CN114917402B - Single-component photo-curing antibacterial silicone gel medical material and preparation method and application thereof - Google Patents
Single-component photo-curing antibacterial silicone gel medical material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a single-component photo-curing antibacterial silica gel medical material, which belongs to the technical field of preparation and application of biomedical materials and is prepared from the following raw materials in percentage by mass: 5-15% of quaternary ammonium salt type mercapto silsesquioxane, 84-94.9% of vinyl silicone oil and 0.1-1% of photoinitiator. According to the invention, the quaternary ammonium salt type sulfhydryl silsesquioxane is used as an antibacterial agent and a cross-linking agent, and a sulfhydryl-alkene click chemistry photocuring material system is designed, so that the obtained silica gel medical material has good surface viscosity and durable antibacterial performance.
Description
Technical Field
The invention belongs to the technical field of preparation and application of biomedical materials, and particularly relates to a single-component photo-curing antibacterial silicone gel medical material and a preparation method and application thereof.
Background
The silica gel material has no toxicity and good biocompatibility, and can be widely used as medical materials in the medical field. The silica gel material with certain viscosity on the surface can be obtained by properly controlling the crosslinking degree of the material in the process of preparing the silica gel material, and the silica gel material with the surface viscosity can be prepared into medical adhesive tapes, wound dressing adhesive layers, scar patches and the like. The traditional preparation method of the silica gel material is to adopt AB bi-component to obtain the silica gel material through hydrosilylation reaction. However, the AB component silicone gel silicone hydride addition system has complex components, poor storage stability, complex preparation process of silicone gel, harsh conditions and complex operation process, and the AB component silicone gel silicone hydride addition system needs to use a noble metal platinum catalyst, so that the raw material cost is high. These disadvantages cause various problems in the actual preparation process of the silica gel material, and seriously affect the quality of the product. Combining UV curing techniques with silicone materials can greatly promote the expansion of silicone material applications. The photo-curing organosilicon material has the advantages of high molding speed, low energy consumption, environmental friendliness and the like of the photo-curing technology and the unique property of good biocompatibility of the organosilicon material, and has become one of research hot spots in the fields of organosilicon and photo-curing technology in recent years. Based on mercapto-alkene photo-curing click chemistry reaction, the designed single-component photo-curing organic silicon gel material system has the advantages of stable component property, good storage stability, high curing efficiency, simple preparation process, strong operability and low raw material cost, and can replace the traditional AB component silicon gel hydrosilylation system. On the other hand, medical devices, which are usually made of silicone gel, need to be in contact with human skin tissue, and bacteria easily invade through various routes to cause infection during the contact between the medical device and human skin tissue. Therefore, the antibacterial performance of the medical silicone gel material is particularly important. In the design and manufacture of medical instruments, the antibacterial material can be used for effectively killing bacteria. Therefore, how to develop a single-component photo-curing antibacterial silicone gel medical material with less addition amount of an antibacterial agent, easy material processing and durable antibacterial performance and a preparation method thereof are technical problems to be solved by the technicians in the field.
Disclosure of Invention
In view of the above, the invention provides a single-component photo-curing antibacterial silicone gel medical material, and a preparation method and application thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a single-component photo-curing antibacterial silicone gel medical material is prepared from the following raw materials in percentage by mass: 5-15% of quaternary ammonium salt type mercapto silsesquioxane, 84-94.9% of vinyl silicone oil and 0.1-1% of photoinitiator.
The beneficial effects of the invention are as follows: according to the invention, the quaternary ammonium salt type sulfhydryl silsesquioxane is used as an antibacterial agent and a cross-linking agent, and a sulfhydryl-alkene click chemistry photocuring material system is designed, so that the obtained silica gel medical material has good surface viscosity and durable antibacterial performance.
Further, the molar ratio of the quaternary ammonium salt group to the mercapto group in the quaternary ammonium salt type mercapto silsesquioxane is (1-6): (2-7).
Further, the vinyl silicone oil is one or a mixture of two of terminal vinyl silicone oil and side chain vinyl silicone oil, and the viscosity of the vinyl silicone oil is 5000-100000cP.
Further, the photoinitiator is one or a mixture of a plurality of photoinitiators 184, a photoinitiator TPO and benzophenone.
The invention also provides a preparation method of the single-component photo-curing antibacterial silicone gel medical material, which comprises the following steps:
(1) Weighing the raw materials according to the single-component photo-curing antibacterial silica gel medical material;
(2) Uniformly stirring quaternary ammonium salt type sulfhydryl silsesquioxane, vinyl silicone oil and a photoinitiator, and irradiating under ultraviolet light to obtain the antibacterial silicone gel.
The beneficial effects of the invention are as follows:
1. the quaternary ammonium salt type sulfhydryl silsesquioxane is used as an antibacterial agent and a cross-linking agent, and quaternary ammonium salt groups exist in the silica gel in a covalent bond form, so that the quaternary ammonium salt type antibacterial silicone gel has good surface tackiness, can endow the silica gel material with good antibacterial performance and can keep the antibacterial performance of the material for a long time. The mercapto silsesquioxane molecule has a cage-shaped nano structure and plays a role in enhancing the mechanical property of the material as a cross-linking agent.
2. The invention adopts a sulfhydryl-alkene click chemical reaction system to form a single-component photo-curing composition, has stable component property and good storage stability, and overcomes the defects of complex components and poor storage stability of an AB component silicone gel hydrosilylation system.
3. The single-component photo-curing antibacterial silica gel medical material adopts an ultraviolet irradiation crosslinking forming process, has the characteristics of high curing efficiency, simple preparation process and strong operability, and overcomes the defects of complex preparation process, harsh conditions and complicated operation process of the traditional AB-component silica gel.
The AB component silicone gel hydrosilylation system needs to use a noble metal platinum catalyst, the raw material cost is high, and the single component photo-curing type antibacterial silicone gel medical material has low raw material cost and obvious price advantage compared with the AB component silicone gel hydrosilylation system.
Further, the stirring rotation speed in the step (2) is 400r/min, and the stirring time is 10h.
Further, the ultraviolet light wavelength in the step (2) is 365nm, and the irradiation time is 2min.
Further, the preparation method of the quaternary ammonium salt type mercapto silsesquioxane in the step (2) comprises the following steps:
adding gamma-mercaptopropyl trimethoxy silane and trimethoxy silicon-based propyl octadecyl dimethyl ammonium chloride into water, stirring at normal temperature until the gamma-mercaptopropyl trimethoxy silane and trimethoxy silicon-based propyl octadecyl dimethyl ammonium chloride are dissolved, then adding hydrochloric acid, heating, continuously stirring, adding saturated sodium carbonate aqueous solution for washing, and vacuumizing an oil layer to remove small molecules to obtain the quaternary ammonium salt type mercaptosilsesquioxane.
Further, the molar ratio of the gamma-mercaptopropyl trimethoxysilane to the trimethoxysilylpropyl octadecyl dimethyl ammonium chloride is (1-7), the volume ratio of the water, the hydrochloric acid and the saturated sodium carbonate aqueous solution is 100:1:100, and 100mL of water is added to each 1g of gamma-mercaptopropyl trimethoxysilane.
Further, the temperature is raised to 80 ℃ and stirring is continued for 10 hours, and the stirring speed is 400r/min.
Further, the oil layer was evacuated for 3 hours to remove small molecules.
The single-component light-cured antibacterial silicone gel medical material or the single-component light-cured antibacterial silicone gel medical material prepared by the method is applied to the preparation of self-adhesive dressing, medical scar plaster and medical adhesive tape material.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the single-component photo-curing antibacterial silicone gel medical material comprises the following steps:
(1) The preparation method of the quaternary ammonium salt type mercapto silsesquioxane comprises the following steps:
adding 5g of gamma-mercaptopropyl trimethoxysilane and 5g of trimethoxy silicon-based propyl octadecyl dimethyl ammonium chloride into 30mL of water, stirring for 1h at normal temperature until the mixture is dissolved, then adding 0.5mL of hydrochloric acid, heating to 80 ℃ and continuously stirring for 10h, wherein the stirring speed is 400r/min, adding 100mL of saturated sodium carbonate aqueous solution for water washing for 3 times each time, and vacuumizing an oil layer for 3h to obtain quaternary ammonium salt type mercaptosilsesquioxane, wherein the yield is 92%;
(2) 0.15g of quaternary ammonium salt type mercapto silsesquioxane, 0.85g of vinyl silicone oil (the vinyl silicone oil is terminal vinyl silicone oil, the side chain vinyl silicone oil is 0.425g respectively) and 0.01g of photoinitiator 184 are uniformly mixed, the viscosity of the vinyl silicone oil is 5000cP, the antibacterial silicone gel is obtained by irradiating the mixture for 5min under the ultraviolet light with the wavelength of 365nm, the initial viscosity of the silicone gel is tested by a rolling ball method, no. 13 steel balls are tested by the rolling ball method, the antibacterial performance of the material is evaluated by a direct contact method, the antibacterial rate of the material to escherichia coli is 80% and the antibacterial rate of staphylococcus aureus is 85% after 7 days.
Example 2
The preparation method of the single-component photo-curing antibacterial silicone gel medical material comprises the following steps:
(1) The preparation method of the quaternary ammonium salt type mercapto silsesquioxane comprises the following steps:
adding 5g of gamma-mercaptopropyl trimethoxysilane and 5g of trimethoxy silicon-based propyl octadecyl dimethyl ammonium chloride into 30mL of water, stirring for 1h at normal temperature until the mixture is dissolved, then adding 0.5mL of hydrochloric acid, heating to 80 ℃ and continuously stirring for 10h, wherein the stirring speed is 400r/min, adding 100mL of saturated sodium carbonate aqueous solution for water washing for 3 times each time, and vacuumizing an oil layer for 3h to obtain quaternary ammonium salt type mercaptosilsesquioxane, wherein the yield is 92%;
(2) 0.25g of quaternary ammonium salt type mercapto silsesquioxane, 0.75g of vinyl silicone oil (the vinyl silicone oil is terminal vinyl silicone oil, the side chain vinyl silicone oil is 0.375g respectively) and 0.01g of photoinitiator 184 are uniformly mixed, the viscosity of the vinyl silicone oil is 10000cP, the antibacterial silicone gel is obtained by irradiating the mixture for 5min under the ultraviolet light with the wavelength of 365nm, the initial viscosity of the silicone gel is tested by a rolling ball method, the antibacterial performance of the material is evaluated by a direct contact method, the antibacterial rate of the material to escherichia coli is 85% and the antibacterial rate of staphylococcus aureus is 90% after 7 days.
Example 3
The preparation method of the single-component photo-curing antibacterial silicone gel medical material comprises the following steps:
(1) The preparation method of the quaternary ammonium salt type mercapto silsesquioxane comprises the following steps:
adding 7g of gamma-mercaptopropyl trimethoxysilane and 3g of trimethoxy silicon-based propyl octadecyl dimethyl ammonium chloride into 30mL of water, stirring for 1h at normal temperature until the mixture is dissolved, then adding 0.5mL of hydrochloric acid, heating to 80 ℃ and continuously stirring for 10h, wherein the stirring speed is 400r/min, adding 100mL of saturated sodium carbonate aqueous solution for water washing for 3 times each time, and vacuumizing an oil layer for 3h to obtain quaternary ammonium salt type mercaptosilsesquioxane with the yield of 90%;
(2) 0.21g of quaternary ammonium salt type mercapto silsesquioxane, 0.79g of vinyl silicone oil (the vinyl silicone oil is terminal vinyl silicone oil, the side chain vinyl silicone oil is 0.395g respectively) and 0.01g of photoinitiator 184 are uniformly mixed, the viscosity of the vinyl silicone oil is 5000cP, the antibacterial silicone gel is obtained by irradiating the mixture for 5min under the ultraviolet light with the wavelength of 365nm, the initial viscosity of the silicone gel is tested by a rolling ball method, no. 13 steel balls are tested by the rolling ball method, the antibacterial performance of the material is evaluated by a direct contact method, the antibacterial rate of the material to escherichia coli is 82% and the antibacterial rate of staphylococcus aureus is 88% after 7 days.
Example 4
The preparation method of the single-component photo-curing antibacterial silicone gel medical material comprises the following steps:
(1) The preparation method of the quaternary ammonium salt type mercapto silsesquioxane comprises the following steps:
adding 7g of gamma-mercaptopropyl trimethoxysilane and 3g of trimethoxy silicon-based propyl octadecyl dimethyl ammonium chloride into 30mL of water, stirring for 1h at normal temperature until the mixture is dissolved, then adding 0.5mL of hydrochloric acid, heating to 80 ℃ and continuously stirring for 10h, wherein the stirring speed is 400r/min, adding 100mL of saturated sodium carbonate aqueous solution for water washing for 3 times each time, and vacuumizing an oil layer for 3h to obtain quaternary ammonium salt type mercaptosilsesquioxane with the yield of 90%;
(2) 0.32g of quaternary ammonium salt type mercapto silsesquioxane, 0.68g of vinyl silicone oil (the vinyl silicone oil is terminal vinyl silicone oil, the side chain vinyl silicone oil is 0.34g respectively) and 0.01g of photoinitiator 184 are uniformly mixed, the viscosity of the vinyl silicone oil is 20000cP, the antibacterial silicone gel is obtained by irradiating the mixture for 5min under 365nm ultraviolet light, the initial viscosity of the silicone gel is tested by a rolling ball method, the antibacterial performance of the material is evaluated by a direct contact method, the antibacterial rate of the material to escherichia coli is 85% and the antibacterial rate to staphylococcus aureus is 90% after 7 days.
Example 5
The preparation method of the single-component photo-curing antibacterial silicone gel medical material comprises the following steps:
(1) The preparation method of the quaternary ammonium salt type mercapto silsesquioxane comprises the following steps:
adding 3g of gamma-mercaptopropyl trimethoxysilane and 7g of trimethoxysilylpropyl octadecyl dimethyl ammonium chloride into 30mL of water, stirring for 1h at normal temperature until the mixture is dissolved, then adding 0.5mL of hydrochloric acid, heating to 80 ℃ and continuously stirring for 10h, wherein the stirring speed is 400r/min, adding 100mL of saturated sodium carbonate aqueous solution for water washing for 3 times each time, and vacuumizing an oil layer for 3h to obtain quaternary ammonium salt type mercaptosilsesquioxane, wherein the yield is 93%;
(2) 0.35g of quaternary ammonium salt type mercapto silsesquioxane, 0.65g of vinyl silicone oil (the vinyl silicone oil is terminal vinyl silicone oil, the side chain vinyl silicone oil is 0.325g respectively) and 0.01g of photoinitiator 184 are uniformly mixed, the viscosity of the vinyl silicone oil is 10000cP, the antibacterial silicone gel is obtained by irradiating the mixture for 5min under the ultraviolet light with the wavelength of 365nm, the initial viscosity of the silicone gel is tested by a rolling ball method, no. 13 steel balls are tested by the rolling ball method, the antibacterial performance of the material is evaluated by a direct contact method, the antibacterial rate of the material to escherichia coli is 88%, and the antibacterial rate of staphylococcus aureus is 94% after 7 days.
Example 6
The preparation method of the single-component photo-curing antibacterial silicone gel medical material comprises the following steps:
(1) The preparation method of the quaternary ammonium salt type mercapto silsesquioxane comprises the following steps:
adding 5g of gamma-mercaptopropyl trimethoxysilane and 5g of trimethoxy silicon-based propyl octadecyl dimethyl ammonium chloride into 30mL of water, stirring for 1h at normal temperature until the mixture is dissolved, then adding 0.5mL of hydrochloric acid, heating to 80 ℃ and continuously stirring for 10h, wherein the stirring speed is 400r/min, adding 100mL of saturated sodium carbonate aqueous solution for water washing for 3 times each time, and vacuumizing an oil layer for 3h to obtain quaternary ammonium salt type mercaptosilsesquioxane, wherein the yield is 92%;
(2) 0.50g of quaternary ammonium salt type mercapto silsesquioxane, 0.50g of vinyl silicone oil (the vinyl silicone oil is terminal vinyl silicone oil, the side chain vinyl silicone oil is 0.25g respectively) and 0.01g of photoinitiator 184 are uniformly mixed, the viscosity of the vinyl silicone oil is 5000cP, the antibacterial silicone gel is obtained by irradiating the mixture for 5min under the ultraviolet light with the wavelength of 365nm, the initial viscosity of the silicone gel is tested by a rolling ball method, no. 11 steel balls are tested by the rolling ball method, the antibacterial performance of the material is evaluated by a direct contact method, the antibacterial rate of the material to escherichia coli is 90% and the antibacterial rate of staphylococcus aureus is 96% after 7 days.
The description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. The single-component photo-curing antibacterial silicone gel medical material is characterized by being prepared from the following raw materials in percentage by mass: 5-15% of quaternary ammonium salt type mercapto silsesquioxane, 84-94.9% of vinyl silicone oil and 0.1-1% of photoinitiator;
the molar ratio of the quaternary ammonium salt group to the sulfhydryl group in the quaternary ammonium salt type sulfhydryl silsesquioxane is (1-6): (2-7);
the preparation method of the quaternary ammonium salt type mercapto silsesquioxane comprises the following steps:
adding gamma-mercaptopropyl trimethoxy silane and trimethoxy silicon-based propyl octadecyl dimethyl ammonium chloride into water, stirring at normal temperature until the gamma-mercaptopropyl trimethoxy silane and trimethoxy silicon-based propyl octadecyl dimethyl ammonium chloride are dissolved, then adding hydrochloric acid, heating, continuously stirring, adding saturated sodium carbonate aqueous solution for washing, and vacuumizing an oil layer to remove small molecules to obtain the quaternary ammonium salt type mercaptosilsesquioxane.
2. The single-component photo-curable antibacterial silicone gel medical material according to claim 1, wherein the vinyl silicone oil is one or a mixture of two of vinyl silicone oil at the end and vinyl silicone oil at the side chain, and the viscosity of the vinyl silicone oil is 5000-100000cP.
3. The single-component photo-curable antibacterial silicone gel medical material according to claim 1, wherein the photoinitiator is one or a mixture of several of photoinitiator 184, photoinitiator TPO and benzophenone.
4. The preparation method of the single-component photo-curing antibacterial silicone gel medical material is characterized by comprising the following steps of:
(1) A single-component photo-curable antibacterial silicone gel medical material according to any one of claims 1 to 3, each raw material being weighed;
(2) Mixing and stirring quaternary ammonium salt type mercapto silsesquioxane, vinyl silicone oil and a photoinitiator uniformly, and irradiating under ultraviolet light to obtain antibacterial silica gel;
the preparation method of the quaternary ammonium salt type mercapto silsesquioxane in the step (2) comprises the following steps:
adding gamma-mercaptopropyl trimethoxy silane and trimethoxy silicon-based propyl octadecyl dimethyl ammonium chloride into water, stirring at normal temperature until the gamma-mercaptopropyl trimethoxy silane and trimethoxy silicon-based propyl octadecyl dimethyl ammonium chloride are dissolved, then adding hydrochloric acid, heating, continuously stirring, adding saturated sodium carbonate aqueous solution for washing, and vacuumizing an oil layer to remove small molecules to obtain the quaternary ammonium salt type mercaptosilsesquioxane.
5. The method for preparing a single-component photo-curable antibacterial silicone gel medical material according to claim 4, wherein the ultraviolet light in the step (2) has a wavelength of 365nm and a radiation time of 2min.
6. The preparation method of the single-component photo-curing antibacterial silica gel medical material is characterized in that the molar ratio of gamma-mercaptopropyl trimethoxysilane to trimethoxy silicon-based propyl octadecyl dimethyl ammonium chloride is (1-7), the volume ratio of water to hydrochloric acid to saturated sodium carbonate aqueous solution is 100:1:100, and 100mL of water is added to each 1g of gamma-mercaptopropyl trimethoxysilane.
7. The method for preparing a single-component photo-curing type antibacterial silicone gel medical material according to claim 4, wherein the temperature is raised to 80 ℃ and stirring is continued for 10 hours, and the stirring speed is 400r/min.
8. Use of the one-component photo-curable antibacterial silicone gel medical material according to any one of claims 1 to 3 or the one-component photo-curable antibacterial silicone gel medical material prepared by the method according to any one of claims 4 to 7 for preparing self-adhesive dressings, medical scar patches and medical adhesive tape materials.
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