CN115975203A - Long-acting antibacterial agent, silicone rubber and preparation method thereof - Google Patents
Long-acting antibacterial agent, silicone rubber and preparation method thereof Download PDFInfo
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- CN115975203A CN115975203A CN202211595414.4A CN202211595414A CN115975203A CN 115975203 A CN115975203 A CN 115975203A CN 202211595414 A CN202211595414 A CN 202211595414A CN 115975203 A CN115975203 A CN 115975203A
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 97
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 74
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 52
- 239000003054 catalyst Substances 0.000 claims description 37
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 30
- 229910052697 platinum Inorganic materials 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 25
- 229920002545 silicone oil Polymers 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 19
- 239000012266 salt solution Substances 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- -1 acrylate quaternary ammonium salt Chemical class 0.000 claims description 11
- 238000007259 addition reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000004599 antimicrobial Substances 0.000 claims description 10
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 210000002445 nipple Anatomy 0.000 claims description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 190000008236 carboplatin Chemical compound 0.000 claims 1
- 229960004562 carboplatin Drugs 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 28
- 229940124350 antibacterial drug Drugs 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 229910021485 fumed silica Inorganic materials 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000010100 anticoagulation Effects 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- JADNEWQXDKBXRI-UHFFFAOYSA-M ethyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;bromide Chemical compound [Br-].CC[N+](C)(C)CCOC(=O)C=C JADNEWQXDKBXRI-UHFFFAOYSA-M 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The application belongs to the technical field of silicone rubber, and particularly relates to a long-acting antibacterial agent, silicone rubber and a preparation method thereof; the long-acting antibacterial agent provided by the application has excellent compatibility with silicone rubber, and the technical effect of slow release of antibacterial drugs is exerted in the silicone rubber, so that the antibacterial time of the silicone rubber is greatly prolonged, and the technical problem that the antibacterial time of the silicone rubber is short because the quaternary ammonium salt antibacterial agent is easily separated out from the silicone rubber in the prior art is solved.
Description
Technical Field
The application belongs to the technical field of silicone rubber, and particularly relates to a long-acting antibacterial agent, silicone rubber and a preparation method thereof.
Background
The silicon rubber is a high polymer material with excellent performances such as good electrical insulation, high temperature resistance, aging resistance, high transparency, good biocompatibility and anticoagulation performance; the industrial grade silicon rubber has good skin affinity, can be used for manufacturing various products which are contacted with the skin of a human body, such as watch watchbands, the food grade silicon rubber is widely applied to various products which can be contacted with food containers, such as hot-pressing pot gaskets, nipples and milk bottles, and the medicinal grade silicon rubber can also be used for human body implantation materials and medical products; in order to reduce microbial pollution, currently, food-grade silicone rubber usually needs to be added with an antibacterial agent to improve the antibacterial property of the silicone rubber.
The antibacterial agent added into the food-grade silicon rubber comprises a natural antibacterial agent, an inorganic antibacterial agent or an organic antibacterial agent, wherein the natural antibacterial agent has limited antibacterial effect and poor heat resistance and cannot be used in a broad-spectrum long-acting manner, the inorganic antibacterial agent mainly takes a silver antibacterial agent, silver (or ions thereof) is fixed on the surface of porous materials such as fluorite and silica gel through methods such as physical adsorption ion exchange and the like to prepare the antibacterial agent, and then the antibacterial agent is added into the silicon rubber to obtain antibacterial capability, however, after the silicon rubber containing the silver antibacterial agent is discarded, the risk of environment pollution caused by heavy metal due to silver ion precipitation exists; the organic antibacterial agent mainly comprises antibiotics and quaternary ammonium salt, for example, the quaternary ammonium salt is mixed into the silicone rubber to endow the silicone rubber with antibacterial performance, and the antibacterial agent can be released from the silicone rubber to exert antibacterial effect.
Disclosure of Invention
In view of the above, the application provides a long-acting antibacterial agent, silicone rubber and a preparation method thereof, which are used for solving the technical problem that in the prior art, a quaternary ammonium salt antibacterial agent is easy to precipitate from silicone rubber, so that the antibacterial time of silicone rubber is short.
In a first aspect, the present application provides a long-acting antimicrobial agent having a chemical structure according to formula I:
in the formula I, R 1 ，R 2 ，R 3 Is alkyl or phenyl or allyl;
n＝2-18；
x is a halogen atom;
a is
or-C-.
Preferably, the second aspect of the present application provides a method for preparing a long-acting antibacterial agent, comprising the steps of:
step S1, stirring hydrogen-containing silicone oil, a p-hydroxyanisole solvent and an organic solvent to obtain a to-be-added mixed solution;
s2, dropwise adding the unsaturated quaternary ammonium salt solution containing the platinum catalyst into the mixed solution to be added for addition reaction to obtain the long-acting antibacterial agent;
in the step S2, the temperature of the addition reaction is 50-90 ℃ and the time is 0.5-4 h.
Preferably, the preparation method of the unsaturated quaternary ammonium salt solution containing the platinum catalyst comprises the following steps:
and step S2.1, stirring the unsaturated quaternary ammonium salt and the platinum catalyst solution at the temperature of between 30 and 60 ℃ for 20 to 60 minutes to obtain the unsaturated quaternary ammonium salt solution containing the platinum catalyst.
Preferably, in step S1, the hydrogen-containing silicone oil has a hydrogen mass fraction of 0.01 to 1.6% and a viscosity of 30 to 600mPa · S.
Preferably, in step S1, the organic solvent includes isopropyl alcohol and/or ethanol.
Preferably, in step S2, the platinum catalyst solution includes an isopropyl alcohol and/or ethanol solution of chloroplatinic acid, and an isopropyl alcohol and/or ethanol solution of platinum katsut.
Preferably, in step S2, the unsaturated quaternary ammonium salt includes one or more of acrylate quaternary ammonium salt, acrylamide quaternary ammonium salt, allyl quaternary ammonium salt, and styrene quaternary ammonium salt.
Preferably, the third aspect of the present application provides a silicone rubber, the composition of which comprises a silicone rubber and the long-acting antibacterial agent.
Preferably, the silicone rubber comprises any one of a silicone rubber nipple, a silicone rubber feeding bottle and a silicone rubber hot-pressing pot gasket.
The fourth aspect of the present application provides a method for preparing silicone rubber, comprising the steps of:
s3, stirring the long-acting antibacterial agent, the silicone oil, the hexamethyldisilazane and the ethynyl cyclohexanol to obtain a silicone rubber solution to be added;
s4, dropwise adding a platinum catalyst solution into the silicone rubber solution to be added to perform silicone rubber addition reaction to obtain silicone rubber;
in the step S4, the temperature of the silicone rubber addition reaction is 110-150 ℃ and the time is 1-45 h.
Preferably, in step S4, the platinum catalyst solution is a kast catalyst;
the concentration of the Kaster catalyst is 2000-5000 ppm.
Preferably, after the step S4, a step of processing and molding the raw silicone rubber by using an open mill or an internal mixer is further included.
In summary, the application provides a long-acting antibacterial agent, silicone rubber and a preparation method thereof, wherein the chemical structural formula of the long-acting antibacterial agent is shown as formula I, the chemical structure of the long-acting antibacterial agent is polysiloxane grafted with quaternary ammonium groups on side chains, after the long-acting antibacterial agent, the silicone oil and a catalyst are subjected to addition preparation to obtain the silicone rubber, the long-acting antibacterial agent has excellent compatibility with the silicone rubber, and the silicone rubber can maintain more than 90% of antibacterial activity after being soaked in water for 24 hours.
Drawings
In order to more clearly illustrate the detailed description of the present application or the technical solutions in the prior art, the drawings needed to be used in the detailed description of the present application or the prior art description will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an infrared spectrum of a long-acting antimicrobial agent as provided in example 2 of the present application;
FIG. 2 is an infrared spectrum of a long-acting antimicrobial agent as provided in example 3 of the present application;
FIG. 3 is an infrared spectrum of a long-acting antimicrobial agent as provided in example 4 of the present application;
FIG. 4 is a schematic chemical structure diagram of a long-acting antimicrobial agent provided in an embodiment of the present application;
FIG. 5 is a schematic representation of a reaction scheme for the preparation of a long-acting antimicrobial agent as provided in example 2 of the present application;
FIG. 6 is a schematic representation of a reaction scheme for the preparation of a long-acting antimicrobial agent as provided in example 3 of the present application;
FIG. 7 is a schematic representation of a reaction scheme for the preparation of a long-acting antimicrobial agent as provided in example 4 herein;
in FIG. 4, R 1 ，R 2 ，R 3 Is alkyl or phenyl or allyl;
n＝2-18；
x is a halogen atom;
a is
or-C-.
Detailed Description
The application provides a long-acting antibacterial agent, silicone rubber and a preparation method thereof, which are used for solving the technical problem that in the prior art, a quaternary ammonium salt antibacterial agent is easy to separate out from silicone rubber, so that the antibacterial time of the silicone rubber is short.
The technical solutions of the present application will be described clearly and completely with reference to the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application.
Example 1
This application is trueThe examples provide a long-acting antibacterial agent having a chemical structure as shown in FIG. 4, wherein R in FIG. 4 1 ，R 2 ，R 3 Is alkyl or phenyl or allyl;
n＝2-18；
x is a halogen atom;
a is
or-C-.
The chemical structure of the long-acting antibacterial agent is polysiloxane with a side chain grafted with a quaternary ammonium group, after the long-acting antibacterial agent, silicone oil and a catalyst are added to prepare silicone rubber, the long-acting antibacterial agent has excellent compatibility with the silicone rubber, and the silicone rubber can maintain more than 90% of antibacterial activity after being soaked in water for 24 hours.
Example 2
The embodiment of the application provides a preparation method of a long-acting antibacterial agent, which comprises the steps of preparing an unsaturated quaternary ammonium salt solution containing a platinum catalyst, preparing a mixed solution to be added and preparing the long-acting antibacterial agent.
Wherein the step of preparing the unsaturated quaternary ammonium salt solution containing the platinum catalyst comprises the steps of stirring and mixing uniformly a solution of 20g of acryloyloxyethyl dimethyl ethyl ammonium bromide, 0.02g of chloroplatinic acid and 50mL of isopropanol, and preheating for 20-60 minutes at 30-60 ℃ to obtain the unsaturated quaternary ammonium salt solution containing the platinum catalyst;
the step of preparing the mixed solution to be added comprises the steps of adding 15.03g of hydrogen-containing silicone oil with the hydrogen mass fraction of 1.0% and the viscosity of 300 mPa.s, 80mL of isopropanol and 0.1g of p-hydroxyanisole into a reactor under the protection of nitrogen, heating while stirring, and preheating the mixed solution to be added in the reactor until the temperature of the mixed solution reaches 70 ℃;
and (3) preparing the long-acting antibacterial agent, namely dropwise adding the unsaturated quaternary ammonium salt solution containing the platinum catalyst into the mixed solution to be added, reacting for 2h at 70 ℃ after dropwise adding is finished, and cooling to room temperature to prepare the long-acting antibacterial agent.
The step of preparing the long-acting antibacterial agent further comprises adsorbing the long-acting antibacterial agent for 1 hour by using 5g of activated carbon after the long-acting antibacterial agent is cooled to room temperature. Filtering the reaction solution, and evaporating under reduced pressure to remove small molecules to obtain the antibacterial agent.
Example 3
The embodiment of the application provides a preparation method of a long-acting antibacterial agent, which comprises the steps of preparing an unsaturated quaternary ammonium salt solution containing a platinum catalyst, preparing a mixed solution to be added and preparing the long-acting antibacterial agent.
Wherein the step of preparing the unsaturated quaternary ammonium salt solution containing the platinum catalyst comprises the steps of stirring and mixing 20g of acrylamido propyl dimethyl butyl ammonium bromide, 0.02g of chloroplatinic acid and 50mL of isopropanol uniformly, and preheating for 20-60 minutes at 30-60 ℃ to obtain the unsaturated quaternary ammonium salt solution containing the platinum catalyst;
the step of preparing the mixed solution to be added comprises the steps of adding 18.75g of hydrogen-containing silicone oil with the hydrogen mass fraction of 1.0 percent and the viscosity of 300 mPa.s, 100mL of isopropanol and 0.1g of p-hydroxyanisole into a reactor under the protection of nitrogen, heating while stirring, and preheating the mixed solution to be added in the reactor until the temperature of the mixed solution reaches 70 ℃;
and (3) preparing the long-acting antibacterial agent, namely dropwise adding the unsaturated quaternary ammonium salt solution containing the platinum catalyst into the mixed solution to be added, reacting for 2 hours at 90 ℃ after dropwise adding is finished, and cooling to room temperature to prepare the long-acting antibacterial agent.
The step of preparing the long-acting antibacterial agent also comprises adsorbing the long-acting antibacterial agent for 1 hour by using 4.5g of activated carbon after the long-acting antibacterial agent is cooled to room temperature. Filtering the reaction solution, and evaporating under reduced pressure to remove small molecules to obtain the antibacterial agent.
Example 4
The embodiment of the application provides a preparation method of a long-acting antibacterial agent, which comprises the steps of preparing an unsaturated quaternary ammonium salt solution containing a platinum catalyst, preparing a mixed solution to be added and preparing the long-acting antibacterial agent.
Wherein the step of preparing the unsaturated quaternary ammonium salt solution containing the platinum catalyst comprises the steps of stirring and uniformly mixing 10g of dimethyl diallyl ammonium chloride, 0.02g of chloroplatinic acid and 50mL of isopropanol solution, and preheating for 20-60 minutes at 30-60 ℃ to obtain the unsaturated quaternary ammonium salt solution containing the platinum catalyst;
the step of preparing the mixed solution to be added comprises the steps of adding 12.41g of hydrogen-containing silicone oil with the hydrogen mass fraction of 1.0% and the viscosity of 300 mPa.s, 80mL of isopropanol and 0.1g of p-hydroxyanisole into a reactor, heating while stirring, and preheating the mixed solution to be added in the reactor until the temperature of the mixed solution to be added reaches 70 ℃;
and (3) preparing the long-acting antibacterial agent, namely dropwise adding the unsaturated quaternary ammonium salt solution containing the platinum catalyst into the mixed solution to be added, reacting for 2 hours at 80 ℃ after dropwise adding is finished, and cooling to room temperature to prepare the long-acting antibacterial agent.
The step of preparing the long-acting antibacterial agent further comprises adsorbing the long-acting antibacterial agent for 1 hour by using 3g of activated carbon after the long-acting antibacterial agent is cooled to room temperature. Filtering the reaction solution, and evaporating under reduced pressure to remove small molecules to obtain the antibacterial agent.
Example 5
The embodiment of the application provides silicon rubber, and the long-acting antibacterial agent prepared in the embodiment 2 is subjected to addition reaction with silicon oil and a catalyst to prepare the silicon rubber.
The preparation method of the silicone rubber comprises the steps of adding 700 parts of 2000cp vinyl silicone oil, 240 parts of 200-specific-surface-area fumed silica, 50 parts of hexamethyldisilazane, 40 parts of 0.5-percent hydrogen-containing silicone oil, 0.3 part of ethynylcyclohexanol and 5 parts of antibacterial agent into a kneader, kneading uniformly at room temperature, adding 1 part of 3000ppm Karster catalyst, stirring uniformly, putting the mixture into a vacuum drying oven at room temperature, fully discharging bubbles, and finally curing at 130 ℃ for 1 hour to form and mold at the temperature of 130 DEG C
Example 6
The embodiment of the application provides silicone rubber, and the long-acting antibacterial agent prepared in the embodiment 3 is subjected to addition reaction with silicone oil and a catalyst to prepare the silicone rubber.
The preparation method of the silicone rubber comprises the steps of adding 720 parts of 2000cp vinyl silicone oil, 250 parts of 200-specific-surface-area fumed silica, 50 parts of hexamethyldisilazane, 30 parts of 0.5-percent hydrogen-containing silicone oil, 0.1 part of ethynylcyclohexanol and 5 parts of antibacterial agent into a kneader, kneading uniformly at room temperature, adding 1 part of 3000ppm Karster catalyst, stirring uniformly, putting the mixture into a vacuum drying oven at room temperature, fully discharging bubbles, and finally curing at 130 ℃ for 1 hour for molding.
Example 7
The embodiment of the application provides silicone rubber, and the long-acting antibacterial agent prepared in the embodiment 4 is subjected to addition reaction with silicone oil and a catalyst to prepare the silicone rubber.
The preparation method of the silicone rubber comprises the steps of adding 740 parts of 2000cp vinyl silicone oil, 260 parts of 200-specific-surface-area fumed silica, 51 parts of hexamethyldisilazane, 32 parts of 0.5-percent hydrogen-containing silicone oil, 0.12 part of ethynylcyclohexanol and 5 parts of antibacterial agent into a kneader, kneading uniformly at room temperature, adding 1.2 parts of 3000ppm Karster catalyst, stirring uniformly, putting the mixture into a vacuum drying oven at room temperature, fully discharging bubbles, and finally curing at 130 ℃ for 1 hour for molding.
In the embodiment 5-7 of the application, after the step of curing for 1 hour at 130 ℃ to obtain the silicon rubber, the method further comprises the step of further processing and molding the silicon rubber to prepare various food-grade silicon rubber products such as silicon rubber nipples, silicon rubber feeding bottles, silicon rubber hot-pressing pot gaskets and the like.
Comparative example 1
The preparation method comprises the steps of adding 720 parts of 2000cp vinyl silicone oil, 250 parts of 200-specific-surface-area fumed silica, 50 parts of hexamethyldisilazane, 30 parts of 0.5% hydrogen-containing silicone oil and 0.1 part of ethynyl cyclohexanol into a kneader, kneading uniformly at room temperature, adding 1 part of 3000ppm Kaster catalyst, stirring uniformly, putting the mixture into a vacuum drying oven at room temperature, fully discharging bubbles, and finally curing for 2 hours at 130 ℃ for molding.
Comparative example 2
The preparation method comprises the steps of adding 730 parts of 2000cp vinyl silicone oil, 250 parts of 200-specific-surface-area fumed silica, 50 parts of hexamethyldisilazane, 30 parts of 0.5% hydrogen-containing silicone oil, 0.11 part of ethynyl cyclohexanol and 5 parts of antibacterial agent into a kneader, kneading uniformly at room temperature, adding 1 part of 3000ppm Kaster catalyst, stirring uniformly, putting the mixture into a vacuum drying oven at room temperature, fully discharging bubbles, and finally curing for 2 hours at 130 ℃ for molding.
Test example 1
This test example was used to test the long-lasting antibacterial performance of the silicone rubbers provided in examples 5 to 7 and the antibacterial performance of the silicone rubbers provided in comparative examples 1 to 2, the antibacterial performance being in accordance with JIS _ Z _2801:2010 antibacterial processed product-antibacterial test method, the antibacterial effect standard was performed, and the antibacterial performance test results are shown in table 1.
TABLE 1
As can be seen from table 1, the silicone rubber provided in comparative example 1 has no antibacterial effect at all, the antibacterial effect is greatly reduced when the silicone rubber provided in comparative example 2 is soaked in water for 24 hours, whereas the silicone rubbers provided in examples 5 to 7 have antibacterial effects, and after the silicone rubbers provided in examples 5 to 7 are soaked in water for 24 hours, the silicone rubbers are further soaked in water according to JIS _ Z _2801:2010, the antibacterial processed product-antibacterial test method, the antibacterial performance test is carried out according to the antibacterial effect standard, and compared with the antibacterial activity before soaking, the antibacterial activity is kept by more than 90%, which shows that the long-acting antibacterial agent in the silicone rubber provided by the application has good compatibility with the silicone rubber and exerts the technical effect of antibacterial drug slow release, so that the antibacterial time of the silicone rubber is greatly prolonged, and the technical problem that the antibacterial time of the silicone rubber is short because the quaternary ammonium salt antibacterial agent is easily separated out from the silicone rubber in the prior art is solved.
Meanwhile, the silicone rubber containing the long-acting antibacterial agent provided by the embodiment of the application has long-acting antibacterial property, and can inhibit the propagation and growth of germs in silicone rubber products and improve the use safety of food-grade silicone rubber products after being used for preparing food-grade silicone rubber products such as silicone rubber nipples, silicone rubber feeding bottles, silicone rubber hot-press pot gaskets and the like.
The above embodiments are only used to illustrate the technical solutions of the present application, and not to limit the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the scope of the technical solutions of the embodiments of the present application.
Claims (10)
1. A long-acting antimicrobial agent having the chemical structure according to formula I:
in the formula I, R 1 ，R 2 ，R 3 Is alkyl or phenyl or allyl;
n＝2-18；
x is a halogen atom;
a is
or-C-.
2. A method of preparing a long-acting antimicrobial agent as claimed in claim 1, comprising the steps of:
step S1, stirring hydrogen-containing silicone oil, a p-hydroxyanisole solvent and an organic solvent to obtain a to-be-added mixed solution;
s2, dropwise adding the unsaturated quaternary ammonium salt solution containing the platinum catalyst into the mixed solution to be added for addition reaction to obtain the long-acting antibacterial agent;
in the step S2, the temperature of the addition reaction is 50-90 ℃ and the time is 0.5-4 h.
3. The method according to claim 2, wherein the step 2, the method for preparing the unsaturated quaternary ammonium salt solution containing the platinum catalyst comprises:
and step S2.1, stirring the unsaturated quaternary ammonium salt and the platinum catalyst solution at the temperature of between 30 and 60 ℃ for 20 to 60 minutes to obtain the unsaturated quaternary ammonium salt solution containing the platinum catalyst.
4. The method according to claim 2, wherein in step S1, the hydrogen-containing silicone oil has a hydrogen mass fraction of 0.01 to 1.6% and a viscosity of 30 to 600 mPas.
5. The method according to claim 2, wherein the unsaturated quaternary ammonium salt in step S2 comprises one or more of acrylate quaternary ammonium salt, acrylamide quaternary ammonium salt, allyl quaternary ammonium salt, and styrene quaternary ammonium salt.
6. The method according to claim 2, wherein the organic solvent comprises isopropyl alcohol and/or ethanol.
7. The production method according to claim 2, wherein in step S2, the platinum catalyst solution includes an isopropyl alcohol and/or ethanol solution of chloroplatinic acid, and an isopropyl alcohol and/or ethanol solution of carboplatin.
8. The silicon rubber is characterized in that the components of the silicon rubber comprise silicon rubber and the long-acting antibacterial agent.
9. The silicone rubber according to claim 8, wherein the silicone rubber comprises any one of a silicone rubber nipple, a silicone rubber feeding bottle, and a silicone rubber autoclave gasket.
10. The method for preparing silicone rubber according to claim 8, wherein step S3, the long-acting antibacterial agent, silicone oil, hexamethyldisilazane, and ethynylcyclohexanol are stirred to obtain a silicone rubber solution to be added;
s4, dropwise adding a platinum catalyst solution into the to-be-added silicone rubber solution to perform silicone rubber addition reaction to obtain silicone rubber;
in the step S4, the temperature of the silicone rubber addition reaction is 110-150 ℃ and the time is 1-45 h.
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