia laryngoscope according to claim 1, characterized in that: The chitosan derivative is prepared by the following preparation process: (1) 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide were added to an ethanol solution of 4-mercaptobutyric acid for activation, and then an acetic acid solution of chitosan was added and reacted in a light-proof and inert gas atmosphere; after the reaction was completed, the intermediate 1 was obtained by dialysis and drying; The structural formula of the intermediate 1 is: (2) adding the intermediate 1, methacryloylethyl sulfobetaine and a photoinitiator into dimethyl sulfoxide, reacting them in an inert gas atmosphere under ultraviolet light irradiation, and post-processing after the reaction to obtain the chitosan derivative.

3. The composite material for anesthesia laryngoscope according to claim 2, characterized in that: The mass ratio of chitosan, 4-mercaptobutyric acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide in step (1) is 1:(1.8-2.0):(1-1.2):(1-1.2); the concentration of 4-mercaptobutyric acid in the ethanol solution of 4-mercaptobutyric acid is 0.02-0.025 g / mL; the concentration of chitosan in the acetic acid solution of chitosan is 0.005-0.01 g / mL; the activation time is 2-3 hours; and the reaction time is 24-36 hours.

4. The composite material for anesthesia laryngoscope according to claim 2, characterized in that: In step (2), the amount ratio of the intermediate 1, methacryloylethyl sulfobetaine, photoinitiator and dimethyl sulfoxide is 1g: (1.5-3)g: (0.015-0.03)g: (50-75)mL; the photoinitiator is benzoin dimethyl ether; and the reaction time is 5-10h.

5. The composite material for anesthesia laryngoscope according to claim 1, characterized in that: The modified hydroxyapatite is prepared by the following preparation process: Dopamine hydrochloride is added to a Tris-HCl buffer solution, and then [2-(5-imidazolyl)ethyl]acrylamide, sodium lauryl sulfate and an emulsifier are added for emulsification. After the emulsification is completed, CuSO4·5H2O and H2O2 solutions are added in sequence. The mixture is then heated to 65-80°C and hydroxyapatite is added for soaking. The mixture is filtered, washed and dried to obtain modified hydroxyapatite.

6. The composite material for anesthesia laryngoscope according to claim 5, characterized in that: The dosage ratio of dopamine hydrochloride, Tris-HCl buffer, [2-(5-imidazolyl)ethyl]acrylamide, sodium lauryl sulfate, emulsifier, CuSO4·5H2O, H2O2 solution and hydroxyapatite is (0.04-0.1) g: (20-50) mL: (0.36-0.90) g: (0.13-0.33) g: (0.26-0.66) g: (0.016-0.04) g: (40-100) μL: (0.08-0.2) g; the emulsifier is octylphenol polyoxyethylene ether; and the concentration of the H2O2 solution is 30 wt%.

7. The composite material for anesthesia laryngoscope according to claim 5, characterized in that: The soaking time is 3-5 hours.

8. The composite material for anesthesia laryngoscope according to claim 1, characterized in that: The average polymerization degree of the polyvinyl chloride is 1200-2400; the plasticizer is at least one of dioctyl phthalate, diisononyl phthalate, butyl benzyl phthalate, and dicyclohexyl phthalate; the lubricant is at least one of silicone oil and stearic acid; and the stabilizer is a calcium zinc stabilizer.

9. The method for preparing the composite material for anesthesia laryngoscope according to any one of claims 1 to 8, characterized in that: The following steps are involved: According to the aforementioned weight proportions, polyvinyl chloride, plasticizer, lubricant, stabilizer, chitosan derivative and modified hydroxyapatite are added into a twin-screw extruder, melt-extruded and granulated to obtain a composite material for anesthesia laryngoscope.

10. The method for preparing the composite material for anesthesia laryngoscope according to claim 9, characterized in that: The temperature range of each zone of the twin-screw extruder is 110-180° C., and the screw speed is 80-100 rpm.

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