A bonding material for orthopedic repair and a method for preparing the same

Abstract

The application discloses a kind of bonding materials for orthopedics repair and preparation method thereof, it is related to medical material technical field.The bonding material for orthopedics repair includes solid phase powder and liquid component;It includes solid phase powder and liquid component;The solid phase powder includes the following weight fraction components: beta-calcium phosphate 40-55 parts, calcium dihydrogen phosphate monohydrate 20-30 parts, hydroxyapatite 10-15 parts, bioactive glass 5-8 parts, modified reinforcing agent 8-12 parts, developing agent 2-3 parts, antibacterial agent 5-8 parts;The liquid component includes the following weight fraction components: disodium hydrogen phosphate 10-20 parts, sodium alginate 4-5 parts, deionized water 50-60 parts.The bonding material for orthopedics repair prepared by the application has good compressive strength and antibacterial property.

Description

Technical Field

[0001] This invention relates to the field of medical materials technology, specifically to an adhesive material for orthopedic repair and its preparation method. Background Technology

[0002] Fractures and bone defects are common bone injuries in surgical clinics. Traditionally, alloys are used as internal fixation devices. These materials are ideal in terms of strength and biocompatibility, but they are prone to corrosion, causing inflammation, and surgical removal can cause secondary damage. With continuous technological advancements, bone cement bonding materials for bone repair, such as polymethyl methacrylate (PMMA) and calcium phosphate, have been widely used. However, PMMA releases a large amount of heat during polymerization, causing burns to tissues and nerves in the surrounding bone repair area, and its exudate is cytotoxic, damaging surrounding normal cells. Calcium phosphate bone cement bonding materials, on the other hand, are increasingly being researched and applied to bone repair bonding materials due to their excellent biocompatibility and ease of molding. However, due to the inherent brittleness of inorganic materials, calcium phosphate bone cement bonding materials have poor mechanical properties, easily failing under external forces. Furthermore, their weak antibacterial properties cannot effectively inhibit bacterial growth and adhesion, easily leading to infection after implantation, thus limiting their application in orthopedic repair.

[0003] Chinese invention patent CN102698316A discloses a rapidly curing viscous bone repair material and its preparation method. The bone repair material is composed of a solid powder and a curing liquid. The solid powder is phosphate bone cement powder, and the curing liquid is prepared by dissolving natural polysaccharides or their derivatives or combinations thereof in an organic acid solution. This invention allows for rapid curing of the solid powder and curing liquid, and the resulting repair material exhibits excellent anti-collapse properties, high mechanical strength, good biocompatibility, and biodegradability, but its antibacterial properties are relatively poor. Summary of the Invention

[0004] In view of the shortcomings of the existing technology, the purpose of this invention is to provide an adhesive material for orthopedic repair and its preparation method.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] A bonding material for orthopedic repair, comprising a solid powder and a liquid component;

[0007] The solid powder comprises the following components in parts by weight: 40-55 parts of β-calcium phosphate, 20-30 parts of calcium dihydrogen phosphate monohydrate, 10-15 parts of hydroxyapatite, 5-8 parts of bioactive glass, 8-12 parts of modifier and reinforcing agent, 2-3 parts of developer, and 5-8 parts of antibacterial agent.

[0008] The liquid phase component comprises the following components in parts by weight: 10-20 parts disodium hydrogen phosphate, 4-5 parts sodium alginate, and 50-60 parts deionized water.

[0009] The modified reinforcing agent is prepared by the following method:

[0010] S1: Pentaerythritol reacts with 6-caprolactone to form a polyester compound; the reaction equation is shown below.

[0011]

[0012] S2: The polyester compound reacts with methacrylic anhydride to form a terminal alkenyl polymer; the reaction equation is shown below.

[0013]

[0014] S3: The terminal alkenyl polymer reacts with dopamine to generate a modified reinforcing agent; the reaction equation is shown below:

[0015]

[0016] In step S1, the molar ratio of pentaerythritol to 6-caprolactone is 1:(24-32).

[0017] In step S2, the molar ratio of the polyester compound to methacrylic anhydride is 1:(4.1-4.3).

[0018] In step S3, the molar ratio of the terminal alkenyl polymer to dopamine is 1:(4.2-4.5).

[0019] The antibacterial agent is prepared by the following method:

[0020] N1:N-vinylimidazol reacts with octadecane bromide to give a quaternary ammonium salt compound; the reaction equation is shown below:

[0021]

[0022] N2: Quaternary ammonium salts react with L-cysteine ​​to yield thioether compounds; the reaction equation is shown below:

[0023]

[0024] N3: Sulfide compounds react with trimesin to form an antibacterial agent; the reaction equation is shown below.

[0025]

[0026] In step N1, the molar ratio of N-vinylimidazolium to bromooctadecane is 1:1.05.

[0027] In step N2, the molar ratio of the quaternary ammonium salt compound to L-cysteine ​​is 1:1.1.

[0028] In step N3, the molar ratio of the sulfide compound to trimesoaldehyde is 3.2:1.

[0029] The developing agent is barium sulfate.

[0030] A method for preparing an adhesive material for orthopedic repair includes the following steps:

[0031] (1) Weigh out the following by weight: 40-55 parts of β-calcium phosphate, 20-30 parts of calcium dihydrogen phosphate monohydrate, 10-15 parts of hydroxyapatite, 5-8 parts of bioactive glass, 8-12 parts of modifier and reinforcing agent, 2-3 parts of developer, 5-8 parts of antibacterial agent; 10-20 parts of disodium hydrogen phosphate, 4-5 parts of sodium alginate, and 50-60 parts of deionized water;

[0032] (2) Mix β-calcium phosphate, calcium dihydrogen phosphate monohydrate, hydroxyapatite, bioactive glass, modifier, developer, and antibacterial agent evenly to obtain solid powder;

[0033] (3) Mix disodium hydrogen phosphate, sodium alginate and deionized water evenly to obtain a liquid phase component;

[0034] (4) Mix the solid powder and liquid components at a mass ratio of 2:1 to obtain the bonding material for orthopedic repair.

[0035] Due to the adoption of the above technical solutions, the beneficial effects of the present invention include:

[0036] The orthopedic repair bonding material prepared in this invention improves its mechanical and antibacterial properties by adding a modifier and an antibacterial agent. The modifier enhances interfacial bonding by forming coordination bonds and prevents rapid crack propagation by absorbing and dispersing stress, thereby increasing the compressive strength of the bonding material. The antibacterial agent achieves its antibacterial effect by disrupting bacterial cell membranes and inhibiting the activity of key enzymes, and also improves the stability of the material's compressive strength by forming coordination bonds. Attached Figure Description

[0037] Figure 1 The 1H NMR spectrum of the quaternary ammonium salt compound prepared in step N1 of Example 4;

[0038] Figure 2 The 1H NMR spectrum of the sulfide compound prepared by step N2 in Example 4;

[0039] Figure 3 The 1H NMR spectrum of the antibacterial agent prepared in step N3 of Example 4;

[0040] Figure 4 The image shows a high-resolution mass spectrum of the antibacterial agent prepared in step N3 of Example 4. Detailed Implementation

[0041] The following description, in conjunction with specific embodiments, provides further details, but the present invention is not limited to these embodiments.

[0042] Example 1: Preparation of the modified reinforcing agent:

[0043] S1: Under nitrogen protection, 1000 ml of anhydrous THF, 0.1 mol of pentaerythritol, 2.4 mol of 6-caprolactone, and 2 g of stannous octoate were added to a reaction vessel, stirred, and heated to 50°C. Under stirring, the vessel was evacuated for 2 h to remove THF. The reaction vessel was then sealed, heated to 100°C, and reacted for 20 h. After cooling to room temperature, 600 ml of chloroform was added, and the mixture was stirred until homogeneous. 1000 ml of methanol was slowly added and stirred to precipitate the precipitate. The precipitate was filtered and dried under vacuum at 50°C for 10 h to obtain a polyester compound with a number-average molecular weight of 2832.

[0044] S2: Under nitrogen protection, 1000 ml THF and 0.1 mol polyester compound were added to the reaction vessel, stirred and mixed, heated to 40 °C, and 0.41 mol methacrylic anhydride was added dropwise over 30 min. The mixture was then refluxed for 8 h, cooled to room temperature, and distilled under reduced pressure at 40 °C for 3 h. 500 ml methanol was added and stirred to precipitate the solid. The solid was filtered and dried under vacuum at 50 °C for 10 h to obtain the terminal alkenyl polymer with a number average molecular weight of 3091.

[0045] S3: Under nitrogen protection, 1000 ml of DMF and 0.1 mol of terminal alkenyl polymer were added to the reactor, stirred and mixed, cooled to 0℃, and under light protection, 100 ml of DMF solution containing 0.42 mol of dopamine was added, stirred for 1 h, heated to 50℃ and stirred for 10 h, the reaction solution was poured into 1500 ml of n-hexane, stirred to precipitate solid, filtered, and vacuum dried at 50℃ for 10 h to obtain the modified reinforcing agent.

[0046] Example 2: Preparation of the modified reinforcing agent:

[0047] S1: Under nitrogen protection, 1000 ml of anhydrous THF, 0.1 mol of pentaerythritol, 2.8 mol of 6-caprolactone, and 2 g of stannous octoate were added to a reaction vessel, stirred, and heated to 50°C. Under stirring, the vessel was evacuated for 2 h to remove THF. The reaction vessel was then sealed, heated to 120°C, and reacted for 18 h. After cooling to room temperature, 600 ml of chloroform was added, and the mixture was stirred until homogeneous. 1000 ml of methanol was slowly added and stirred to precipitate the precipitate. The precipitate was filtered and dried under vacuum at 50°C for 10 h to obtain a polyester compound with a number-average molecular weight of 3298.

[0048] S2: Under nitrogen protection, 1000 ml THF and 0.1 mol polyester compound were added to the reaction vessel, stirred and mixed, heated to 40 °C, and 0.42 mol methacrylic anhydride was added dropwise over 30 min. The mixture was then refluxed for 10 h, cooled to room temperature, and distilled under reduced pressure at 50 °C for 3 h. 500 ml methanol was added and stirred to precipitate the solid. The solid was filtered and dried under vacuum at 50 °C for 10 h to obtain the terminal alkenyl polymer with a number average molecular weight of 3554.

[0049] S3: Under nitrogen protection, 1000 ml of DMF and 0.1 mol of terminal alkenyl polymer were added to the reactor and stirred until homogeneous. The mixture was cooled to 0°C and, under light protection, 100 ml of DMF solution containing 0.43 mol of dopamine was added. The mixture was stirred for 1 h, then heated to 55°C and stirred for another 9 h. The reaction solution was poured into 1500 ml of n-hexane and stirred until a solid precipitated. The solid was filtered and dried under vacuum at 65°C for 10 h to obtain the modified reinforcing agent.

[0050] Example 3: Preparation of the modified reinforcing agent:

[0051] S1: Under nitrogen protection, 1000 ml of anhydrous THF, 0.1 mol of pentaerythritol, 3.2 mol of 6-caprolactone, and 2 g of stannous octoate were added to a reaction vessel, stirred, and heated to 50°C. Under stirring, the vessel was evacuated for 2 h to remove THF. The reaction vessel was then sealed, heated to 130°C, and reacted for 15 h. After cooling to room temperature, 600 ml of chloroform was added, and the mixture was stirred until homogeneous. 1000 ml of methanol was slowly added and stirred to precipitate the precipitate. The precipitate was filtered and dried under vacuum at 50°C for 10 h to obtain a polyester compound with a number-average molecular weight of 3743.

[0052] S2: Under nitrogen protection, 1000 ml THF and 0.1 mol polyester compound were added to the reaction vessel, stirred and mixed, heated to 40 °C, and 0.43 mol methacrylic anhydride was added dropwise over 30 min. The mixture was then refluxed for 12 h, cooled to room temperature, and distilled under reduced pressure at 40 °C for 3 h. 500 ml methanol was added and stirred to precipitate the solid. The solid was filtered and dried under vacuum at 50 °C for 10 h to obtain the terminal alkenyl polymer with a number average molecular weight of 4002.

[0053] S3: Under nitrogen protection, 1000 ml of DMF and 0.1 mol of terminal alkenyl polymer were added to the reactor and stirred until homogeneous. The mixture was cooled to 0°C and, under light protection, 100 ml of DMF solution containing 0.45 mol of dopamine was added. The mixture was stirred for 1 h, then heated to 60°C and stirred for another 8 h. The reaction solution was poured into 1500 ml of n-hexane and stirred until a solid precipitated. The solid was filtered and dried under vacuum at 50°C for 10 h to obtain the modified reinforcing agent.

[0054] Example 4: Preparation of antibacterial agent:

[0055] N1: 300 ml of ethyl acetate, 0.1 mol of N-vinylimidazole, and 0.105 mol of bromooctadecane were added to a reaction vessel, stirred and mixed, heated to 50 °C, and reacted for 8 h. The mixture was then cooled to 0 °C to precipitate a solid, kept at this temperature for 2 h, filtered, and recrystallized using a mixed solution of 120 ml of ethyl acetate and anhydrous ethanol (ethyl acetate to anhydrous ethanol volume ratio of 8:2). The solution was filtered again and dried under vacuum at 60 °C for 10 h to obtain the quaternary ammonium salt compound; its 1H NMR spectrum is shown below. Figure 1 The following are the 1H NMR spectral data: 1 H NMR (300 MHz, DMSO- d 6) δ 9.95 (s, 1H), 8.06 (s, 1H), 7.62 (d, J = 3.7 Hz, 2H), 5.90 - 5.73(m, 2H), 4.39 (s, 2H), 2.04 (s, 2H), 1.39 (s, 2H), 1.34 (s, 2H), 1.32 - 1.24 (m, 27H), 0.89 (s, 3H);

[0056] N2: Add 300 ml of methanol, 0.1 mol of quaternary ammonium salt compound, and 0.11 mol of L-cysteine ​​to a reaction vessel, stir and mix thoroughly. Under nitrogen protection, add 1 g of photoinitiator I2959, and stir at an intensity of 8.4 mW / cm². 2 The reaction mixture was irradiated under a 365nm ultraviolet LED lamp for 8 hours at room temperature. The reaction solution was then distilled under reduced pressure at 40℃ for 3 hours. Recrystallization was performed using 150 ml of a mixed solution of ethyl acetate and anhydrous ethanol (ethyl acetate to anhydrous ethanol volume ratio of 8:2). The solution was filtered and dried under vacuum at 60℃ for 10 hours to obtain the sulfide compound. Its 1H NMR spectrum is shown below. Figure 2 The following are the 1H NMR spectral data: 1 H NMR (300 MHz, DMSO- d 6) δ12.41 (s, 1H), 9.58 (s, 1H), 7.99 (s, 1H), 7.56 (s, 1H), 4.41 (s, 2H), 4.09(s, 2H), 3.47 (d, J = 0.5 Hz, 1H), 3.19 - 2.76 (m, 6H), 2.04 (s, 2H), 1.39 (d, J = 1.1 Hz, 2H), 1.34 (s, 2H), 1.32 - 1.24 (m, 26H), 0.89 (s, 3H);

[0057] N3: 800 ml of anhydrous ethanol, 0.32 mol of sulfide compound, and 0.1 mol of trimesin were added to a reaction vessel, followed by 2 g of acetic acid. The mixture was refluxed for 8 h, cooled to room temperature, and distilled under reduced pressure at 50 °C for 3 h. Recrystallization was performed using a mixed solvent of 300 ml of acetone and anhydrous ethanol (volume ratio of acetone to anhydrous ethanol 9:1). The solution was then dried under vacuum at 50 °C for 12 h to obtain the antibacterial agent produced in the reaction. Its 1H NMR spectrum is shown below. Figure 3 The following are the 1H NMR spectral data: 1 H NMR (300 MHz, DMSO- d 6) δ 12.69 (s, 3H), 9.58 (s, 3H), 8.34 (s, 0.7 Hz, 3H), 7.99 (s, 3H), 7.59 - 7.50 (m, 6H), 4.42 (d, J = 5.0 Hz, 9H), 4.09 (s, 6H), 3.38 (d, J = 12.3 Hz, 6H), 2.92 (d, J = 3.3 Hz, 6H), 2.04 (s, 6H), 1.43 - 1.33 (m, 12H), 1.32 - 1.22 (m, 78H), 0.89 (s, 9H); its high-resolution mass spectrum is shown below. Figure 4 As shown, HRMS (m / z): 1514.0685 [M+H] + .

[0058] Example 5: Preparation of bonding materials for orthopedic repair:

[0059] (1) Weigh the following by weight: 40g of β-calcium phosphate, 20g of calcium dihydrogen phosphate monohydrate, 10g of hydroxyapatite, 5g of bioactive glass, 8g of modifier and reinforcing agent (prepared in Example 1), 2g of barium sulfate (developer), 5g of antibacterial agent (prepared in Example 4); 10g of disodium hydrogen phosphate, 4g of sodium alginate, and 50g of deionized water;

[0060] (2) Add β-calcium phosphate, calcium dihydrogen phosphate monohydrate, hydroxyapatite, bioactive glass, modifier, barium sulfate, and antibacterial agent to the reactor and stir at 300 r / min for 30 min to obtain solid powder.

[0061] (3) Add disodium hydrogen phosphate, sodium alginate and deionized water to the reaction vessel, stir at 300 r / min for 20 min at 60℃, cool to room temperature to obtain liquid phase component;

[0062] (4) Mix 80g of solid powder with 40g of liquid component and stir at 100r / min for 20min to obtain bonding material for orthopedic repair.

[0063] Example 6: Preparation of bonding materials for orthopedic repair:

[0064] (1) Weigh the following by weight: 50g of β-calcium phosphate, 26g of calcium dihydrogen phosphate monohydrate, 12g of hydroxyapatite, 6g of bioactive glass, 10g of modifier and reinforcing agent (prepared in Example 2), 2.5g of barium sulfate (developer), 7g of antibacterial agent (prepared in Example 4); 15g of disodium hydrogen phosphate, 4.5g of sodium alginate, and 55g of deionized water;

[0065] (2) Add β-calcium phosphate, calcium dihydrogen phosphate monohydrate, hydroxyapatite, bioactive glass, modifier, barium sulfate, and antibacterial agent to the reactor and stir at 300 r / min for 30 min to obtain solid powder.

[0066] (3) Add disodium hydrogen phosphate, sodium alginate and deionized water to the reaction vessel, stir at 300 r / min for 30 min at 60 °C, and cool to room temperature to obtain the liquid phase component;

[0067] (4) Mix 80g of solid powder with 40g of liquid component and stir at 100r / min for 20min to obtain bonding material for orthopedic repair.

[0068] Example 7: Preparation of bonding materials for orthopedic repair:

[0069] (1) Weigh the following by weight: 55g of β-calcium phosphate, 30g of calcium dihydrogen phosphate monohydrate, 15g of hydroxyapatite, 8g of bioactive glass, 12g of modifier and reinforcing agent (prepared in Example 3), 3g of barium sulfate (developer), 8g of antibacterial agent (prepared in Example 4); 20g of disodium hydrogen phosphate, 5g of sodium alginate, and 60g of deionized water;

[0070] (2) Add β-calcium phosphate, calcium dihydrogen phosphate monohydrate, hydroxyapatite, bioactive glass, modifier, barium sulfate, and antibacterial agent to the reactor and stir at 300 r / min for 30 min to obtain solid powder.

[0071] (3) Add disodium hydrogen phosphate, sodium alginate and deionized water to the reaction vessel, stir at 300 r / min for 40 min at 60 °C, and cool to room temperature to obtain the liquid phase component;

[0072] (4) Mix 80g of solid powder with 40g of liquid component and stir at 100r / min for 20min to obtain bonding material for orthopedic repair.

[0073] Comparative Example 1

[0074] The raw material composition and process of the bonding material used for orthopedic repair are basically the same as those in Example 6, except that the modified reinforcing agent is replaced with an equal weight of polyester compound (prepared in step S1 of Example 2).

[0075] Comparative Example 2

[0076] The raw material composition and process of the bonding material used for orthopedic repair are basically the same as those in Example 6, except that the modified reinforcing agent is replaced with an equal weight of a modified reinforcing agent prepared by the following method:

[0077] The preparation method of the modified reinforcing agent is basically the same as that in Example 2, except that 6-caprolactone in step S1 is replaced with an equimolar amount of L-lactide.

[0078] Comparative Example 3

[0079] The raw material composition and process of the bonding material used for orthopedic repair are basically the same as those in Example 6, except that the modified reinforcing agent is replaced with an equal weight of a modified reinforcing agent prepared by the following method:

[0080] The preparation method of the modified reinforcing agent is basically the same as that in Example 2, except that pentaerythritol in step S1 is replaced with an equimolar amount of glycerol.

[0081] Comparative Example 4

[0082] The raw material composition and process of the bonding material used for orthopedic repair are basically the same as those in Example 6, except that the modified reinforcing agent is replaced with an equal weight of a modified reinforcing agent prepared by the following method:

[0083] The preparation method of the modified reinforcing agent is basically the same as that in Example 2, except that the dopamine in step S3 is replaced with an equimolar amount of p-hydroxyphenylethylamine.

[0084] Comparative Example 5

[0085] The raw material composition and process of the bonding material used for orthopedic repair are basically the same as those in Example 6, except that the antibacterial agent is replaced with an equal weight of an antibacterial agent prepared by the following method:

[0086] The preparation method of the antibacterial agent is basically the same as that in Example 4, except that N-vinylimidazole in step N1 is replaced with an equimolar amount of dimethylallylamine.

[0087] Comparative Example 6

[0088] The raw material composition and process of the bonding material used for orthopedic repair are basically the same as those in Example 6, except that the antibacterial agent is replaced with an equal weight of an antibacterial agent prepared by the following method:

[0089] The preparation method of the antibacterial agent is basically the same as that in Example 4, except that L-cysteine ​​in step N2 is replaced with an equimolar amount of 2-aminoethanethiol.

[0090] Comparative Example 7

[0091] The raw material composition and process of the bonding material used for orthopedic repair are basically the same as those in Example 6, except that the antibacterial agent is replaced with an equal weight of an antibacterial agent prepared by the following method:

[0092] N1: Add 300 ml of ethyl acetate, 0.1 mol of N-vinylimidazole, and 0.105 mol of bromooctadecane to a reaction vessel, stir and mix well, heat to 50 °C, react for 8 h, cool to 0 °C to precipitate solid, keep warm for 2 h, filter, recrystallize using a mixed solution of 120 ml of ethyl acetate and anhydrous ethanol (ethyl acetate to anhydrous ethanol volume ratio of 8:2), filter, and dry under vacuum at 60 °C for 10 h to obtain the quaternary ammonium salt compound;

[0093] N2: Add 300 ml of methanol, 0.1 mol of quaternary ammonium salt compound, and 0.11 mol of L-cysteine ​​to a reaction vessel, stir and mix thoroughly. Under nitrogen protection, add 1 g of photoinitiator I2959, and stir at an intensity of 8.4 mW / cm². 2 Irradiated under a 365nm ultraviolet LED lamp for 8 hours, the reaction temperature was room temperature, the reaction solution was distilled under reduced pressure at 40℃ for 3 hours, recrystallized using a mixed solution of 150ml ethyl acetate and anhydrous ethanol (the volume ratio of ethyl acetate to anhydrous ethanol was 8:2), filtered, and dried under vacuum at 60℃ for 10 hours to obtain the sulfide compound.

[0094] N3: Under nitrogen protection, 800 ml of DMF and 0.1 mol of trimesic acid were added to the reaction vessel and stirred until homogeneous. Then, 0.35 mol of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, 0.35 mol of N-hydroxysuccinimide and 0.1 mol of triethylamine were added. The mixture was stirred at room temperature for 2 h to activate the carboxyl groups. 0.32 mol of thioether compound was added and the mixture was heated to 65 °C and reacted for 6 h. The mixture was poured into 1000 ml of ice water and stirred to precipitate the solid. The solid was filtered and dried under vacuum at 60 °C for 24 h to obtain the antibacterial agent.

[0095] The hydroxyapatite used in the examples and comparative examples of this application is model HAP03-20, produced by Nanjing Junzhuo Biotechnology Co., Ltd.; the bioactive glass is model medical grade HQ-BG45s-D1, produced by Kunshan Huaqiao Science and Technology New Materials Co., Ltd.; the sodium alginate is medical grade, with a viscosity of 600 mPa·s, produced by Qingdao Mingyue Marine New Materials Technology Co., Ltd.

[0096] The bonding materials for orthopedic repair prepared in Examples 5-7 and Comparative Examples 1-7 were prepared into test specimens according to the following method: The bonding material was filled into a cylindrical mold, and a stainless steel cylindrical indenter (φ=5.6mm) was used to apply a force of 700 kPa to the material in the stainless steel mold and hold it for 10 seconds to remove air bubbles inside the bonding material. Then, it was cured at 37°C and 98% humidity for 24 hours, demolded, and the specimens were obtained. The above specimens were subjected to compressive strength tests (specimen size φ6mm×12mm) and antibacterial performance tests (specimen size φ6mm×3mm), and the test results are shown in Table 1.

[0097] Compressive strength test: Place the specimen on the circular tray of the universal testing machine, adjust the upper tray to fit the bonding material sample, set the pressure rate to 0.5 mm / min, and record the maximum load F tested. max Calculate the compressive strength of the specimen σ=4F max / πd 2 d is the diameter.

[0098] Antibacterial performance test: Using a sterile throat swab, the tip of the swab was completely immersed in a bacterial suspension (Staphylococcus aureus (ATCC 25923), bacterial concentration 1.5 × 10⁻⁶). 8 In a solution of CFU / mL, gently press the tube wall to remove excess bacterial solution, then spread the bacterial suspension evenly onto MH agar medium. Spread the sample evenly on the medium and place it in a 37°C bacterial incubator for 24 hours. Remove the medium, take an optical photograph, observe whether an inhibition zone appears around the sample, and measure the diameter of the inhibition zone.

[0099] Table 1 Performance Test Data

[0100]

[0101] As can be seen from the data in Table 1, the bonding materials for orthopedic repair prepared in Examples 5, 6, and 7 of this application have excellent compressive strength and antibacterial properties.

[0102] The modified reinforcing agent prepared in this invention contains a four-armed polyester structure and a catechol structure. When added to bonding materials used in orthopedic repair, it enhances compressive strength. The four-armed structure forms a "mesh support" within the bonding material, absorbing and dispersing stress to prevent rapid crack propagation under external forces. The flexible polyester structure dissipates energy through the stretching and slippage of molecular chains, reducing brittle fracture of the bonding material. The catechol structure forms stable coordination bonds with calcium ions in the bonding material, effectively strengthening the bond between the modified reinforcing agent and the inorganic interface, thereby improving the compressive strength of the bonding material.

[0103] The antibacterial agent prepared in this invention contains imidazole quaternary ammonium salt, long-chain alkyl groups, Schiff bases, and carboxyl groups. Adding it to the bonding material for orthopedic repair enhances its antibacterial properties. Specifically, the quaternary ammonium salt cation adsorbs negatively charged bacteria through electrostatic interactions, disrupting their cell membrane phospholipid bilayer. The relatively low hydrophobicity of the imidazole ring allows the imidazole quaternary ammonium salt to more easily penetrate the microbial cell interior, potentially concentrating more on the cell membrane surface and damaging the membrane structure, but struggling to penetrate deep into the cell interior. The long-chain alkyl groups of the imidazole structure penetrate deep into the hydrophobic nucleus of bacteria, leading to leakage of intracellular substances. The Schiff base can bind to the active sites of enzymes, inhibiting enzyme activity and thus blocking the metabolic pathways of microorganisms, preventing normal growth and reproduction. The carboxyl groups can enhance the formation of stable coordination bonds with calcium ions in the bonding material, strengthening the binding ability of the antibacterial agent to the bonding material and reducing its interference with compressive strength. The antibacterial agent used in Comparative Example 6 does not contain carboxyl groups, resulting in poor compatibility with the bonding material and a decrease in its compressive strength.

[0104] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. However, any modifications, alterations, and variations made by those skilled in the art without departing from the scope of the present invention based on the disclosed technical content are equivalent embodiments of the present invention. Furthermore, any modifications, alterations, and variations made to the above embodiments based on the essential technology of the present invention are still within the protection scope of the present invention.

Claims

1. An adhesive material for orthopedic repair, characterized in that, It contains solid powder and liquid components; The solid powder comprises the following components in parts by weight: 40-55 parts of β-calcium phosphate, 20-30 parts of calcium dihydrogen phosphate monohydrate, 10-15 parts of hydroxyapatite, 5-8 parts of bioactive glass, 8-12 parts of modifier and reinforcing agent, 2-3 parts of developer, and 5-8 parts of antibacterial agent. The liquid phase component comprises the following components in parts by weight: 10-20 parts disodium hydrogen phosphate, 4-5 parts sodium alginate, and 50-60 parts deionized water. The modified reinforcing agent is prepared by the following method: S1: Pentaerythritol reacts with 6-caprolactone to form a polyester compound. S2: Polyester compounds react with methacrylic anhydride to form terminal alkenyl polymers. S3: Terminal alkenyl polymers react with dopamine to generate modified reinforcing agents.

2. The adhesive material for orthopedic repair according to claim 1, characterized in that, In step S1, the molar ratio of pentaerythritol to 6-caprolactone is 1:(24-32).

3. The adhesive material for orthopedic repair according to claim 1, characterized in that, In step S2, the molar ratio of the polyester compound to methacrylic anhydride is 1:(4.1-4.3).

4. The adhesive material for orthopedic repair according to claim 1, characterized in that, In step S3, the molar ratio of the terminal alkenyl polymer to dopamine is 1:(4.2-4.5).

5. The adhesive material for orthopedic repair according to claim 1, characterized in that, The antibacterial agent is prepared by the following method: N1: The reaction of N-vinylimidazolium with octadecane bromide yields a quaternary ammonium salt compound. N2: Quaternary ammonium salt compounds react with L-cysteine ​​to give thioether compounds. N3: Thioether compounds react with pyromellitic methyl ether to form antibacterial agents.

6. The adhesive material for orthopedic repair according to claim 5, characterized in that, In step N1, the molar ratio of N-vinylimidazolium to bromooctadecane is 1:1.

05.

7. The adhesive material for orthopedic repair according to claim 5, characterized in that, In step N2, the molar ratio of the quaternary ammonium salt compound to L-cysteine ​​is 1:1.

1.

8. The adhesive material for orthopedic repair according to claim 5, characterized in that, In step N3, the molar ratio of the sulfide compound to trimesoaldehyde is 3.2:

1.

9. The adhesive material for orthopedic repair according to claim 1, characterized in that, The developing agent is barium sulfate.

10. A method for preparing an adhesive material for orthopedic repair according to any one of claims 1-9, characterized in that, Includes the following steps: (1) Weigh out the following by weight: 40-55 parts of β-calcium phosphate, 20-30 parts of calcium dihydrogen phosphate monohydrate, 10-15 parts of hydroxyapatite, 5-8 parts of bioactive glass, 8-12 parts of modifier and reinforcing agent, 2-3 parts of developer, 5-8 parts of antibacterial agent; 10-20 parts of disodium hydrogen phosphate, 4-5 parts of sodium alginate, and 50-60 parts of deionized water; (2) Mix β-calcium phosphate, calcium dihydrogen phosphate monohydrate, hydroxyapatite, bioactive glass, modifier, developer, and antibacterial agent evenly to obtain solid powder; (3) Mix disodium hydrogen phosphate, sodium alginate and deionized water evenly to obtain a liquid phase component; (4) Mix the solid powder and liquid components at a mass ratio of 2:1 to obtain the bonding material for orthopedic repair.

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