Application of a Multifunctional Silane Coupling Agent in the Surface Modification of Bioactive Glass

Abstract

The present invention uses commercially available 3-aminopropylsilane coupling agent, diallylamino polyether acrylate, and an alkylating agent, or γ-propanesultone, or γ-butyrolactone as raw materials, and through an aza-Michael addition reaction and a quaternization reaction, a multifunctional silane coupling agent containing one or more quaternary ammonium cations, or sulfobetaine, or carboxybetaine in its molecular structure is prepared, which is used for the surface modification of bioactive glass, and the bioactivity, antibacterial and antifungal properties, and hydrophilicity enhancement effects after the surface modification of bioactive glass are obtained.

Description

Technical Field

[0001] The present invention relates to the application of a multifunctional silane coupling agent in the surface modification of bioactive glass, and particularly to the use of a multifunctional silane coupling agent containing diallyl quaternary ammonium cations, sulfobetaine or carboxybetaine in the molecular structure for the surface modification of bioactive glass, belonging to the field of functional materials. Technical Background

[0002] Bioactive glass is an inorganic material mainly composed of the quaternary chemical composition of SiO2-CaO-P2O5-Na2O. The reason why bioactive glass has biological activity is mainly that the alkaline earth metal and alkali metal ions connected by non-bridging oxygen in the three-dimensional network of bioactive glass are released in an aqueous medium, and Ca 2+ or Na + is easily soluble in water to form a hydrated silicic acid gel layer, so it is called bioactive glass. For decades, a large number of studies have confirmed that bioactive glass has good osteogenic properties, good biocompatibility and self-degradation properties. When used as a material for repairing bone defects, bioactive glass can rapidly regenerate bone tissue, and the structure and mechanical properties of the regenerated bone are well matched with the bone defect site; there are also studies showing that bioactive glass can promote the regeneration of soft tissues such as skin and has a significant function of promoting the healing of skin wounds. Some scholars cultured bioactive glass with intestinal epithelial cells and found that bioactive glass can promote the proliferation of intestinal epithelial cells. However, the dispersibility of bioactive glass particles in the human body or organic polymers is very poor, and the combination of bioactive glass and the organic phase is relatively loose, which affects the mechanical properties and use functions of the composite material. To solve these problems, relevant studies at home and abroad, such as CN201210358478.2, CN201611163396.7, CN201811478997.6, CN201911356221.1, etc., have been publicly reported to use silane coupling agents to modify the surface of bioactive glass, improve the interfacial compatibility between bioactive glass and organic polymers through chemical bonding, improve its binding ability and dispersibility with organic polymers, and enhance the mechanical properties of the composite material.

[0003] A silane coupling agent is an organosilicon compound with a hydrolyzable group and a functional group in its molecular structure, and its structure is usually represented as Y n SiX (4-n), where X represents a hydrolyzable group, including alkoxy groups, acyl groups, chlorine atoms, etc.; Y in the molecular structure of the silane coupling agent represents a functional group, including alkenyl groups, epoxy groups, amino groups, mercapto groups, hydroxyl groups, isocyanate groups, haloalkyl groups, etc.; n is an integer selected from 1 to 3; when the X group hydrolyzes, Si-X is converted to Si-OH, and the hydroxyl groups in Si-OH can not only dehydrate and condense with each other to form Si-O-Si bonds, but also combine with Si-OH on the surface of glass, silica, ceramics, some metal materials or in other molecules to form Si-O-Si bonds. In this way, functional groups such as alkenyl groups, epoxy groups, amino groups, mercapto groups, hydroxyl groups, isocyanate groups, halogen atoms, etc. that can undergo chemical reactions can be introduced onto the surface of glass, silica, ceramics, or some metal materials. Therefore, silane coupling agents are mainly used for surface modification of silica materials or ceramics, etc., or to improve the interfacial compatibility of their composite materials. According to the characteristics of the functional groups of existing silane coupling agents, the surface characteristics of the materials to be treated, the modification requirements, and the application needs in some new fields, the re-functionalization of the silane coupling agents has attracted people's attention. The re-functionalization of existing silane coupling agents is mainly achieved by bonding structural units with more powerful functions to the functional groups, thereby endowing the materials to be modified with new functions and uses. For example, CN201010503258.5, CN201610807720.8, CN202010940152.5, CN202110914812.7, CN201610766177.1, CN202010446615.2, CN201910559445.6, CN201811365280.0, CN201310134973.X, etc. have disclosed silane coupling agents carrying quaternary ammonium cations, zwitterions, or containing polyether chains, and there are also copolymers of zwitterionic olefin monomers and olefin silane coupling agents, etc. As surface modifiers for inorganic materials such as the glass or silica gel, positive effects have been achieved.

[0004] In view of this, in combination with the previous research results of this research group, such as ZL201910993648.6, ZL2021107850204, ZL201910994314.0, ZL201811189217, CN2023100519084, CN202310116727.5, CN 202310116725.6, etc., the inventor carried out a re-functionalization design on the commercially available 3-aminopropylsilane coupling agent, and created a multifunctional silane coupling agent with a novel molecular structure. The hydrolyzable group in the molecular structure of the multifunctional silane coupling agent is still the traditional trialkoxy group; and the amino group in the 3-aminopropylsilane coupling agent successively undergoes an almost quantitative aza-Michael addition reaction with diallylamino polyether acrylate, and then a quaternization reaction with an alkylating agent, propanesultone or the quaternary ammonium salt of γ-butyrolactone, so that there is more than one quaternary ammonium cation, or sulfobetaine, or carboxybetaine in the molecular structure of the multifunctional silane coupling agent. Thus, when the multifunctional silane coupling agent of the present invention is used for the surface modification of bioactive glass, not only can the enhanced effects of biocompatibility, antibacterial and hydrophilic properties of the surface-modified bioactive glass be obtained; at the same time, the diallylammonium remaining on the surface-modified bioactive glass also has the property of participating in the copolymerization reaction with olefin monomers. Summary of the Invention

[0005] The present invention provides an application of a multifunctional silane coupling agent in the surface modification of bioactive glass, which is characterized in that it is realized through the following process: according to the mass ratio of multifunctional silane coupling agent / methanol or ethanol / water of 2-20:5-50:5-50, successively weigh methanol or ethanol, multifunctional silane coupling agent and water, and prepare a multifunctional silane coupling agent solution at room temperature. Then, under stirring, add bioactive glass, heat up to 50-90 °C and react for 2-20 hours; end the reaction process, cool the reaction product to room temperature, filter and wash, and send the filter cake to a vacuum drying oven, and vacuum dry at a controlled temperature of 25-65 °C until constant weight to obtain surface-modified bioactive glass.

[0006] Wherein the dosage of the multifunctional silane coupling agent is 5-500% of the mass of the bioactive glass particles.

[0007] The multifunctional silane coupling agent has the structures shown in general formula (A), general formula (A'), general formula (A"), general formula (A''') or general formula (A"''):

[0008]

[0009]

[0010] Among them, R in the general formula (A), general formula (A'), general formula (A''), general formula (A''') or general formula (A'''') is selected from C1-C 18 hydrocarbyl, R1 is selected from H or methyl, n is selected from natural numbers between 1 and 2000. When Y is selected from C1-C 18 hydrocarbyl or when, X - is selected from Cl - , Br - , I - or p-CH3C6H4SO3 - one of them. When Y is selected from -CH2CH2CH2SO3 - , or -CH2CH2CH2CO2 - when, X - does not select any counter anions; among them, R2 is selected from C1-C 18 hydrocarbyl, m is selected from natural numbers between 0 and 2000.

[0011] Existing relevant research results and application tests have taught us that: the structural units in the multifunctional silane coupling agent described in the present invention can, according to its functions and properties and the actual application needs, purposefully optimize the selection of Y, R1 and R2 on N + . For example, if the hydrophilic function needs to be emphasized, Y of the multifunctional silane coupling agent is preferably CH3, R1 and R2 are preferably H or CH3, and n is preferably 1-3; if the hydrophilic, antibacterial and sterilizing functions need to be emphasized, Y of the multifunctional silane coupling agent is preferably C 12 H 25 or C7H8, n is preferably 1-3, and R1 and R2 are preferably H or CH3; if the main purposes are modification such as hydrophilicity, antibacterial, antifouling, biocompatibility, and anti-blood coagulation, Y is preferably C 12 H 25 or C7H8, R2 is selected as CH3, and n is preferably 8-25. In addition, compared with the prior art, one molecule of the multifunctional silane coupling agent can endow the surface of bioactive glass with multiple hydrophilic groups, and the surface modification of bioactive glass is more effective.

[0012] The preparation method of the multifunctional silane coupling agent of the present invention is to dissolve 3-aminopropyl silane coupling agent in a solvent, control the temperature at 5-35°C, under N2 protection, start stirring and slowly add diallylamino polyether acrylate. The dosage of diallylamino polyether acrylate is 2.0-2.2 times the molar amount of the 3-aminopropyl silane coupling agent; after the addition of diallylamino polyether acrylate is completed, slowly raise the temperature of the reaction system to 35-90°C and react for 2-20 hours to end the Michael addition reaction process; keep the reaction temperature, add an alkylating agent, or propanesultone, or γ-butyrolactone to the reaction system. The dosage of the alkylating agent, or propanesultone, or γ-butyrolactone is 1.0-3.5 times the molar amount of the 3-aminopropyl silane coupling agent, and continue to react for 2-20 hours to end the quaternization reaction process; then rotary evaporate to remove part of the solvent, and then cool the temperature of the reaction product system to room temperature to precipitate the crude product. The crude product is further purified to obtain the multifunctional silane coupling agent with the structure shown in general formula (A).

[0013] Among them, the 3-aminopropyl silane coupling agent has the structure shown in general formula (B):

[0014]

[0015] Among them, R in general formula (B) is selected from C1-C 18 hydrocarbon group.

[0016] The solvent refers to one or more of methanol, ethanol, propanol, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylformamide, N,N-diethylformamide or hexamethylphosphoramide; the dosage of the solvent is 1-10 times the mass of general formula (B).

[0017] The diallylamino polyether acrylate has the structure shown in general formula (C):

[0018]

[0019] Among them, R1 in general formula (C) is selected from H or methyl, and n is a natural number between 1 and 2000.

[0020] The alkylating agent has the structure shown in general formula (D):

[0021] Y-X

[0022] General formula (D)

[0023] Among them, Y in general formula (D) is selected from C1-C 18 hydrocarbon group or X is selected from one of Cl, Br, I or p-CH3C6H4SO3, where m is selected from natural numbers between 0 and 2000, and R2 is selected from C1-C18 hydrocarbon groups.

[0024] The beneficial effects of the application of a multifunctional silane coupling agent in the surface modification of bioactive glass provided by the present invention are as follows:

[0025] ① The structure of the multifunctional silane coupling agent described in the present invention is novel, the preparation method is simple, most of the preparation raw materials are commercially available products, the product yields in each step of the preparation process are high, the purification technology of the multifunctional silane coupling agent is simple and reliable, and the process is simple and easy to implement.

[0026] ② The multifunctional silane coupling agent described in the present invention is easily soluble in water and can be dissolved in a large amount of methanol or ethanol. The use method of the multifunctional silane coupling agent is simple, and almost no volatile toxic organic substances are generated.

[0027] ③ Using the multifunctional silane coupling agent described in the present invention to modify the surface of bioactive glass, the process is simple and the modification effect is remarkable. Detailed implementation mode

[0028] In order to further understand the present invention, it is specifically described by way of examples, and the purpose is to better understand the content of the present invention. Therefore, the surface modification of bioactive glass by the multifunctional silane coupling agent not listed in the examples should not be regarded as a limitation to the protection scope of the present invention.

[0029] Example 1 Preparation of surface-modified bioactive glass (A-1)

[0030] Step 1: Preparation of the multifunctional silane coupling agent of formula (A-1):

[0031]

[0032] Dissolve 78 grams (about 0.202 mol) of diallylamino polyether methacrylate of formula (C-1) in 320 grams of methanol and put it into a reaction kettle. Start stirring. Under the protection of N2, slowly add 22 grams (about 0.1 mol) of commercially available amino silane coupling agent of KH-550 grade at a controlled temperature of 10-15 °C. After the feeding of the KH-550 amino silane coupling agent is completed, raise the reaction temperature to 35-45 °C and react for 12 hours. Then add 44 grams of benzyl chloride (about 0.349 mol) into the reaction kettle, raise the reaction temperature to 70-90 °C and react for 20 hours. Then, rotary evaporate to remove part of the methanol, and then lower the temperature of the reaction product system to room temperature. White solid substances will precipitate. Filter, wash with dehydrated acetone, and dry in vacuum to obtain the multifunctional silane coupling agent of formula (A-1).

[0033] KH-550 is the commercial abbreviation of 3-aminopropyltriethoxysilane. The aza-Michael addition reaction product of it and diallylamino polyether methacrylate of formula (C-1), after sampling, separation and purification, the yield of the intermediate tertiary amine was calculated to be about 98.3%, and the yield of the multifunctional silane coupling agent of formula (A-1) was about 89.7%. The IR spectrum of the multifunctional silane coupling agent also showed strong absorption peaks near 1726 nm and 1108 nm; the results of elemental analysis (theoretical value %): C 61.45 (62.00), H 8.03 (8.47), N 3.01 (3.10), indicating that it 70 H 114 Cl3N3O 14 Si is in agreement. The product of the multifunctional silane coupling agent of formula (A-1) was also analyzed by nuclear magnetic resonance and mass spectrometry, and it was confirmed that the chemical structure of the product in the preparation process of the present invention was in agreement with the theoretical design.

[0034] Step 2. Preparation of surface-modified bioactive glass (A-1): Weigh 86 g of ethanol, 14 g of the multifunctional silane coupling agent of formula (A-1), and 100 g of water, and sequentially add them into a reaction flask at room temperature, and stir evenly to prepare a multifunctional silane coupling agent solution. Then put 30 g of calcium phosphate silicate bioactive glass with a particle size ≤ 10 μm (purchased from Wuhan Kemike Biopharmaceutical Technology Co., Ltd.) into it. After ultrasonic treatment for 0.5 h, the temperature was raised to 70-80 °C and stirred for 6 h to end the reaction process. After cooling and filtering, the filter cake was washed three times with ethanol, and vacuum dried at a controlled temperature of 50-55 °C to constant weight to obtain 40.8 g of surface-modified bioactive glass (A-1).

[0035] Using the same method and procedure, 29.2 g of a blank sample of bioactive glass was prepared. It can be calculated that the net weight gain of the surface-modified bioactive glass (A-1) was 11.6 g. From this, the reaction efficiency of the multifunctional silane coupling agent of formula (A-1) on the surface of the bioactive glass was deduced to be 91.7%.

[0036] In the IR spectrum of the surface-modified bioactive glass (A-1) relative to the blank sample of bioactive glass, medium-strong and strong absorption peaks were increased at 2932 nm, 2873 nm, 1724 nm, 1164 nm, etc., which should belong to the vibration absorption of methyl, methylene, ester carbonyl and C-O-C respectively, indicating that the surface-modified bioactive glass (A-1) has the structural characteristics of carboxylic ester and ether bond.

[0037] Preparation of surface-modified bioactive glass (A-1’) in Comparative Example 1

[0038] According to the method and steps of Example 1, 14 g of the aza-Michael addition reaction product of KH-550 amino silane coupling agent and diallylamino polyether methacrylate of formula (C-1) was weighed and used to surface-treat 30 g of calcium phosphate-silicate-based bioactive glass powder with a particle size ≤ 10 μm produced by Wuhan Kemic Biopharmaceutical Technology Co., Ltd., to obtain 40.4 g of surface-modified bioactive glass (A-1').

[0039] By calculating that the net weight gain of the surface-modified bioactive glass (A-1') relative to the bioactive glass blank sample is 11.2 g, it shows that the reaction efficiency of the aza-Michael addition product on the surface of the bioactive glass is 90.3%. The surface-modified bioactive glass (A-1') was analyzed and characterized using analytical instruments, and it was proved that the surface-modified bioactive glass (A-1') has structural units of carboxylic acid esters and ether bonds.

[0040] Preparation of surface-modified bioactive glass (A-2) in Example 2

[0041] According to the operation method of Step 1 in Example 1, 2-(N,N-diallylamino)ethyl methacrylate was used instead of diallylamino polyether methacrylate of formula (C-1), and benzyl chloride was replaced with ω-methoxypolyethylene glycol-400 p-toluenesulfonate to prepare a multifunctional silane coupling agent of formula (A-2) with a yield of 91.4%. The IR spectrum, 1 1H-NMR, mass spectrometry analysis and elemental analysis results (theoretical values %): C 53.09 (55.50), H 7.93 (8.80), N 1.64 (1.72), indicating that it is basically consistent with the molecular formula C 114 H 213 N3O 44 S2Si of formula (A-2), and thus it was determined that the chemical structure of the multifunctional silane coupling agent product of formula (A-2) is consistent with the theoretical design.

[0042]

[0043] Using the method and procedure of Step 2 in Example 1, the multifunctional silane coupling agent of formula (A-2) was used to surface-modify the calcium phosphate-silicate-based bioactive glass powder with a particle size ≤ 10 μm produced by Wuhan Kemic Biopharmaceutical Technology Co., Ltd. to obtain surface-modified bioactive glass (A-2). By means of IR spectrum analysis, it was determined that the surface-modified bioactive glass (A-2) has the structural characteristics of carboxylic acid esters and ether bonds.

[0044] Preparation of surface-modified bioactive glass (A-3) in Example 3

[0045] According to the method and operation steps of Example 1, replace the calcium phosphate-silicate bioactive glass powder with a particle size ≤10 μm produced by Wuhan Kemike Biopharmaceutical Technology Co., Ltd. in Step 2 of Example 1 with bioactive glass produced by Hebei Yougu Biotech Co., Ltd. with a SiO₂ content of 45%, a CaO₂ content of 24.5%, a Na₂O content of 24.5%, and a P₂O₅ content of 6.0%, brand name Yougulin, and a particle size ≤45 μm powder to obtain surface-modified bioactive glass (A-3). By means of infrared spectroscopy analysis, it is determined that the surface-modified bioactive glass (A-3) has the structural characteristics of carboxylic acid esters and ether bonds.

[0046] Preparation of surface-modified bioactive glass (A-3’) in Comparative Example 2

[0047] According to the operation procedure of Step 2 in Example 1, take the aza-Michael addition reaction product of KH-550 amino silane coupling agent and diallylamino polyether methacrylate of formula (C-1) in Step 1 of Example 1 to perform surface modification treatment on the bioactive glass produced by Hebei Yougu Biotech Co., Ltd. with a SiO₂ content of 45%, a CaO₂ content of 24.5%, a Na₂O content of 24.5%, and a P₂O₅ content of 6.0% to obtain surface-modified bioactive glass (A-3’).

[0048] Preparation of surface-modified bioactive glass (A-4) in Example 4

[0049] According to the method and operation steps of Example 1, replace the KH-550 amino silane coupling agent in Step 1 with a KH-540 amino silane coupling agent, replace the diallylamino polyether methacrylate of formula (C-1) with 2-(N,N-diallylamino)ethyl methacrylate, and replace benzyl chloride with dodecyl bromide to obtain the multifunctional silane coupling agent of formula (A-4) with a yield of 73.3%. The IR spectrum, 1 ¹H-NMR, mass spectrometry analysis and elemental analysis results (theoretical values %): C 53.18 (55.69), H 9.38 (10.00), Br 17.61 (19.50), indicating that it basically coincides with the designed molecular formula C 57 H 122 Br₃N₃O₇Si, thus confirming that the chemical structure of formula (A-4) coincides with the theoretical design.

[0050]

[0051] According to the method and operation steps of Example 1, the calcium phosphate-silicate bioactive glass powder with a particle size ≤ 10 μm produced by Wuhan Kemike Biopharmaceutical Technology Co., Ltd. in Step 2 was replaced with nano-bioactive glass (the nano-bioactive glass was self-made according to the publicly disclosed technology of ZL02110586.3). The nano-bioactive glass was surface-modified with the multifunctional silane coupling agent of formula (A-4) to obtain surface-modified nano-bioactive glass (A-4). By means of infrared spectrum analysis, it was proved that the surface-modified nano-bioactive glass (A-4) had the structural characteristics of carboxylate and ether bonds.

[0052] Example 5 Characteristics of bioactive glass before and after surface modification in Examples 1 to 4

[0053] 1.5 g of the surface-modified bioactive glass in Examples 1 to 4 was respectively taken, and tablets were made using a tablet press. The pure water contact angles of each tablet were measured statically using a contact angle measuring instrument, and the results are shown in Table 1.

[0054] Table 1 Measurement results of water contact angles of bioactive glasses in Examples 1 to 4

[0055] Example 1 2 3 4 Comparative Example 1 Comparative Example 2 Blank Water contact angle (°) 0 0 0 0 23.4 25.2 10.7

[0056] The results in Table 1 confirmed that after the surface treatment of the bioactive glass with the multifunctional silane coupling agent of the present invention, its hydrophilicity was significantly improved; when the bioactive glass was modified with an organic amine-based silane coupling agent, its hydrophilicity decreased.

Claims

1. Application of a multifunctional silane coupling agent in surface modification of bioactive glass, characterized in that It is achieved through the following steps: Weigh methanol or ethanol, multifunctional silane coupling agent, and water in sequence according to the mass ratio of multifunctional silane coupling agent / methanol or ethanol / water being 2 - 20:5 - 50:5 - 50, and prepare the multifunctional silane coupling agent solution at room temperature. Then, put bioactive glass into it under stirring, raise the temperature to 50 - 90 °C and react for 2 - 20 hours; end the reaction process, let the temperature of the reaction system drop to room temperature, filter, wash the filter cake with methanol or ethanol, and then send the filter cake into a vacuum drying oven, and vacuum dry it at a controlled temperature of 25 - 65 °C until constant weight to obtain surface-modified bioactive glass; wherein the dosage of the multifunctional silane coupling agent is 5 - 500% of the mass of bioactive glass particles; the multifunctional silane coupling agent has a structure shown in one of general formula (A), general formula (A'), general formula (A"), general formula (A''') or general formula (A""); Among them, R in the general formula (A), general formula (A'), general formula (A"), general formula (A"') or general formula (A"") is selected from C1-C 18 hydrocarbyl, R1 is selected from H or methyl, n is a natural number between 1 and 2000. When Y is selected from C1-C 18 hydrocarbyl or when, X - is selected from Cl - , Br - , I - or p-CH3C6H4SO3 - in one kind. When Y is selected from -CH2CH2CH2SO3 - or -CH2CH2CH2CO2 - when, X - does not select any counter anion; wherein R2 is selected from C1 to C 18 hydrocarbyl, and m is a natural number selected from 0 to 2000.

2. The application of a multifunctional silane coupling agent in the surface modification of bioactive glass according to claim 1, characterized in that the preparation method of the multifunctional silane coupling agent is to dissolve 3-aminopropylsilane coupling agent in a solvent, control the temperature at 5 - 35 °C, under N2 protection, start stirring and slowly add diallylamino polyether acrylate, and the dosage of diallylamino polyether acrylate is 2.0 - 2.2 times the molar amount of the 3-aminopropylsilane coupling agent; after the feeding of diallylamino polyether acrylate is completed, slowly raise the temperature of the reaction system to 35 - 90 °C and react for 2 - 20 hours to end the Michael addition reaction process; keep the reaction temperature, add an alkylating agent, or propanesultone, or γ-butyrolactone into the reaction system, and the dosage of the alkylating agent, or propanesultone, or γ-butyrolactone is 1.0 - 3.5 times the molar amount of the 3-aminopropylsilane coupling agent, and continue to react for 2 - 20 hours to end the quaternization reaction process; then rotary evaporate to remove part of the solvent, and then cool down to room temperature to precipitate the crude product, and the crude product is further purified to obtain the multifunctional silane coupling agent with the structure shown in general formula (A); wherein the dosage of the solvent is 1 - 10 times the mass of the 3-aminopropylsilane coupling agent.

3. The application of a multifunctional silane coupling agent in the surface modification of bioactive glass according to claim 2, characterized in that the 3-aminopropylsilane coupling agent has a structure shown in general formula (B); Among them, R in the general formula (B) is selected from C1-C 18 hydrocarbyl group.

4. The application of a multifunctional silane coupling agent in the surface modification of bioactive glass according to claim 2, characterized in that the solvent refers to one or more of methanol, ethanol, propanol, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylformamide, N,N-diethylformamide or hexamethylphosphoramide.

5. The application of a multifunctional silane coupling agent in the surface modification of bioactive glass according to claim 2, wherein the diallylamino polyether acrylate has a structure shown in general formula (C); wherein R1 in general formula (C) is selected from H or methyl, and n is a natural number between 1 and 2000.

6. The application of a multifunctional silane coupling agent in the surface modification of bioactive glass according to claim 2, wherein the alkylating agent has a structure shown in general formula (D); Y - X General formula (D) Among them, when Y in the general formula (D) is selected from C1-C 18 hydrocarbyl or when, X is selected from one of Cl, Br, I or p-CH3C6H4SO3; where m is selected from natural numbers between 0 and 2000, and R2 is selected from C1-C 18 hydrocarbyl groups.

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