CN115260411A - Medical composite material and preparation method thereof - Google Patents

Medical composite material and preparation method thereof Download PDF

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CN115260411A
CN115260411A CN202211144151.5A CN202211144151A CN115260411A CN 115260411 A CN115260411 A CN 115260411A CN 202211144151 A CN202211144151 A CN 202211144151A CN 115260411 A CN115260411 A CN 115260411A
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silicon rubber
deionized water
composite material
stirring
reaction
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罗小坤
陈海霞
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Nantong Weihua Innovative Materials Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/04Macromolecular materials
    • A61L29/041Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A61L29/042Rubbers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/08Materials for coatings
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/08Materials for coatings
    • A61L29/10Inorganic materials
    • A61L29/103Carbon
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/14Materials characterised by their function or physical properties, e.g. lubricating compositions
    • A61L29/16Biologically active materials, e.g. therapeutic substances
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F2/00Processes of polymerisation
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F2/00Processes of polymerisation
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K9/12Adsorbed ingredients, e.g. ingredients on carriers
    • AHUMAN NECESSITIES
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    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/108Elemental carbon, e.g. charcoal
    • AHUMAN NECESSITIES
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    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/20Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
    • A61L2300/216Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with other specific functional groups, e.g. aldehydes, ketones, phenols, quaternary phosphonium groups
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404Biocides, antimicrobial agents, antiseptic agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/606Coatings
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Abstract

The invention discloses a medical composite material and a preparation method thereof, and the preparation method comprises the following steps: preparing an intermediate, adding the intermediate into deionized water, heating to 70 ℃, introducing methane chloride, keeping the temperature for reaction for 5 hours, washing after the reaction is finished, and standing for 30min to obtain a graft; ultrasonically cleaning silicon rubber by using an ethanol aqueous solution with the volume fraction of 50% for 30min, drying, then treating for 5min by using oxygen plasma, placing the silicon rubber in an initiator mixed solution after the treatment is finished, sealing and storing for 2h at 37 ℃, taking out and drying for 2h to prepare the pretreated silicon rubber; the prepared graft is added into deionized water, the pretreated silicon rubber is added, ultraviolet illumination is carried out for 5min, and then the silicon rubber is ultrasonically cleaned for 5min by ethanol aqueous solution with the volume fraction of 50 percent to prepare the medical composite material which can be used for preparing medical instruments such as medical catheters and the like and has excellent antibacterial performance.

Description

Medical composite material and preparation method thereof
Technical Field
The invention relates to the technical field of medical instruments, in particular to a medical composite material and a preparation method thereof.
Background
The silicon rubber product is widely applied to the fields of medical treatment, life, industry and the like. Such as medical catheters, prosthesis, occluders, artificial trachea, artificial lungs, artificial bones, silicone rubber duodenum and the like, and also used for mobile phone shells, nipples for children and the like. But due to its special structure, the surface is easily attached with bacteria and fungi to cause diseases to human beings.
In daily life, a variety of pathogenic microorganisms are widely distributed in nature and pose a threat to human health. Escherichia coli and staphylococcus aureus are the most common pathogenic bacteria, which have long plagued human life, and the antibacterial property detection of the antibacterial material at the present stage is also represented by Escherichia coli and staphylococcus aureus.
In the prior art, when the silicon rubber is subjected to antibacterial modification, modification is usually performed by simple blending of antibacterial agents, such as addition of nano silver particles, but the antibacterial silicon rubber prepared by the modification method has short antibacterial duration, poor fusion with the antibacterial agent and single antibacterial property, so that the antibacterial effect is limited.
Disclosure of Invention
In order to solve the technical problems, the invention provides a medical composite material and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a medical composite material comprises the following steps:
step S1, adding methyl methacrylate and dimethylaminoethanol into a reaction kettle, stirring at a constant speed, adding a catalyst and a polymerization inhibitor, stirring at a constant speed, heating to 105-125 ℃, refluxing for 4 hours, distilling under reduced pressure after the reaction is finished to remove unreacted methyl methacrylate and dimethylaminoethanol to obtain an intermediate, adding the intermediate into deionized water, heating to 70 ℃, introducing methane chloride, reacting at a constant temperature for 5 hours, washing after the reaction is finished, standing for 30 minutes, removing by-products under reduced pressure to obtain a graft, controlling the molar ratio of methyl methacrylate to dimethylaminoethanol to be 2-2.25: 1, controlling the dosage of the catalyst to be 1-1.5 percent of the sum of the weights of methyl methacrylate and dimethylaminoethanol, controlling the dosage of the polymerization inhibitor to be 0.1-0.3 percent of the weight of the catalyst, and controlling the molar ratio of the intermediate, the methane chloride and the deionized water to be 1: 0.2-0.3;
in the step S1, methyl methacrylate and dimethyl aminoethanol react under the action of a catalyst to generate an intermediate, and then the intermediate reacts with methane chloride to generate a graft, wherein the reaction process is as follows:
Figure 66891DEST_PATH_IMAGE002
in the structure, the synthesized graft has a quaternary ammonium salt structure at one end and can participate in polymerization of carbon-carbon double bonds, and the grafted body can be endowed with excellent antibacterial performance.
S2, adding benzophenone and benzoin dimethyl ether into acetone, stirring at a constant speed for 30min to prepare initiator mixed solution, controlling the dosage ratio of the benzophenone, the benzoin dimethyl ether and the acetone to be 0.705: 0.075: 20mL, ultrasonically cleaning silicon rubber by using ethanol aqueous solution with the volume fraction of 50% for 30min, drying, then treating for 5min by using oxygen plasma, placing the silicon rubber into the initiator mixed solution after the treatment is finished, sealing and storing for 2h at 37 ℃, taking out and naturally drying for 2h to prepare pretreated silicon rubber, and controlling the weight ratio of the initiator mixed solution to the silicon rubber to be 20: 2-2.5;
and S3, adding the graft obtained in the step S1 into deionized water, adding pretreated silicon rubber, irradiating for 5min by ultraviolet light, then ultrasonically cleaning for 5min by using an ethanol aqueous solution with the volume fraction of 50% to remove unreacted monomer and initiator mixed solution, and preparing the medical composite material, wherein the weight ratio of the graft to the deionized water to the pretreated silicon rubber is controlled to be 0.5-0.8: 1: 3-5.
In the step S2, benzophenone and benzoin dimethyl ether are used as photoinitiators at the same time for compounding, oxygen plasma is used for treating the surface of silicon rubber to enable hydrophilic hydroxyl groups to be generated on the surface of the silicon rubber, the silicon rubber is soaked in initiator mixed liquid to facilitate the photoinitiator to be adsorbed on the surface of the silicon rubber to prepare pretreated silicon rubber, then in the step S3, under ultraviolet illumination, the benzophenone in the photoinitiator can capture hydrogen atoms on the surface of the silicon rubber to generate active free radicals, and the benzoin dimethyl ether can be uniformly cracked to enable the surface of the silicon rubber to generate free radicals, so that double bonds of a graft are polymerized and grafted on the silicon rubber, and the silicon rubber is endowed with good antibacterial performance.
Further, the method comprises the following steps: the silicone rubber is prepared by the following steps:
step S11, adding sodium silicate and sodium bicarbonate into deionized water, heating to 90-95 ℃, uniformly stirring and reacting for 20min, adding the sodium silicate again, uniformly stirring for 5min, adding the sodium bicarbonate, uniformly stirring and reacting for 1h, adding holmium nitrate and silver nitrate, uniformly stirring and reacting for 1h, cooling, filtering and drying after the reaction is finished to obtain the antibacterial white carbon black, wherein the dosage ratio of the sodium silicate to the sodium bicarbonate to the deionized water is controlled to be 0.01 mol: 100mL, and the dosage ratio of the holmium nitrate to the deionized water is controlled to be 0.5 mmol: 0.05 mol: 1000mL;
in the step S11, sodium silicate and sodium bicarbonate are used as raw materials, a white carbon black matrix is prepared through a sol-gel method, rare earth elements holmium and silver ions are loaded on the prepared white carbon black matrix to prepare the antibacterial white carbon black, and the antibacterial effect of silver can be improved by introducing the rare earth elements.
And S12, adding the antibacterial white carbon black into petroleum ether, performing ultrasonic treatment, pouring into silicon rubber latex, performing vacuum filtration after uniform stirring, stirring at a constant speed of 200r/min, adding a curing agent, continuously stirring until no bubbles are generated, pouring into a mold, and curing for 10-12 hours to obtain the silicon rubber, wherein the dosage ratio of the antibacterial white carbon black, the petroleum ether, the silicon rubber latex to the curing agent is controlled to be 0.20-0.25 g: 10-15 mL: 50-60 g: 1-2g.
A medical composite material is prepared by the preparation method.
The invention has the beneficial effects that:
the invention relates to a medical composite material, which is an antibacterial silicone rubber material, can be used for preparing medical devices such as medical catheters and the like, and has excellent antibacterial performance, wherein in the preparation process, antibacterial white carbon black is prepared firstly, then the antibacterial white carbon black is used as a filler to be blended with silicone rubber latex, and is solidified to prepare silicone rubber with antibacterial performance, and then benzophenone and benzoin dimethyl ether are used as photoinitiators to be compounded for use, oxygen plasma is used for treating the surface of the silicone rubber, so that hydrophilic hydroxyl groups are generated on the surface of the silicone rubber, the silicone rubber is soaked in initiator mixed liquid, so that the photoinitiators are conveniently adsorbed on the surface of the silicone rubber, and pretreated silicone rubber is prepared;
according to the invention, the blended white carbon black antibacterial agent can release antibacterial factors to realize an antibacterial effect, and the graft is polymerized in a structural network of a substrate to directly play a role in bacteria adhered to the surface, and synergistic antibacterial is carried out through two modes.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The silicone rubber is prepared by the following steps:
step S11, adding sodium silicate and sodium bicarbonate into deionized water, heating to 90 ℃, uniformly stirring and reacting for 20min, adding sodium silicate again, uniformly stirring for 5min, adding sodium bicarbonate, uniformly stirring and reacting for 1h, adding holmium nitrate and silver nitrate, uniformly stirring and reacting for 1h, cooling, suction filtering and drying after the reaction is finished to obtain the antibacterial white carbon black, wherein the dosage ratio of the sodium silicate, the sodium bicarbonate and the deionized water is controlled to be 0.01 mol: 100mL, and the dosage ratio of the holmium nitrate, the silver nitrate and the deionized water is controlled to be 0.5 mmol: 0.05 mol: 1000mL;
and S12, adding the antibacterial white carbon black into petroleum ether, performing ultrasonic treatment, pouring into silicon rubber latex, performing vacuum filtration after uniform stirring, stirring at a constant speed of 200r/min, adding a curing agent, namely alkyl diethanolamide, continuously stirring until no bubbles are generated, pouring into a mold, and curing for 10 hours to obtain the silicon rubber, wherein the dosage ratio of the antibacterial white carbon black, the petroleum ether, the silicon rubber latex to the curing agent is controlled to be 0.20 g: 10 mL: 50 g: 1g.
Example 2
The silicone rubber is prepared by the following steps:
step S11, adding sodium silicate and sodium bicarbonate into deionized water, heating to 92 ℃, stirring at a constant speed and reacting for 20min, adding the sodium silicate again, stirring at a constant speed for 5min, adding the sodium bicarbonate, stirring at a constant speed and reacting for 1h, adding holmium nitrate and silver nitrate, stirring at a constant speed and reacting for 1h, cooling, filtering and drying after the reaction is finished to obtain the antibacterial white carbon black, wherein the dosage ratio of the sodium silicate, the sodium bicarbonate and the deionized water is controlled to be 0.01 mol: 100mL, and the dosage ratio of the holmium nitrate, the silver nitrate and the deionized water is controlled to be 0.5 mmol: 0.05 mol: 1000mL;
and S12, adding the antibacterial white carbon black into petroleum ether, performing ultrasonic treatment, pouring into silicon rubber latex, performing vacuum filtration after uniform stirring, stirring at a constant speed of 200r/min, adding a curing agent, namely alkyl diethanolamide, continuously stirring until no bubbles are generated, pouring into a mold, and curing for 11 hours to obtain the silicon rubber, wherein the dosage ratio of the antibacterial white carbon black, the petroleum ether, the silicon rubber latex to the curing agent is controlled to be 0.22g to 12mL to 55g to 1.5g.
Example 3
The silicone rubber is prepared by the following steps:
step S11, adding sodium silicate and sodium bicarbonate into deionized water, heating to 95 ℃, uniformly stirring and reacting for 20min, adding the sodium silicate again, uniformly stirring for 5min, adding the sodium bicarbonate, uniformly stirring and reacting for 1h, adding holmium nitrate and silver nitrate, uniformly stirring and reacting for 1h, cooling, filtering and drying after the reaction is finished to obtain the antibacterial white carbon black, wherein the dosage ratio of the sodium silicate, the sodium bicarbonate and the deionized water is controlled to be 0.01 mol: 100mL, and the dosage ratio of the holmium nitrate, the silver nitrate and the deionized water is controlled to be 0.5 mmol: 0.05 mol: 1000mL;
and S12, adding the antibacterial white carbon black into petroleum ether, performing ultrasonic treatment, pouring into silicon rubber latex, performing vacuum filtration after uniform stirring, stirring at a constant speed of 200r/min, adding a curing agent, namely alkyl diethanolamide, continuously stirring until no bubbles are generated, pouring into a mold, and curing for 12 hours to obtain the silicon rubber, wherein the dosage ratio of the antibacterial white carbon black, the petroleum ether, the silicon rubber latex to the curing agent is controlled to be 0.25 g: 15 mL: 60 g: 2g.
Example 4
A preparation method of a medical composite material comprises the following steps:
step S1, adding methyl methacrylate and dimethylaminoethanol into a reaction kettle, stirring at a constant speed, adding benzoyl peroxide and hydroquinone, stirring at a constant speed, heating to 105 ℃, carrying out reflux reaction for 4 hours, carrying out reduced pressure distillation after the reaction is finished to remove unreacted methyl methacrylate and dimethylaminoethanol to obtain an intermediate, adding the intermediate into deionized water, heating to 70 ℃, introducing methane chloride, carrying out heat preservation reaction for 5 hours, washing after the reaction is finished, standing for 30 minutes, and removing by-products under reduced pressure to obtain a graft, wherein the molar ratio of the methyl methacrylate to the dimethylaminoethanol is controlled to be 2: 1, the dosage of the benzoyl peroxide is 1 percent of the sum of the methyl methacrylate and the dimethylaminoethanol, the dosage of the hydroquinone is 0.1 percent of the weight of a catalyst, and the molar ratio of the intermediate, the methane chloride and the deionized water is 1: 0.2;
step S2, adding benzophenone and benzoin dimethyl ether into acetone, stirring at a constant speed for 30min to prepare initiator mixed solution, controlling the using amount ratio of the benzophenone, the benzoin dimethyl ether and the acetone to be 0.705: 0.075: 20mL, ultrasonically cleaning silicon rubber for 30min by using ethanol aqueous solution with the volume fraction of 50%, drying, treating for 5min by using oxygen plasma, placing the silicon rubber into the initiator mixed solution after the treatment is finished, sealing and storing for 2h at 37 ℃, taking out and naturally drying for 2h to prepare pretreated silicon rubber, and controlling the weight ratio of the initiator mixed solution to the silicon rubber to be 20: 2;
and S3, adding the graft obtained in the step S1 into deionized water, adding pretreated silicon rubber, irradiating for 5min by ultraviolet light, then ultrasonically cleaning for 5min by using an ethanol aqueous solution with the volume fraction of 50% to remove unreacted monomer and initiator mixed solution, and preparing the medical composite material, wherein the weight ratio of the graft to the deionized water to the pretreated silicon rubber is controlled to be 0.5: 1: 3.
Example 5
A preparation method of a medical composite material comprises the following steps:
step S1, adding methyl methacrylate and dimethylaminoethanol into a reaction kettle, stirring at a constant speed, adding benzoyl peroxide and hydroquinone, stirring at a constant speed, heating to 120 ℃, carrying out reflux reaction for 4 hours, carrying out reduced pressure distillation after the reaction is finished to remove unreacted methyl methacrylate and dimethylaminoethanol to obtain an intermediate, then adding the intermediate into deionized water, heating to 70 ℃, introducing methyl chloride, carrying out heat preservation reaction for 5 hours, washing and standing for 30 minutes after the reaction is finished, removing by-products under reduced pressure to obtain a graft, controlling the molar ratio of methyl methacrylate to dimethylaminoethanol to be 2.15: 1, controlling the dosage of benzoyl peroxide to be 1.2% of the sum of the weights of methyl methacrylate and dimethylaminoethanol, controlling the dosage of hydroquinone to be 0.2% of the weight of a catalyst, and controlling the molar ratio of the intermediate, the methyl chloride and the deionized water to be 1: 0.3;
step S2, adding benzophenone and benzoin dimethyl ether into acetone, stirring at a constant speed for 30min to prepare initiator mixed solution, controlling the using amount ratio of the benzophenone, the benzoin dimethyl ether and the acetone to be 0.705: 0.075: 20mL, ultrasonically cleaning silicon rubber for 30min by using ethanol aqueous solution with the volume fraction of 50%, drying, treating for 5min by using oxygen plasma, placing the silicon rubber into the initiator mixed solution after the treatment is finished, sealing and storing for 2h at 37 ℃, taking out and naturally drying for 2h to prepare pretreated silicon rubber, and controlling the weight ratio of the initiator mixed solution to the silicon rubber to be 20: 2.3;
and S3, adding the graft obtained in the step S1 into deionized water, adding pretreated silicon rubber, irradiating for 5min by ultraviolet light, then ultrasonically cleaning for 5min by using an ethanol aqueous solution with the volume fraction of 50% to remove unreacted monomer and initiator mixed solution, and preparing the medical composite material, wherein the weight ratio of the graft to the deionized water to the pretreated silicon rubber is controlled to be 0.6: 1: 4.
Example 6
A preparation method of a medical composite material comprises the following steps:
step S1, adding methyl methacrylate and dimethylaminoethanol into a reaction kettle, stirring at a constant speed, adding benzoyl peroxide and hydroquinone, stirring at a constant speed, heating to 125 ℃, carrying out reflux reaction for 4 hours, carrying out reduced pressure distillation after the reaction is finished to remove unreacted methyl methacrylate and dimethylaminoethanol to obtain an intermediate, then adding the intermediate into deionized water, heating to 70 ℃, introducing methyl chloride, carrying out heat preservation reaction for 5 hours, washing and standing for 30 minutes after the reaction is finished, removing by-products under reduced pressure to obtain a graft, controlling the molar ratio of methyl methacrylate to dimethylaminoethanol to be 2.25: 1, controlling the dosage of benzoyl peroxide to be 1-1.5 percent of the sum of the weight of methyl methacrylate and dimethylaminoethanol, the dosage of hydroquinone to be 0.3 percent of the weight of a catalyst, and controlling the molar ratio of the intermediate, the methyl chloride and the deionized water to be 1: 0.3;
s2, adding benzophenone and benzoin dimethyl ether into acetone, stirring at a constant speed for 30min to prepare initiator mixed solution, controlling the dosage ratio of the benzophenone, the benzoin dimethyl ether and the acetone to be 0.705: 0.075: 20mL, ultrasonically cleaning silicon rubber by using ethanol aqueous solution with the volume fraction of 50% for 30min, drying, treating for 5min by using oxygen plasma, placing the silicon rubber into the initiator mixed solution after the treatment is finished, sealing and storing for 2h at 37 ℃, taking out and naturally drying for 2h to prepare pretreated silicon rubber, and controlling the weight ratio of the initiator mixed solution to the silicon rubber to be 20: 2.5;
and S3, adding the graft obtained in the step S1 into deionized water, adding pretreated silicon rubber, irradiating for 5min by ultraviolet light, then ultrasonically cleaning for 5min by using an ethanol aqueous solution with the volume fraction of 50% to remove unreacted monomer and initiator mixed solution, and preparing the medical composite material, wherein the weight ratio of the graft to the deionized water to the pretreated silicon rubber is controlled to be 0.8: 1: 5.
Comparative example 1
Compared with the example 4, the antibacterial white carbon black is not added into the silicon rubber.
Comparative example 2
In comparison with example 4, the surface of the silicone rubber of this comparative example has no graft polymer.
Comparative example 3
This comparative example is an antibacterial silicone rubber material produced by a commercially available company.
Comparative example 4
Compared with example 4, the comparative example uses graphene to replace antibacterial white carbon black.
Shearing the silicon rubber materials prepared in the examples 4-6 and the comparative examples 1-3 into samples to be tested with the size of 50 multiplied by 50mm, soaking the samples for 1min by using ethanol solution with the volume fraction of 70%, taking out the samples, washing the samples by using sterile water, and sterilizing other experimental instruments for 20min at the temperature of 121 ℃; the sample to be tested is placed in a sterilized flat dish, 1.0 plus or minus 0.1mL of prepared bacteria are respectively dripped on the sample to be tested, and three parallel samples are prepared in each group. Attaching the covering film to a sample to be detected by using tweezers to ensure that the bacterial liquid is uniformly dispersed on a control sample and an experimental sample; numbering, and putting the flat dish into a constant-temperature incubator at 37 ℃ for 24 hours; after culturing, growing and propagating single cells to form colonies, counting the number of the colonies, calculating the number of bacteria in the sample, and comparing the number of bacteria in the blank sample with the number of bacteria in the detection sample to obtain the sterilization rate; the results are shown in the table:
Figure 921714DEST_PATH_IMAGE004
it can be seen from the above table that the silicone rubbers prepared in examples 4 to 6 of the present invention have more excellent antibacterial properties, and compared to comparative example 4, the present invention has more excellent antibacterial properties, and further compared to comparative example 4, the present invention has synergistic antibacterial effects.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.

Claims (5)

1. A preparation method of a medical composite material is characterized by comprising the following steps: the method comprises the following steps:
step S1, adding methyl methacrylate and dimethylaminoethanol into a reaction kettle, stirring at a constant speed, adding a catalyst and a polymerization inhibitor, stirring at a constant speed, heating to 105-125 ℃, performing reflux reaction for 4 hours, performing reduced pressure distillation after the reaction is finished to obtain an intermediate, adding the intermediate into deionized water, heating to 70 ℃, introducing methane chloride, performing heat preservation reaction for 5 hours, washing after the reaction is finished, standing for 30 minutes, and removing a byproduct under reduced pressure to obtain a graft;
s2, adding benzophenone and benzoin dimethyl ether into acetone, stirring at a constant speed for 30min to prepare an initiator mixed solution, controlling the dosage ratio of the benzophenone, the benzoin dimethyl ether and the acetone to be 0.705: 0.075: 20mL, ultrasonically cleaning silicon rubber for 30min by using an ethanol aqueous solution with the volume fraction of 50%, drying, treating for 5min by using oxygen plasma, placing the silicon rubber into the initiator mixed solution after the treatment is finished, sealing and storing for 2h at 37 ℃, taking out and drying for 2h to prepare the pretreated silicon rubber;
and S3, adding the graft obtained in the step S1 into deionized water, adding pretreated silicon rubber, irradiating for 5min by using ultraviolet light, and then ultrasonically cleaning for 5min by using an ethanol aqueous solution with the volume fraction of 50% to obtain the medical composite material.
2. The method for preparing a medical composite material according to claim 1, wherein the method comprises the following steps: in the step S1, the molar ratio of methyl methacrylate to dimethylaminoethanol is controlled to be 2-2.25: 1, the dosage of the catalyst is 1-1.5% of the sum of the weight of methyl methacrylate and dimethylaminoethanol, the dosage of the polymerization inhibitor is 0.1-0.3% of the weight of the catalyst, the molar ratio of the intermediate, methyl chloride and deionized water is 1: 0.2-0.3, the weight ratio of the initiator mixed solution to the silicone rubber is controlled to be 20: 2-2.5 in the step S2, and the weight ratio of the graft, the deionized water and the pretreated silicone rubber is controlled to be 0.5-0.8: 1: 3-5 in the step S3.
3. The method for preparing a medical composite material according to claim 1, wherein the method comprises the following steps: the silicone rubber is prepared by the following steps:
step S11, adding sodium silicate and sodium bicarbonate into deionized water, heating to 90-95 ℃, uniformly stirring and reacting for 20min, adding the sodium silicate again, uniformly stirring for 5min, adding the sodium bicarbonate, uniformly stirring and reacting for 1h, adding holmium nitrate and silver nitrate, uniformly stirring and reacting for 1h, cooling, filtering and drying after the reaction is finished, and obtaining the antibacterial white carbon black;
and S12, adding the antibacterial white carbon black into petroleum ether, performing ultrasonic treatment, pouring into the silicone rubber latex, uniformly stirring, performing vacuum filtration, uniformly stirring at a rotating speed of 200r/min, adding a curing agent, continuously stirring until no bubbles are generated, pouring into a mold, and curing for 10-12 hours to obtain the silicone rubber.
4. A method for preparing a medical composite material according to claim 3, characterized in that: in the step S11, the dosage ratio of the sodium silicate, the sodium bicarbonate and the deionized water is controlled to be 0.01 mol: 100mL, the dosage ratio of the holmium nitrate, the silver nitrate and the deionized water is controlled to be 0.5 mmol: 0.05 mol: 1000mL, and the dosage ratio of the antibacterial white carbon black, the petroleum ether, the silicon rubber latex and the curing agent is controlled to be 0.20-0.25 g: 10-15 mL: 50-60 g: 1-2g in the step S12.
5. A medical composite material, characterized by being prepared by the preparation method of any one of claims 1 to 4.
CN202211144151.5A 2022-09-20 2022-09-20 Medical composite material and preparation method thereof Pending CN115260411A (en)

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