CN117049794A - Application of functional silane coupling agent in surface modification of bioactive glass - Google Patents

Application of functional silane coupling agent in surface modification of bioactive glass Download PDF

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CN117049794A
CN117049794A CN202311027279.8A CN202311027279A CN117049794A CN 117049794 A CN117049794 A CN 117049794A CN 202311027279 A CN202311027279 A CN 202311027279A CN 117049794 A CN117049794 A CN 117049794A
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coupling agent
silane coupling
bioactive glass
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reaction
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骆昱晖
周子林
范倩倩
李�杰
贾雪梦
张田林
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Jiangsu Ocean University
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    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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Abstract

The invention takes commercial 3-aminopropyl silane coupling agent, hydroxyethyl methacrylate or hydroxyethyl acrylate and one of alkylating agent, polyether sulfonate, gamma-propane sultone or gamma-butyrolactone as raw materials, and the functional silane coupling agent which contains dihydroxyl quaternary ammonium cations, dihydroxyl sulfobetaines or dihydroxyl carboxyl betaines in the molecular structure and is prepared through Michael addition reaction and quaternary ammonium salt reaction is used for surface modification of bioactive glass, so that the biocompatibility, antibacterial and bacteriostasis performance and hydrophilicity enhancement effects of the surface modified bioactive glass are obtained.

Description

Application of functional silane coupling agent in surface modification of bioactive glass
Technical Field
The invention relates to application of a functional silane coupling agent in surface modification of bioactive glass, in particular to application of a silane coupling agent containing dihydroxyl quaternary ammonium cations, dihydroxyl sulfobetaines or dihydroxyl carboxyl betaines in a molecular structure in surface modification of bioactive glass, belonging to the field of functional composite materials.
Technical Field
The bioactive glass is prepared from SiO 2 -CaO-P 2 O 5 -Na 2 The inorganic material composed of O quaternary chemical components mainly has biological activity mainly because alkali metal and alkaline earth metal ions connected by non-bridging oxygen in the three-dimensional network of the biological activity glass are in aqueous medium, na + Or Ca 2+ Is readily water soluble and releases to form a hydrogel layer of hydrous silicic acid, and is therefore referred to as bioactive glass. For decades, a great number of researches have proved that the bioactive glass particles have good osteogenesis performance, good biocompatibility and self-degradation performance, and the bioactive glass can quickly regenerate bone tissues when being used as a bone defect repairing material, and the structure and mechanical properties of regenerated bone have good matching degree with bone defect positions; also, the research shows that the bioactive glass can promote the regeneration of soft tissues such as skin and the like, and has the function of obviously promoting the healing of skin wound surfaces. The biologically active glass was cultured with intestinal epithelial cells by a learner and found that the biologically active glass can promote proliferation of intestinal epithelial cells. However, the dispersibility of the bioactive glass powder in human bodies or organic polymers is poor, and the combination of the bioactive glass and the organic phase is loose, so that the mechanical property and the use function of the composite material are affected. In order to solve the problems, related researches such as CN201210358478.2, CN201611163396.7, CN201811478997.6 and CN201911356221.1 and the like at home and abroad are disclosed, wherein the surface of the bioactive glass is modified by utilizing a silane coupling agent, the interfacial compatibility of the bioactive glass and an organic polymer is improved by a chemical bonding mode, and the binding capacity and dispersibility of the bioactive glass and the organic polymer are improved.
The silane coupling agent is a compound whose molecular structure contains hydrolytic group and functional groupOrganosilicon compounds capable of radicals, the structure of which is generally denoted Y n SiX (4-n) Wherein X in the molecular structure of the silane coupling agent represents a hydrolyzable group including alkoxy, acyl, chlorine atom and the like; y represents a functional group including alkenyl, epoxy, amino, mercapto, hydroxyl, isocyanate, haloalkyl, etc.; n is selected from integers of 1 to 3. When the X groups are hydrolyzed, si-X is converted into Si-OH, hydroxyl groups in the Si-OH can be dehydrated and condensed to generate Si-O-Si bonds, and can be combined with Si-OH on the surfaces of glass, silicon dioxide, ceramics and some metal materials or in other molecules to form Si-O-Si bonds, so that functional groups such as alkenyl groups, epoxy groups, amino groups, mercapto groups, hydroxyl groups, isocyanate groups, halogen atoms and the like which can be subjected to chemical reaction can be introduced on the surfaces of the glass, the silicon dioxide, the ceramics or some metal materials. Therefore, the silane coupling agent is mainly applied to surface modification of silica materials or ceramics and the like or improvement of interface compatibility of composite materials thereof. According to the characteristics of functional groups of the existing silane coupling agent, the surface characteristics of materials to be treated, the modification requirements and the application requirements of some new fields, the re-functionalization of the existing silane coupling agent attracts attention. The re-functionalization of the silane coupling agent is mainly realized by bonding a structural unit with stronger function through a functional group, so that a new function and a new application of the material to be modified are provided, for example, CN201010503258.5, CN201610807720.8, CN202010940152.5, CN202110914812.7, CN201610766177.1, CN202010446615.2, CN201910559445.6, CN201811365280.0, CN201310134973.X and the like disclose that the silane coupling agent carries quaternary ammonium cations, zwitterions or contains polyether chains, and also copolymers containing zwitterionic olefin monomers and olefin silane coupling agents and the like are used as the surface modifying agent of inorganic materials such as glass or silica gel and the like, and positive effects are obtained.
In view of this, in combination with previous research results of the subject groups ZL201910993648.6, ZL2021107850204, ZL201910994314.0, ZL201811189217, CN2023100519084, CN202310116727.5, CN 202310116725.6, etc., the present inventors have made a re-functionalization design of commercially available 3-aminopropyl silane coupling agents, creating a dihydroxyl functionalized silane coupling agent containing quaternary ammonium cations, sulfobetaines, or carboxybetaines in the molecular structure. The functional silane coupling agent is prepared from commercial 3-aminopropyl silane coupling agent, hydroxyethyl acrylate, and one of an alkylating agent, gamma-propane sultone or gamma-butyrolactone by means of aza-Michael addition reaction and quaternization reaction. The hydrolyzable group in the molecular structure of the functional silane coupling agent is still traditional trialkoxy; the primary amino in the 3-aminopropyl silane coupling agent is firstly subjected to an almost quantitative aza-Michael addition reaction with acrylate hydroxyethyl, and then is subjected to a quaternary ammonification reaction with an alkylating agent, or gamma-propane sultone, or gamma-butyrolactone, so that the dihydroxyl functionalized silane coupling agent containing quaternary ammonium cations, or sulfobetaines, or carboxybetaines is prepared. Therefore, the functional silane coupling agent is used for surface modification of bioactive glass, and can obtain the enhancement effects of the surface modified bioactive glass on biocompatibility, antibacterial property, bacteriostasis and hydrophilicity.
Disclosure of Invention
The invention provides an application of a functional silane coupling agent in the surface modification of bioactive glass, which is realized through the following processes: sequentially weighing methanol or ethanol, a functional silane coupling agent and water according to the mass ratio of the methanol or ethanol to the functional silane coupling agent to the water of 5-50:5-50, preparing a functional silane coupling agent solution at room temperature, stirring, adding bioactive glass particles, heating to 50-90 ℃ for reacting for 2-20 hours, and ending the reaction process; and then cooling the reaction product to room temperature, filtering, washing a filter cake by using methanol or ethanol, sending the washed filter cake into a vacuum drying phase, and vacuum drying at the temperature of 25-65 ℃ to constant weight to obtain the surface modified bioactive glass.
Wherein the dosage of the functional silane coupling agent is 5-500% of the mass of the bioactive glass particles.
The functional silane coupling agent has a structure shown in a general formula (A):
wherein R in formula (A) is selected from C 1 ～C 18 Hydrocarbyl radicals, R 1 Selected from H or methyl, when Y is selected from C 1 ～C 18 Hydrocarbon radicals or radicalsWhen X is - Selected from Cl - 、Br - 、I - Or p-CH 3 C 6 H 4 SO 3 - One of the following; when Y is selected from-CH 2 CH 2 CH 2 SO 3 - or-CH 2 CH 2 CH 2 CO 2 - When X is - No counter anions were selected.
Wherein R is 2 Selected from C 1 ～C 18 Hydrocarbyl groups, m is selected from natural numbers between 0 and 2000.
Relevant research results and application experiments have taught us: the structural unit in the functional silane coupling agent of the invention can function, act and performance according to actual needs, and is suitable for N + Upper Y, R 1 And R is 2 The purpose optimization selection can be performed. If too much emphasis is placed on the hydrophilic function, Y of the silane diol is preferably CH 3 、R 2 Preferably H or CH 3 The method comprises the steps of carrying out a first treatment on the surface of the If the hydrophilic, antibacterial and sterilizing functions are emphasized, the silane diol Y is preferably C 12 H 25 Or C 7 H 8 ，R 1 And R is 2 Preferably CH 3 The method comprises the steps of carrying out a first treatment on the surface of the If the modification such as hydrophilicity, antibiosis, antifouling, biocompatibility and anticoagulation is the main purpose, Y is preferableR 2 CH selection 3 M is preferably 8 to 25.
The preparation method of the functional silane coupling agent comprises the steps of dissolving a 3-aminopropyl silane coupling agent with a structure shown in a general formula (B) in a solvent, controlling the temperature to be 5-35 ℃, starting stirring, and slowly adding hydroxyethyl methacrylate or hydroxyethyl acrylate, wherein the dosage of the hydroxyethyl methacrylate or the hydroxyethyl acrylate is 2.0-2.2 times of the molar quantity of the 3-aminopropyl silane coupling agent; slowly increasing the temperature of a reaction system to 35-90 ℃ for reaction for 2-20 hours after the charging of the hydroxyethyl methacrylate or the hydroxyethyl acrylate is finished, and ending the aza-Michael addition reaction process; maintaining the reaction temperature, adding an alkylating reagent or propane sultone or gamma-butyrolactone into a reaction system, wherein the dosage of the alkylating reagent or propane sultone or gamma-butyrolactone is 1.0-1.5 times of the molar quantity of the 3-aminopropyl silane coupling agent, and after continuing to react for 2-20 hours, ending the quaternization reaction process; and then removing part of the solvent by rotary evaporation, reducing the temperature of a reaction system to room temperature, separating out a crude product, and purifying the crude product to obtain the functionalized silane coupling agent with the structure shown in the general formula (A).
Wherein the 3-aminopropyl silane coupling agent has a structure shown in a general formula (B):
wherein R in the general formula (B) is selected from C1-C18 hydrocarbon groups.
The solvent refers to one or more than two of methanol, ethanol, propanol, tetrahydrofuran, 1, 4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide, N-diethylformamide or hexamethylphosphoramide; the amount of the solvent is 1 to 10 times the mass of the general formula (B).
The alkylating agent has a structure shown in a general formula (C):
Y-X
general formula (C)
Wherein Y in the formula (C) is selected from C 1 ～C 18 Hydrocarbon radicals or radicalsWhen X is selected from Cl, br, I or p-CH 3 C 6 H 4 SO 3 Wherein m is selected from natural numbers between 0 and 2000, R 2 Selected from C 1 ～C 18 A hydrocarbon group.
The invention provides the beneficial effects of the application of a functional silane coupling agent in the surface modification of bioactive glass, which are as follows:
(1) the functionalized silane coupling agent has the advantages of novel structure, simple preparation method, most of preparation raw materials are commercial products, the product yield in each step of preparation process is high, the purification technology of the dihydroxyl functionalized silane coupling agent is simple, and the technical process is easy to implement.
(2) The functional silane coupling agent is easy to dissolve in water and in a large amount of alcohol solvent, and has a simple use method and almost no volatile toxic organic matters.
(3) The functional silane coupling agent is used for carrying out surface modification on bioactive glass, and has simple technical process and remarkable modification effect.
Detailed Description
For a further understanding of the present invention, it is to be understood that the present invention is specifically described by way of examples, and is for the purpose of better understanding of the present invention. Therefore, the use of the functionalized silane coupling agents not listed in the examples for the surface modification of bioactive glass should not be construed as limiting the scope of the invention.
Example 1 preparation of surface-modified bioactive glass (A-1)
Step one, preparation of a functional silane coupling agent of the formula (A-1):
30 g (about 0.215 mol) of hydroxyethyl methacrylate is dissolved in 320 g of methanol to be put into a reaction kettle, stirring is started, the commercial brand KH-550 aminosilane coupling agent 22 g (about 0.1 mol) is slowly added under the protection of N2 at the temperature of 10-15 ℃, after the KH-550 aminosilane coupling agent is completely added, the reaction temperature is gradually increased to 35-45 ℃ to continue the reaction for 12 hours, 15 g of benzyl chloride (about 0.119 mol) is added into the reaction kettle, the reaction temperature is increased to 70-90 ℃ to react for 20 hours, part of methanol is removed by rotary evaporation, the temperature of a reaction product system is reduced to room temperature, a beige solid substance is separated out, and the functional silane coupling agent of the formula (A-1) is prepared by vacuum drying at the temperature of 35-45 ℃ after washing three times by dehydrated acetone.
KH-550 is a commercial brand of 3-aminopropyl triethoxysilane, and the yield of intermediate tertiary amine is about 99.5% and the yield of the multifunctional silane coupling agent of formula (A-1) is about 91.4% through sampling, separating and purifying the product of the aza-Michael addition reaction of hydroxyethyl methacrylate. The IR spectrogram of the functionalized silane coupling agent of the formula (A-1) also shows strong absorption peaks near 3458nm, 2934nm, 2876nm, 1726nm and 1108 nm; c56.45 (56.78), H8.33 (8.51), N2.27 (2.37) and the functional silane coupling agent product structure and theoretical design molecular formula C shown in the formula (A-1) 28 H 50 ClNO 8 Si is identical. The functional silane coupling agent product of the formula (A-1) is subjected to nuclear magnetic resonance and mass spectrometry analysis, and the chemical structure of the product in the preparation process is confirmed to be consistent with the theoretical design.
Step two, preparing surface modified bioactive glass (A-1): 76 g of ethanol, 21.3 g of the functional silane coupling agent of the formula (A-1) and 100 g of water are weighed, sequentially added into a reaction flask at room temperature, and stirred uniformly to prepare a functional silane coupling agent solution of the formula (A-1). Then 30 g of calcium phosphorus silicon bioactive glass (purchased from Wohan gram biomedical technology Co., ltd.) with the particle size less than or equal to 10 μm is put into the reaction kettle, after ultrasonic treatment for 0.5 hour, the temperature is raised to 70-80 ℃ and stirred for 6 hours, the reaction process is ended, the temperature is reduced and filtered, the filter cake is washed three times by ethanol, and the constant weight is dried in vacuum at the temperature of 50-55 ℃ to obtain 47.8 g of surface modified bioactive glass (A-1).
29.2 g of the bioactive glass blank sample prepared by the same method and procedure can calculate 8.6 g of net weight gain of the surface modified bioactive glass (A-1), thereby deducing that the reaction efficiency of the functionalized silane coupling agent of the formula (A-1) on the surface of the bioactive glass is 92.3%.
In the IR spectrum diagram of the surface modified bioactive glass (A-1) relative to a bioactive glass blank sample, the middle strong-strong absorption peaks are added at a plurality of positions such as 3454nm, 2930nm, 2878nm, 1724nm and 1106nm, and the vibration absorption peaks respectively belong to hydroxyl, methyl, methylene, ester carbonyl and C-O-C, so that the surface modified bioactive glass (A-1) has the structural characteristics of hydroxyl, carboxylate and ether bonds.
Example 2 preparation of surface-modified bioactive glass (A-2)
According to the procedure of step one of example 1, benzyl chloride was changed to ω -methoxypolyethylene glycol-400 p-toluenesulfonate to obtain a functionalized silane coupling agent of formula (A-2) in a yield of 91.4%. IR spectrum of multifunctional silane coupling agent of formula (A-2), 1 C53.09 (53.86), H8.62 (8.83), N1.04 (1.10), indicating the formula C with formula (A-2) 57 H 111 NO 25 The SSi is basically consistent, so that the chemical structure of the functionalized silane coupling agent product of the formula (A-2) is judged to be consistent with the theoretical design.
The procedure of the second step of example 1 was followed, using a functional silane coupling agent of the formula (A-2) for surface modification treatment of calcium-phosphorus-silicon-based bioactive glass powder having a particle diameter of 10 μm or less, which was produced by Wohan Kemi biomedical technology Co., ltd, to obtain a surface-modified bioactive glass (A-2). By using IR spectrum analysis means, it was confirmed that the surface-modified bioactive glass (A-2) had structural characteristics of hydroxyl group, carboxylate and ether bond.
Example 3 preparation of surface-modified bioactive glass (A-3)
According to the method and the operation steps of the embodiment 1, the calcium phosphorus silicon bioactive glass powder with the particle diameter less than or equal to 10 mu m produced by the Wuhan Ke Mike biomedical technology Co., ltd in the second embodiment 1 is changed into SiO produced by Hebei excellent solid biotechnology Co., ltd 2 Content of 45%, caO 2 Content of 24.5%, na 2 O content 24.5%, P 2 O 5 The bioactive glass with the content of 6.0 percent is named as euonyolin, and the particle size is less than or equal to 45 mu m powder, so as to prepare the surface modified bioactive glass (A-3). Judging by adopting an infrared spectrum analysis meansThe surface-modified bioactive glass (A-3) has the structural characteristics of hydroxyl, carboxylate and ether bond.
Example 4 preparation of surface-modified bioactive glass (A-4)
According to the method and the operation procedure of example 1, KH-550 aminosilane coupling agent in the first step was changed to KH-540 aminosilane coupling agent, benzyl chloride was changed to bromododecane, and the functionalized silane coupling agent of formula (A-4) was obtained in a yield of 78.1%. IR spectrum of the functionalized silane coupling agent of the formula (A-4), 1 C55.18 (55.39), H9.78 (9.94), br11.61 (12.71), which shows structural compliance with the product of formula (A-4) with the design formula C 29 H 62 BrNO 6 Si, thereby confirming that the chemical structure of formula (A-4) matches the theoretical design.
According to the method and the operation steps of the embodiment 1, the calcium phosphorus silicon bioactive glass powder with the particle size less than or equal to 10 mu m produced by the Wuhank biomedical technology Co., ltd in the second step is changed into nano bioactive glass (the nano bioactive glass is self-made according to the ZL02110586.3 published technology). And (3) carrying out surface modification treatment on the nano bioactive glass by using the functionalized silane coupling agent shown in the formula (A-4) to obtain the surface modified nano bioactive glass (A-4). The infrared spectrum analysis means is adopted to prove that the surface modified nanometer bioactive glass (A-4) has the structural characteristics of hydroxyl, carboxylate and ether bond.
Example 5 characteristics of bioactive glass before and after surface modification in examples 1 to 4
1.5 g of the surface-modified bioactive glass in examples 1 to 4 was taken and pressed by a pressing machine, and the contact angle of pure water of each pressed sheet was measured under static conditions by a contact angle measuring instrument, and the results are shown in Table 1.
Table 1 results of measuring water contact angle of each sample in examples 1 to 4
Examples 1 2 3 4 Blank space
Water contact angle (°) 0 0 0 0 10.5
The results in Table 1 demonstrate that the hydrophilicity of the bioactive glass is significantly improved after surface treatment.

Claims (6)

1. The application of the functionalized silane coupling agent in the surface modification of the bioactive glass is characterized by comprising the following steps: sequentially weighing methanol or ethanol, a functional silane coupling agent and water according to the mass ratio of the methanol or ethanol to the functional silane coupling agent to the water of 5-50:5-50, preparing a functional silane coupling agent solution at room temperature, stirring, adding bioactive glass particles, heating to 50-90 ℃ for reacting for 2-20 hours, and ending the reaction process; then cooling the reaction product to room temperature, filtering, washing a filter cake by using methanol or ethanol, sending the washed filter cake into a vacuum drying phase, and vacuum drying at the temperature of 25-65 ℃ to constant weight to obtain the surface modified bioactive glass;
wherein the dosage of the functional silane coupling agent is 5-500% of the mass of the bioactive glass particles.
2. The use of a functionalized silane coupling agent according to claim 1 for modifying the surface of bioactive glass, wherein the functionalized silane coupling agent has the structure of formula (a):
wherein R in the formula (A) is C 1 ～C 18 Hydrocarbyl radicals, R 1 Selecting H or methyl, when Y selects C 1 ～C 18 Hydrocarbon radicals or radicalsWhen X is - Selecting Cl - 、Br - 、I - Or p-CH 3 C 6 H 4 SO 3 - One of the following; when Y selects-CH 2 CH 2 CH 2 SO 3 - or-CH 2 CH 2 CH 2 CO 2 - When X is - Any counter anions are not selected;
wherein R is 2 Selecting C 1 ～C 18 Hydrocarbyl groups, m is selected from natural numbers between 0 and 2000.
3. The application of the functionalized silane coupling agent in the surface modification of bioactive glass according to claim 1, which is characterized in that the preparation method of the functionalized silane coupling agent is to dissolve the 3-aminopropyl silane coupling agent with the structure shown in the general formula (B) in a solvent, control the temperature to 5-35 ℃, start stirring and slowly add hydroxyethyl methacrylate or hydroxyethyl acrylate, wherein the dosage of the hydroxyethyl methacrylate or hydroxyethyl acrylate is 2.0-2.2 times of the molar quantity of the 3-aminopropyl silane coupling agent; slowly raising the temperature of the reaction system to 35-90 ℃ for 2-20 hours after the charging of the hydroxyethyl methacrylate or the hydroxyethyl acrylate is finished, and ending the Michael addition reaction process; maintaining the reaction temperature, adding an alkylating reagent or propane sultone or gamma-butyrolactone into a reaction system, wherein the dosage of the alkylating reagent or propane sultone or gamma-butyrolactone is 1.0-1.5 times of the molar quantity of the 3-aminopropyl silane coupling agent, and after continuing to react for 2-20 hours, ending the quaternization reaction process; then removing part of solvent by rotary evaporation, reducing the temperature of a reaction system to room temperature, separating out a crude product, and purifying the crude product to obtain the functionalized silane coupling agent with the structure shown in the general formula (A);
wherein the dosage of the solvent is 1 to 10 times of the mass of the 3-aminopropyl silane coupling agent.
4. The use of a functionalized silane coupling agent according to claim 3 for modifying the surface of bioactive glass, wherein the 3-aminopropyl silane coupling agent has the structure of formula (B):
wherein R in the general formula (B) is C 1 ～C 18 A hydrocarbon group.
5. The method of modifying a surface of a bioactive glass, wherein the solvent is one or more of methanol, ethanol, propanol, tetrahydrofuran, 1, 4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide, N-diethylformamide, and hexamethylphosphoramide.
6. Use of a functionalized silane coupling agent according to claim 3 for modifying the surface of bioactive glass, wherein the alkylating agent has the structure of formula (C):
Y-X
general formula (C)
Wherein Y in the general formula (C) is C 1 ～C 18 Hydrocarbon radicals or radicalsWhen X is Cl, br, I or p-CH 3 C 6 H 4 SO 3 Wherein m is selected from natural numbers between 0 and 2000, R 2 Selecting C 1 ～C 18 A hydrocarbon group.
CN202311027279.8A 2023-08-16 2023-08-16 Application of functional silane coupling agent in surface modification of bioactive glass Pending CN117049794A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118078644A (en) * 2024-04-23 2024-05-28 北京大学口腔医学院 Dental composite resin and preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118078644A (en) * 2024-04-23 2024-05-28 北京大学口腔医学院 Dental composite resin and preparation method and application thereof

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