CN112280088A - Long-acting antibacterial silicone rubber and preparation method thereof - Google Patents
Long-acting antibacterial silicone rubber and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention discloses a long-acting antibacterial silicone rubber and a preparation method thereof, wherein a compact cross-linked reticular polyimidazole layer is bonded on the surface of the silicone rubber, and the thickness of the cross-linked reticular polyimidazole layer is 1-30 mu m. The long-acting antibacterial silicone rubber and the preparation method thereof provided by the invention solve the problem that the existing antibacterial silicone rubber is difficult to give consideration to both biocompatibility and long-acting antibacterial property in a physiological environment, and have a good application prospect.
Description
Technical Field
The invention relates to the field of medical silicon rubber materials, in particular to long-acting antibacterial silicon rubber and a preparation method thereof.
Background
The silicon rubber has excellent biological safety and chemical inertness, and is widely applied to medical instruments for implantation or interventional therapy, such as catheters, drainage tubes, breathing catheters, cervical occluders, wound dressings and other fields. However, as exogenous artificial materials, the surfaces of silicone rubber are easy to generate bacterial adhesion and proliferation phenomena during implantation/intervention, and the more the silicone rubber is easy to generate bacterial adhesion and infection along with the increase of implantation time, even a biological film is formed on the surfaces, and finally the implanted materials need to be replaced, thus causing huge burden to medical workers and patients. It is counted that the bacterial infection caused by the use of silicone rubber accounts for 40% of the total number of nosocomial infections each year, and the bacterial infection rate of silicone rubber is increasing year by year. Therefore, it is important to impart antibacterial property to the surface of silicone rubber, and particularly, for silicone rubber materials which are to be implanted or left in the body for a long time, not only the surface thereof but also the surface thereof is required to have excellent long-lasting antibacterial property.
Currently, there are two main ways to research and develop antibacterial silicone rubber:
1) adding antibiotics or antibacterial macromolecules on the surface: the antibiotic or the organic antibacterial agent is combined with the silicon rubber by means of bulk addition or surface coating. For example, in Chinese patent CN 201558397U, "slow release amikacin-carrying silicone rubber", polylactic acid-polyglycolic acid carrying amikacin is coated on the surface of the silicone rubber, and antibacterial effect is obtained by slow release of amikacin. However, the combination force of the antibiotics and the silicon rubber substrate is weak, slow release cannot be realized, the antibiotics are burst released at the early stage of implantation, the later-stage antibacterial performance is greatly reduced, long-acting antibiosis cannot be realized, and the antibiotic is used in a large amount, so that the drug resistance of bacteria is generated, and the antibiotic is ineffective. For example, CN 104712815A activates silicon rubber by a silane coupling agent, and then cellulose, chitosan, chondroitin sulfate, antibacterial polyamino acid or polypeptide is grafted to the surface of the silicon rubber to obtain the antibacterial silicon rubber with the surface containing the organic macromolecular brush. However, since The organic macromolecules exist on The surface of The silica gel in The form of a molecular brush and no chemical bonds exist among molecules, more importantly, The organic macromolecules are easily degraded in a physiological environment, such as polylysine and polyglutamic acid, and The like, under The physiological conditions and The action of trypsin (The Biochemical journal 1964,91(3), 431-6), and long-acting antibacterial property cannot be guaranteed after degradation.
2) Adding antibacterial metal ions or nano particles to the body or the surface: compounding inorganic antibacterial agent carrying silver, copper or zinc with silicone rubber, and releasing antibacterial metal ions (Ag)+、Cu2+Or Zn2+) Or the nano particles and the surface of the silicon rubber are fineThe antibacterial effect is realized. For example, Chinese patent CN 105238057A loads antibacterial metal ions and white carbon black and then compounds the antibacterial metal ions and white carbon black with a silica gel substrate to prepare the antibacterial silicone rubber. For example, in the chinese patent application CN2778285Y "antibacterial silicone rubber", the surface layer of silicone rubber is coated with nano silver to prepare the antibacterial silicone rubber. However, the continuous precipitation and accumulation of antibacterial metal ions or nanoparticles can destroy the microenvironment balance of surrounding tissues, interfere the normal growth of surrounding cells, generate cytotoxicity and have poor biocompatibility. In view of this, the regulatory agency has issued announcements (e.g., No. 146 announcement in 2006, No. 105 announcement in 2012, No. 225 announcement in 2015) many times to regulate the application of nano-silver and silver ions in medical devices.
Therefore, the existing technical scheme can not give consideration to the long-acting antibacterial performance and the biocompatibility of the material, and can not meet the antibacterial performance required by the long-term implantation of the silicon rubber. .
Disclosure of Invention
The invention aims to solve the first technical problem of providing long-acting antibacterial silicone rubber. The antibacterial silicone rubber and the preparation method thereof provided by the invention solve the problem that the existing antibacterial silicone rubber is difficult to take biocompatibility and long-acting antibacterial property into consideration, and have better application prospects.
The second technical problem to be solved by the invention is to provide a preparation method of the long-acting antibacterial silicone rubber.
In order to solve the first technical problem, the invention adopts the following technical scheme:
the long-acting antibacterial silicone rubber is characterized in that a compact cross-linked reticular polyimidazole layer is bonded on the surface of the silicone rubber, and the thickness of the cross-linked reticular polyimidazole layer is 1-30 mu m.
Preferably, the polyimidazole is a crosslinked copolymer of a vinylimidazole salt or an allylimidazole salt and a poly-vinyl or allyl compound, the vinylimidazole salt or the allylimidazole salt having the following structure:
vinylimidazole salts:
allyl imidazole salt:
wherein R in the formula is any one of the following structures:
CH3、CH2CH3、CH2(CH2)2CH3、CH2(CH2)4CH3、CH2(CH2)6CH3；
X-is any one of the structures shown below:
Cl-Br-BF4 -NO3 -PF6 -CH3SO4 -。
preferably, the multi-vinyl or allyl compound is one or more of N, N-methylene diacrylamide, 1, 6-hexanediol diacrylate, pentaerythritol diacrylate, 1, 3-propanediol diacrylate, ethylene glycol dimethacrylate and polyethylene glycol diacrylate.
In order to solve the second technical problem, the invention adopts the following technical scheme:
a preparation method of long-acting antibacterial silicone rubber comprises the following steps:
s1, soaking the silicon rubber in an alcohol solution containing 5-20% of one or more of vinyl silane coupling agents or methacryloxy silane coupling agents for reaction for 2-24 hours (the reaction temperature is 30-60 ℃, and the reaction temperature is 3 cm)2Adding 1mL of reaction solution into the silicon rubber), and carrying out ultrasonic washing after the reaction is finished to obtain modified silicon rubber;
s2, preparing a mixed aqueous solution containing imidazolium salt, an initiator and a multi-vinyl or allyl compound, wherein the concentration of the imidazolium salt in the mixed aqueous solution is 0.2-2g/mL, the mass of the initiator is 0.01-2% of that of the imidazolium salt, and the multi-vinyl or allyl compound is 1-10% of the molar fraction of the imidazolium salt;
s3, soaking the modified silicon rubber in the S1 in the mixed aqueous solution in the S2, and reacting for 0.5 to 12 hours under certain initiation conditions; and taking out the silicon rubber after the reaction is finished, and performing conventional post-treatment to obtain the long-acting antibacterial silicon rubber.
Preferably, in step S1, in step S1, the vinyl silane coupling agent is one or more of vinyl triacetoxysilane, vinyl tris (2-methoxyethoxy) silane, vinyl triisopropoxysilane, vinyl triethoxysilane, and vinyl trimethoxysilane; the methacryloxy silane coupling agent is one or more of gamma-methacryloxy propyl trimethoxy silane, gamma-methacryloxy propyl triisopropoxy silane, gamma-methacryloxy methyl dimethoxy silane and gamma-methacryloxy propyl triethoxy silane.
Preferably, the imidazolium salt in S2 is one or two of vinylimidazolium salt and allylimidazolium salt; the structure of the vinylimidazole salt or allylimidazole salt is shown as follows:
vinylimidazole salts:
allyl imidazole salt:
wherein R in the formula is any one of the following structures:
CH3、CH2CH3、CH2(CH2)2CH3、CH2(CH2)4CH3、CH2(CH2)6CH3；
X-is any one of the structures shown below:
Cl-Br-BF4 -NO3 -PF6 -CH3SO4 -。
preferably, in step S2, the poly vinyl or allyl compound is one or more of N, N-methylene bisacrylamide, 1, 6-hexanediol diacrylate, pentaerythritol diacrylate, 1, 3-propanediol diacrylate, ethylene glycol dimethacrylate, and polyethylene glycol diacrylate.
More preferably, the molecular weight of the polyethylene glycol segment in the polyethylene glycol diacrylate is 100-1000.
Preferably, in step S2, the initiator is one or more of an azo-based radical initiator and a peroxide-based radical initiator.
More preferably, the initiator is one or more of ammonium persulfate, potassium persulfate, hydrogen peroxide, azodiisobutyramidine hydrochloride and benzoyl peroxide;
preferably, in step S3, the certain initiation condition is ultraviolet light irradiation initiation, gamma ray irradiation initiation, microwave initiation or heating initiation.
Preferably, in step S3, the conventional post-treatment includes ultrasonic cleaning, drying, packaging and sterilization steps.
As a further improvement of the technical solution, before performing step S1, the surface of the silicone rubber is activated, for example, the surface of the silicone rubber is activated by using a plasma modification technique or a surface hydrophilic modification technique, so as to improve the reaction efficiency of S1.
Further, the plasma modification technique comprises the following steps:
s10, placing the silicon rubber into plasma modification equipment, treating the surface of the silicon rubber for 10-60 minutes by adopting oxygen plasma or nitrogen plasma, taking out the silicon rubber and immediately carrying out the step S1;
further, the surface hydrophilic modification technology comprises the following steps:
s10, the silicone rubber is put into the mixed solution of sulfuric acid and hydrogen peroxide, soaked for 1-30 minutes, taken out, cleaned and dried, and then the step S1 is immediately carried out.
Any range recited herein is intended to include the endpoints and any number between the endpoints and any subrange subsumed therein or defined therein.
The starting materials of the present invention are commercially available, unless otherwise specified, and the equipment used in the present invention may be any equipment conventionally used in the art or may be any equipment known in the art.
Compared with the prior art, the invention has the following beneficial effects:
1) the crosslinked polyimidazole layer bonded on the surface of the silicon rubber has a stable and compact chemical structure, the thickness of the crosslinked polyimidazole layer reaches 1-30 mu m, no toxic and harmful chemical micromolecules are separated out, the crosslinked polyimidazole layer can not be degraded in a physiological environment, the crosslinked polyimidazole layer can be used for long-acting antibiosis, and the antibacterial rate of the crosslinked polyimidazole layer to bacteria is still over 99 percent after the crosslinked polyimidazole layer is soaked in a simulated physiological environment (37 ℃ and simulated body fluid) for 30 days.
2) The crosslinked polyimidazole layer and the surface of the silicon rubber are chemically and covalently bonded, the bonding force is strong, and the risk of tissue inflammation caused by coating debris generated by coating falling off is avoided.
3) The interaction between the positively charged imidazole ring in the polyimidazole layer and the surface of the bacterial cell membrane is crosslinked through the surface of the silicon rubber, and the interaction does not act on the DNA of bacteria like the traditional Antibiotics, so that the generation of super-resistant bacteria is not caused (Word Notes on Antibiotics,2009, Vol, No.4), and the preparation has the advantage of no drug resistance.
The antibacterial silicone rubber and the preparation method thereof provided by the invention solve the problem that the existing antibacterial silicone rubber is difficult to take biocompatibility and long-acting antibacterial property into consideration, and have better application prospects.
Drawings
FIG. 1 is an infrared spectrum of a surface-crosslinked polyimidazole layer of silicone rubber obtained in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of a surface cross-linked polyimidazole layer of silicone rubber obtained in example 1 of the present invention.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
As one aspect of the invention, the invention provides long-acting antibacterial silicone rubber, wherein a compact cross-linked reticular polyimidazole layer is bonded on the surface of the silicone rubber, and the thickness of the cross-linked reticular polyimidazole layer is 1-30 μm.
After the long-acting antibacterial silicone rubber is soaked in a simulated physiological environment (37 ℃ and simulated body fluid) for 30 days, the antibacterial rate of the long-acting antibacterial silicone rubber on bacteria still exceeds 99 percent, and the bacterial species comprise escherichia coli, staphylococcus aureus, staphylococcus epidermidis, pseudomonas aeruginosa, candida albicans, streptococcus pneumoniae and the like; the long-acting antibacterial silicone rubber has cytotoxicity on mouse fibroblast not more than grade 1, no subcutaneous stimulation reaction and good biocompatibility.
In certain embodiments of the present invention, the polyimidazole is a crosslinked copolymer of a vinylimidazolium salt or an allylimidazolium salt and a poly-vinyl or allylic compound, the monomers of the vinylimidazolium salt or the allylimidazolium salt having the structure:
vinylimidazole salts:
allyl imidazole salt:
wherein R in the formula is any one of the following structures:
CH3、CH2CH3、CH2(CH2)2CH3、CH2(CH2)4CH3、CH2(CH2)6CH3；
X-is any one of the structures shown below:
Cl-Br-BF4 -NO3 -PF6 -CH3SO4 -；
the multi-vinyl or allyl compound is one or more of N, N-methylene diacrylamide, 1, 6-hexanediol diacrylate, pentaerythritol diacrylate, 1, 3-propylene glycol diacrylate, ethylene glycol dimethacrylate and polyethylene glycol diacrylate;
preferably, the molecular weight of the polyethylene glycol segment in the polyethylene glycol diacrylate is 100-1000.
As another aspect of the present invention, the present invention provides a method for preparing a long-acting antibacterial silicone rubber, comprising the steps of:
s1, soaking the silicon rubber in an alcohol solution containing 5-20% of one or more of vinyl silane coupling agents or methacryloxy silane coupling agents for reaction for 2-24 hours (the reaction temperature is 30-60 ℃, and the reaction temperature is 3 cm)2Adding 1mL of reaction solution into the silicon rubber), and carrying out ultrasonic washing after the reaction is finished to obtain modified silicon rubber;
s2, preparing a mixed aqueous solution containing imidazolium salt, an initiator and a multi-vinyl or allyl compound, wherein the concentration of the imidazolium salt in the mixed aqueous solution is 0.2-2g/mL, the mass of the initiator is 0.01-2% of that of the imidazolium salt, and the multi-vinyl or allyl compound is 1-10% of the molar fraction of the imidazolium salt;
s3, soaking the modified silicon rubber in the S1 in the mixed aqueous solution of S2, and reacting for 0.5-12 hours under the initiation condition; and taking out the silicon rubber after the reaction is finished, and performing conventional post-treatment to obtain the long-acting antibacterial silicon rubber.
The antibacterial silicone rubber is formed by in-situ polymerization and crosslinking of one or more of an initiator, vinyl imidazole salt and allyl imidazole salt, and a multi-vinyl or allyl compound on the surface of silicone rubber under a certain initiating condition, and normal physiological activities of bacteria are inhibited by utilizing the interaction of an imidazole ring with positive electricity and a cell membrane with negative electricity on the surface of the bacteria under a physiological environment, so that an antibacterial function is realized; the crosslinked polyimidazole layer has stable chemical performance under physiological conditions, does not have precipitation of other harmful chemical substances or shedding of coating scraps, is not degradable, and can realize long-acting antibiosis.
In certain embodiments of the present invention, in step S1, the vinyl silane coupling agent is one or more of vinyl triacetoxysilane, vinyl tris (2-methoxyethoxy) silane, vinyl triisopropoxysilane, vinyl triethoxysilane, vinyl trimethoxysilane; the methacryloxy silane coupling agent is one or more of gamma-methacryloxy propyl trimethoxy silane, gamma-methacryloxy propyl triisopropoxy silane, gamma-methacryloxy methyl dimethoxy silane and gamma-methacryloxy propyl triethoxy silane.
In certain embodiments of the present invention, in step S2, the imidazolium salt is one or both of a vinylimidazolium salt and an allylimidazolium salt; the structure of the vinylimidazole salt or allylimidazole salt is shown as follows:
vinylimidazole salts:
allyl imidazole salt:
wherein R in the formula is any one of the following structures:
CH3、CH2CH3、CH2(CH2)2CH3、CH2(CH2)4CH3、CH2(CH2)6CH3；
X-is any one of the structures shown below:
Cl-Br-BF4 -NO3 -PF6 -CH3SO4 -。
in some embodiments of the present invention, in step S2, the poly vinyl or allyl compound is one or more of N, N-methylene bisacrylamide, 1, 6-hexanediol diacrylate, pentaerythritol diacrylate, 1, 3-propanediol diacrylate, ethylene glycol dimethacrylate, and polyethylene glycol diacrylate;
in certain preferred embodiments of the present invention, the molecular weight of the polyethylene glycol segment in the polyethylene glycol diacrylate is 100-1000.
In certain embodiments of the present invention, in step S2, the initiator is one or more of an azo-based radical initiator, a peroxide-based radical initiator.
In certain embodiments of the invention, the initiator is one or more of ammonium persulfate, potassium persulfate, hydrogen peroxide, azobisisobutyramidine hydrochloride, benzoyl peroxide;
in some embodiments of the present invention, in step S3, the certain initiation condition is ultraviolet light irradiation initiation, gamma ray irradiation initiation, microwave initiation or heating initiation.
In certain embodiments of the present invention, the conventional post-treatment comprises steps of ultrasonic cleaning, drying, packaging and sterilization in step S3.
As a further improvement of the technical solution, before performing step S1, the surface of the silicone rubber may be subjected to an activation treatment, such as activating the surface of the silicone rubber by using a plasma modification technique or a surface hydrophilic modification technique, to improve the reaction efficiency of S1.
In certain embodiments of the present invention, the plasma modification technique comprises the steps of:
s10, placing the silicon rubber into plasma modification equipment, treating the surface of the silicon rubber for 10-60 minutes by adopting oxygen plasma or nitrogen plasma, taking out the silicon rubber and immediately carrying out the step S1;
in certain embodiments of the present invention, the surface hydrophilic modification technique comprises the steps of:
s10, the silicone rubber is put into the mixed solution of sulfuric acid and hydrogen peroxide, soaked for 1-30 minutes, taken out, cleaned and dried, and then the step S1 is immediately carried out.
Example 1
A preparation method of long-acting antibacterial silicone rubber comprises the following steps:
s1, placing the silicon rubber into a mixed solution of sulfuric acid and hydrogen peroxide (volume ratio is 7:3), soaking for 1 minute, taking out the silicon rubber, cleaning and airing, then soaking the silicon rubber into an ethanol solution containing 15% of gamma-methacryloxypropyltriethoxysilane, reacting for 18 hours at 50 ℃, taking out the silicon rubber, ultrasonically cleaning and airing to obtain modified silicon rubber;
s2, respectively dissolving 1-allyl-3-butylimidazolium tetrafluoroborate, azobisisobutyramidine hydrochloride and 1, 3-propanediol diacrylate in deionized water to prepare a functional reaction solution, wherein the concentration of the 1-allyl-3-butylimidazolium tetrafluoroborate in the aqueous solution is 1.3g/mL, the mass of the azobisisobutyramidine hydrochloride is 0.5% of that of the 1-allyl-3-butylimidazolium tetrafluoroborate, and the mass of the 1, 3-propanediol diacrylate is 6% of the mole number of the 1-allyl-3-butylimidazolium tetrafluoroborate;
s3, soaking the modified silicon rubber in the S1 in the functional reaction solution in the S2, and carrying out ultraviolet irradiation to react for 10 hours; and taking out the silicon rubber, ultrasonically cleaning the silicon rubber for 3 times by using deionized water, airing, packaging and sterilizing to obtain the long-acting antibacterial silicon rubber.
Example 2
A preparation method of long-acting antibacterial silicone rubber comprises the following steps:
s1, soaking the silicone rubber in an ethanol solution containing 20% of vinyl tris (2-methoxyethoxy) silane, reacting for 24 hours at 30 ℃, taking out the silicone rubber, ultrasonically cleaning and airing to obtain modified silicone rubber;
s2, sequentially dissolving 1-vinyl-3-ethylimidazole chloride, potassium persulfate and N, N-methylene bisacrylamide in deionized water to prepare a functional reaction solution, wherein the mass concentration of the 1-vinyl-3-ethylimidazole chloride in the aqueous solution is 1.2g/mL, the mass of the potassium persulfate is 0.01% of that of the 1-vinyl-3-ethylimidazole chloride, and the mole number of the N, N-methylene bisacrylamide is 8% of that of the 1-vinyl-3-ethylimidazole chloride;
s3, soaking the silicon rubber in the S1 in the functional reaction solution of S2, irradiating by ultraviolet light, and reacting for 12 hours; and taking out the silicon rubber, ultrasonically cleaning the silicon rubber for 2 times by using deionized water, airing, packaging and sterilizing to obtain the long-acting antibacterial silicon rubber.
Example 3
A preparation method of long-acting antibacterial silicone rubber comprises the following steps:
s1, placing the silicon rubber into plasma modification equipment, treating the surface of the silicon rubber for 60 minutes by adopting oxygen plasma, taking out the silicon rubber, immediately soaking the silicon rubber in an ethanol solution containing 15% of gamma-methacryloxypropyltrimethoxysilane, reacting for 24 hours at 60 ℃, taking out the silicon rubber, ultrasonically cleaning and airing to obtain modified silicon rubber;
s2, sequentially dissolving 1-vinyl-3-butylimidazole tetrafluoroborate, azobisisobutyramidine hydrochloride and pentaerythritol diacrylate in deionized water to prepare a functional reaction solution, wherein the mass concentration of the 1-vinyl-3-ethylimidazole tetrafluoroborate in the aqueous solution is 1.6g/mL, the mass of the azobisisobutyramidine hydrochloride is 1% of that of the 1-vinyl-3-ethylimidazole tetrafluoroborate, and the mole number of the pentaerythritol diacrylate is 10% of that of the 1-vinyl-3-butylimidazole tetrafluoroborate;
s3, soaking the silicon rubber in the S1 in the functional reaction solution in the S2, irradiating by ultraviolet light, and reacting for 6 hours; and taking out the silicon rubber, ultrasonically cleaning the silicon rubber for 3 times by using deionized water, airing, packaging and sterilizing to obtain the long-acting antibacterial silicon rubber.
Example 4
A preparation method of long-acting antibacterial silicone rubber comprises the following steps:
s1, soaking the silicone rubber in an ethanol solution containing 5% of vinyl triisopropoxysilane, reacting for 6 hours at 30 ℃, taking out the silicone rubber, ultrasonically cleaning and airing to obtain modified silicone rubber;
s2, sequentially dissolving 1-vinyl-3-hexyl imidazole nitrate, benzoyl peroxide and 1, 3-propylene glycol diacrylate in deionized water to prepare a functional reaction solution, wherein the concentration of the 1-vinyl-3-hexyl imidazole nitrate in the aqueous solution is 0.4g/mL, the mass of the benzoyl peroxide is 0.5% of that of the 1-vinyl-3-hexyl imidazole nitrate, and the mole number of the 1, 3-propylene glycol diacrylate is 3% of that of the 1-vinyl-3-hexyl imidazole nitrate;
s3, soaking the modified silicon rubber in the S1 in the functional reaction solution in the S2, heating the solution to 80 ℃ by microwaves, and reacting the solution for 12 hours; and taking out the silicon rubber, ultrasonically cleaning the silicon rubber for 3 times by using deionized water, airing, packaging and sterilizing to obtain the long-acting antibacterial silicon rubber.
Example 5
A preparation method of long-acting antibacterial silicone rubber comprises the following steps:
s1, soaking the silicone rubber in an isopropanol solution containing 5% of vinyl trimethoxy silane, reacting for 6 hours at 40 ℃, taking out the silicone rubber, ultrasonically cleaning and airing to obtain modified silicone rubber;
s2, dissolving 1-vinyl-3-octylimidazole hexafluorophosphate and ethylene glycol dimethacrylate in deionized water, adding 30% of hydrogen peroxide solution to prepare a functional reaction solution, wherein the concentration of the 1-vinyl-3-octylimidazole hexafluorophosphate in the solution is 0.7g/mL, the mass of the hydrogen peroxide is 1.5% of that of the 1-vinyl-3-octylimidazole hexafluorophosphate, and the mole number of the ethylene glycol dimethacrylate is 4% of that of the 1-vinyl-3-octylimidazole hexafluorophosphate;
s3, soaking the modified silicon rubber in the S1 in the functional reaction solution in the S2, irradiating gamma rays, and reacting for 6 hours; and taking out the silicon rubber, ultrasonically cleaning the silicon rubber for 3 times by using deionized water, airing, packaging and sterilizing to obtain the long-acting antibacterial silicon rubber.
Example 6
A preparation method of long-acting antibacterial silicone rubber comprises the following steps:
s1, soaking the silicone rubber in an isopropanol solution containing 8% of gamma-methacryloxypropyl triisopropoxysilane, reacting for 8 hours at 30 ℃, taking out the silicone rubber, ultrasonically cleaning and drying to obtain modified silicone rubber;
s2, dissolving 1-vinyl-3-methylimidazole methyl sulfate, benzoyl peroxide and polyethylene glycol diacrylate (the molecular weight of a polyethylene glycol chain segment is 100) in deionized water to prepare a functional reaction solution, wherein the mass concentration of 1-vinyl-3-octylimidazole hexafluorophosphate in the aqueous solution is 0.6g/mL, the mass of benzoyl peroxide is 0.5% of that of 1-vinyl-3-octylimidazole hexafluorophosphate, and the mole number of the polyethylene glycol diacrylate is 4% of that of 1-vinyl-3-methylimidazole methyl sulfate;
s3, soaking the modified silicon rubber in the S1 in the functional reaction solution in the S2, heating the solution to 80 ℃ by microwaves, and reacting the solution for 1 hour; and taking out the silicon rubber, ultrasonically cleaning the silicon rubber for 3 times by using deionized water, airing, packaging and sterilizing to obtain the long-acting antibacterial silicon rubber.
Example 7
A preparation method of long-acting antibacterial silicone rubber comprises the following steps:
s1, soaking the silicone rubber in an ethanol solution containing 12% of gamma-methacryloyloxymethyldimethoxysilane, reacting at 60 ℃ for 12 hours, taking out the silicone rubber, ultrasonically cleaning and airing to obtain modified silicone rubber;
s2, respectively dissolving 1-allyl-3-methylimidazole chloride salt, 1-vinyl-3-methylimidazole chloride salt, ammonium persulfate and polyethylene glycol diacrylate (the molecular weight of a polyethylene glycol chain segment is 100) in deionized water to prepare a functional reaction solution, wherein the mass ratio of the 1-allyl-3-methylimidazole chloride salt to the 1-vinyl-3-methylimidazole chloride salt is 1:1, the concentration of the imidazolium salt in an aqueous solution is 1g/mL, the mass of the ammonium persulfate is 0.7% of the mass of the imidazolium salt, and the mole number of the polyethylene glycol diacrylate (the molecular weight of the polyethylene glycol chain segment is 100) is 3% of that of the imidazolium salt;
s2, activating the silicone rubber, and bonding unsaturated carbon-carbon bonds on the surface of the silicone rubber: soaking silicon rubber in a mixed solution of sulfuric acid and hydrogen peroxide for 1 minute (the volume ratio of the sulfuric acid to the hydrogen peroxide is 3:1), taking out the silicon rubber, ultrasonically washing the silicon rubber by using deionized water, then soaking the silicon rubber in an ethanol solution containing 10% of vinyltriethoxysilane, reacting for 24 hours, taking out the silicon rubber, ultrasonically washing the silicon rubber by using ethanol, and airing;
s3, soaking the modified silicon rubber in the S1 in the functional reaction solution in the S2, heating the solution to 70 ℃ by microwaves, and reacting the solution for 3 hours; and taking out the silicon rubber, ultrasonically cleaning the silicon rubber for 3 times by using deionized water, airing, packaging and sterilizing to obtain the long-acting antibacterial silicon rubber.
Example 8
A preparation method of long-acting antibacterial silicone rubber comprises the following steps:
s1, soaking the silicone rubber in an ethanol solution containing 7% of gamma-methacryloyloxymethyldimethoxysilane, reacting for 4 hours at 60 ℃, taking out the silicone rubber, ultrasonically cleaning and airing to obtain modified silicone rubber;
s2, respectively dissolving 1-allyl-3-ethylimidazole bromide, potassium persulfate and 1, 6-hexanediol diacrylate in deionized water to prepare a functional reaction solution, wherein the concentration of the 1-allyl-3-ethylimidazole bromide in the aqueous solution is 0.4g/mL, the mass of the potassium persulfate is 1% of that of the 1-allyl-3-ethylimidazole bromide, and the mole number of the 1, 6-hexanediol diacrylate is 2% of that of the 1-allyl-3-ethylimidazole bromide;
s3, soaking the modified silicon rubber in the S1 in the functional reaction solution in the S2, and carrying out ultraviolet irradiation to react for 5 hours; and taking out the silicon rubber, ultrasonically cleaning the silicon rubber for 3 times by using deionized water, airing, packaging and sterilizing to obtain the long-acting antibacterial silicon rubber.
Example 9
A preparation method of long-acting antibacterial silicone rubber comprises the following steps:
s1, soaking the silicone rubber in an ethanol solution containing 5% of vinyl triacetoxysilane, reacting for 2 hours at 30 ℃, taking out the silicone rubber, ultrasonically cleaning and airing to obtain modified silicone rubber;
s2, sequentially dissolving 1-vinyl-3-methylimidazole bromine salt, ammonium persulfate and 1, 6-hexanediol diacrylate in deionized water to prepare a functional reaction solution, wherein the concentration of the 1-vinyl-3-methylimidazole bromine salt in the aqueous solution is 0.2g/mL, the mass of the ammonium persulfate is 2% of that of the 1-vinyl-3-methylimidazole bromine salt, and the mole number of the 1, 6-hexanediol diacrylate is 1% of that of the 1-vinyl-3-methylimidazole bromine salt;
s3, soaking the modified silicon rubber in the S1 in the functional reaction solution of S2, heating the solution to 60 ℃ by microwave, and reacting the solution for 0.5 hour; and taking out the silicon rubber, ultrasonically cleaning the silicon rubber for 2 times by using deionized water, airing, packaging and sterilizing to obtain the long-acting antibacterial silicon rubber.
Example 10
A preparation method of long-acting antibacterial silicone rubber comprises the following steps:
s1, soaking the silicone rubber in an ethanol solution containing 20% of vinyl trimethoxy silane, reacting for 12 hours at 60 ℃, taking out the silicone rubber, ultrasonically cleaning and airing to obtain modified silicone rubber;
s2, respectively dissolving 1-allyl-3-hexyl imidazole nitrate, benzoyl peroxide and ethylene glycol dimethacrylate in deionized water to prepare a functional reaction solution, wherein the concentration of the 1-allyl-3-hexyl imidazole nitrate in the aqueous solution is 2g/mL, the mass of the benzoyl peroxide is 1% of that of the 1-allyl-3-hexyl imidazole nitrate, and the mole number of the ethylene glycol dimethacrylate is 7.5% of that of the 1-allyl-3-hexyl imidazole nitrate;
s3, soaking the modified silicon rubber in the S1 in the functional reaction solution in the S2, heating the solution to 90 ℃ by microwaves, and reacting the solution for 10 hours; and taking out the silicon rubber, ultrasonically cleaning the silicon rubber for 3 times by using deionized water, airing, packaging and sterilizing to obtain the long-acting antibacterial silicon rubber.
The thickness of the cross-linked polyimidazole layer of the long-acting antibacterial silicone rubber obtained in the above examples 1-10 is tested, the biological performance evaluation (cytotoxicity and intradermal reaction) is performed on the long-acting antibacterial silicone rubber according to the GB/T16886 series standard, the silicone rubber is soaked in simulated body fluid at 37 ℃ for 30 days, and then the antibacterial performance of the silicone rubber is tested according to the antibacterial determination of ISO 22196-2011 plastic and other nonporous surfaces, 2-3 bacteria are selected in each example for testing, and the test results are shown in Table 1:
table 1: long-acting antibacterial and biological Properties of examples 1-10
In order to further understand the technical solution and effect of the present invention, the following is a specific case of the comparative example.
Comparative example 1
A surface modification method of silicone rubber comprises the following steps:
s1, soaking the silicone rubber in an ethanol solution containing 20% of vinyl trimethoxy silane, reacting for 12 hours at 60 ℃, taking out the silicone rubber, ultrasonically cleaning and airing to obtain modified silicone rubber;
s2, respectively dissolving 1-allyl-3-hexyl imidazole nitrate and benzoyl peroxide in deionized water to prepare a functional reaction solution, wherein the concentration of the 1-allyl-3-hexyl imidazole nitrate in the aqueous solution is 2.4g/mL, and the mass of the benzoyl peroxide is 1% of that of the 1-allyl-3-hexyl imidazole nitrate;
s3, soaking the modified silicon rubber in the S1 in the functional reaction solution in the S2, heating the solution to 90 ℃ by microwaves, and reacting the solution for 10 hours; and taking out the silicon rubber, ultrasonically cleaning the silicon rubber for 3 times by using deionized water, airing, packaging and sterilizing to obtain the surface modified silicon rubber.
Comparative example 2
A surface modification method of silicone rubber comprises the following steps:
s1, soaking the silicone rubber in an isopropanol solution containing 10% of vinyl trimethoxy silane, reacting for 8 hours at 40 ℃, taking out the silicone rubber, ultrasonically cleaning and airing to obtain modified silicone rubber;
s2, respectively dissolving 1-vinyl-3-methylimidazole bromine salt and benzoyl peroxide in deionized water to prepare a functional reaction solution, wherein the concentration of the 1-vinyl-3-methylimidazole bromine salt in the aqueous solution is 1g/mL, and the mass of the benzoyl peroxide is 10% of that of the 1-vinyl-3-methylimidazole bromine salt;
s3, soaking the modified silicon rubber in the S1 in the functional reaction solution in the S2, irradiating by ultraviolet light, and reacting for 12 hours; taking out the silicon rubber; and taking out the silicon rubber, ultrasonically cleaning the silicon rubber for 3 times by using deionized water, airing, packaging and sterilizing to obtain the surface modified silicon rubber.
Comparative example 3
A surface modification method of silicone rubber comprises the following steps:
s1, soaking the silicone rubber in an isopropanol solution containing 5% of vinyltriethoxysilane, reacting for 12 hours at 60 ℃, taking out the silicone rubber, ultrasonically cleaning and airing to obtain modified silicone rubber;
s2, respectively dissolving 1-vinyl-3-octylimidazole hexafluorophosphate, ammonium persulfate and 1, 6-hexanediol diacrylate in deionized water to prepare a functional reaction solution, wherein the concentration of the 1-vinyl-3-octylimidazole hexafluorophosphate in the aqueous solution is 0.08g/mL, the mass of the ammonium persulfate is 1% of that of the 1-vinyl-3-octylimidazole hexafluorophosphate, and the mole number of the 1, 6-hexanediol diacrylate is 5% of that of the 1-vinyl-3-octylimidazole hexafluorophosphate;
s3, soaking the modified silicon rubber in the S1 in the functional reaction solution in the S2, irradiating by ultraviolet light, and reacting for 12 hours; and taking out the silicon rubber, ultrasonically cleaning the silicon rubber for 3 times by using deionized water, airing, packaging and sterilizing to obtain the surface modified silicon rubber.
The modified silicone rubbers obtained in the above comparative examples 1 to 3 were evaluated for biological properties (cytotoxicity and intradermal reaction) according to the GB/T16886 series of standards. After the obtained modified silicone rubber is placed in simulated body fluid at 37 ℃ and soaked for 30 days, the antibacterial performance of the modified silicone rubber is tested according to ISO 22196-2011 plastic and other nonporous surface antibacterial property determination, 2-3 bacteria are selected to test the modified silicone rubber in each comparative example, and the thickness of a silicone rubber surface modified layer is tested. The test results are shown in table 2:
table 2: antibacterial and biological Properties of comparative examples 1-3
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Not all embodiments are exhaustive. All obvious changes and modifications which are obvious to the technical scheme of the invention are covered by the protection scope of the invention.
Claims (10)
1. A long-acting antibacterial silicone rubber is characterized in that: a compact cross-linked reticular polyimidazole layer is bonded on the surface of the silicon rubber, and the thickness of the cross-linked reticular polyimidazole layer is 1-30 mu m.
2. The long-acting antibacterial silicone rubber according to claim 1, characterized in that: the polyimidazole layer is a crosslinked copolymer of vinyl imidazolium salt or allyl imidazolium salt and a polybasic vinyl or allyl compound, and the vinyl imidazolium salt or the allyl imidazolium salt has the following structure:
vinylimidazole salts:
allyl imidazole salt:
wherein R in the formula is any one of the following structures:
CH3、CH2CH3、CH2(CH2)2CH3、CH2(CH2)4CH3、CH2(CH2)6CH3；
X-is any one of the structures shown below:
Cl- Br- BF4 - NO3 - PF6 - CH3SO4 -；
the multi-vinyl or allyl compound is one or more of N, N-methylene diacrylamide, 1, 6-hexanediol diacrylate, pentaerythritol diacrylate, 1, 3-propylene glycol diacrylate, ethylene glycol dimethacrylate and polyethylene glycol diacrylate;
preferably, the molecular weight of the polyethylene glycol segment in the polyethylene glycol diacrylate is 100-1000.
3. A method for preparing the long-acting antibacterial silicone rubber according to claim 2, characterized in that: the method comprises the following steps:
s1, soaking the silicon rubber in alcohol solution containing 5-20% of one or more of vinyl silane coupling agents or methacryloxy silane coupling agents for reaction for 2-24 hours at the reaction temperature of 30-60 ℃ and 3cm2Adding 1mL of reaction solution into the silicon rubber, and carrying out ultrasonic washing after the reaction is finished to obtain modified silicon rubber;
s2, preparing a mixed aqueous solution containing imidazolium salt, an initiator and a multi-vinyl or allyl compound, wherein the concentration of the imidazolium salt in the mixed aqueous solution is 0.2-2g/mL, the mass of the initiator is 0.01-2% of that of the imidazolium salt, and the multi-vinyl or allyl compound is 1-10% of the molar fraction of the imidazolium salt;
s3, soaking the modified silicon rubber in the S1 in the mixed aqueous solution in the S2, and reacting for 0.5 to 12 hours under certain initiation conditions; and taking out the silicon rubber after the reaction is finished, and performing conventional post-treatment to obtain the long-acting antibacterial silicon rubber.
4. The method for preparing a long-acting antibacterial silicone rubber according to claim 3, characterized in that:
in step S1, the vinyl silane coupling agent is one or more of vinyl triacetoxysilane, vinyl tris (2-methoxyethoxy) silane, vinyl triisopropoxysilane, vinyl triethoxysilane, and vinyl trimethoxysilane; the methacryloxy silane coupling agent is one or more of gamma-methacryloxy propyl trimethoxy silane, gamma-methacryloxy propyl triisopropoxy silane, gamma-methacryloxy methyl dimethoxy silane and gamma-methacryloxy propyl triethoxy silane.
5. The method for preparing a long-acting antibacterial silicone rubber according to claim 3, characterized in that:
in step S2, the imidazolium salt is one or two of a vinylimidazolium salt and an allylimidazolium salt; the structure of the vinylimidazole salt or allylimidazole salt is shown as follows:
vinylimidazole salts:
allyl imidazole salt:
wherein R in the formula is any one of the following structures:
CH3、CH2CH3、CH2(CH2)2CH3、CH2(CH2)4CH3、CH2(CH2)6CH3；
X-is any one of the structures shown below:
Cl- Br- BF4 - NO3 - PF6 - CH3SO4 -。
6. the method for preparing a long-acting antibacterial silicone rubber according to claim 3, characterized in that:
in step S2, the poly-vinyl or allyl compound is one or more of N, N-methylene bisacrylamide, 1, 6-hexanediol diacrylate, pentaerythritol diacrylate, 1, 3-propanediol diacrylate, ethylene glycol dimethacrylate, and polyethylene glycol diacrylate;
preferably, the molecular weight of the polyethylene glycol segment in the polyethylene glycol diacrylate is 100-1000.
7. The method for preparing a long-acting antibacterial silicone rubber according to claim 3, characterized in that:
in step S2, the initiator is one or more of an azo-based radical initiator and a peroxide-based radical initiator;
preferably, the initiator is one or more of ammonium persulfate, potassium persulfate, hydrogen peroxide, azodiisobutyramidine hydrochloride and benzoyl peroxide.
8. The method for preparing a long-acting antibacterial silicone rubber according to claim 3, characterized in that:
in step S3, the certain initiation condition is ultraviolet irradiation initiation, gamma ray irradiation initiation, microwave initiation, or heating initiation; the conventional post-treatment comprises the steps of ultrasonic cleaning, drying, packaging and sterilization.
9. The method for preparing a long-acting antibacterial silicone rubber according to claim 3, characterized in that: before the step S1, the silicone rubber surface may be subjected to an activation treatment, such as activating the silicone rubber surface using a plasma modification technique or a surface hydrophilic modification technique, to improve the reaction efficiency of S1.
10. The method for preparing a long-acting antibacterial silicone rubber according to claim 9, characterized in that: the plasma modification technology comprises the following steps:
s10, placing the silicon rubber into plasma modification equipment, treating the surface of the silicon rubber for 10-60 minutes by adopting oxygen plasma or nitrogen plasma, taking out the silicon rubber and immediately carrying out the step S1;
the surface hydrophilic modification technology comprises the following steps:
s10, the silicone rubber is put into the mixed solution of sulfuric acid and hydrogen peroxide, soaked for 1-30 minutes, taken out, cleaned and dried, and then the step S1 is immediately carried out.
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