CN115491036A - Antibacterial and anti-allergic liquid silica gel and preparation method thereof - Google Patents
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Abstract
The application relates to an antibacterial and antiallergic liquid silica gel and a preparation method thereof, wherein the antibacterial and antiallergic liquid silica gel comprises, by mass, 100 to 120 parts of hydroxyl-terminated polysiloxane, 20 to 30 parts of histidine, 15 to 25 parts of silver nitrate, 20 to 30 parts of amino-containing silane coupling agent, 15 to 25 parts of cinnamaldehyde, 10 to 15 parts of ethyl orthosilicate and 3 to 5 parts of vulcanizing agent. Histidine and silver ions are introduced through the terminal hydroxyl of polysiloxane, and then cinnamaldehyde is introduced through the silane coupling agent, so that the introduction of two-component antibacterial agents can be realized, the antibacterial property of the liquid silica gel can be improved under the synergistic effect of the two antibacterial agents, and the drug resistance of a strain is reduced. Further introduce gaseous phase nanometer titanium dioxide in this application not only can assist reinforcing antibacterial effect, can improve the ageing resistance of silica gel moreover, prolong liquid silica gel's life.
Description
Technical Field
The application relates to the technical field of liquid silica gel preparation, in particular to antibacterial and anti-allergy liquid silica gel and a preparation method thereof.
Background
Compared with solid high-temperature vulcanized silicone rubber, the liquid silicone rubber is liquid rubber and has the characteristics of good fluidity and high vulcanization speed. Moreover, the liquid silica gel is safer and more environment-friendly, and can completely meet the requirements of food and medical grade; therefore, the method has wide application in the fields of food and medicine.
The liquid silica gel has excellent transparency, tear strength, rebound resilience, yellowing resistance, heat stability, water resistance, good air permeability, heat aging resistance and weather resistance, moderate viscosity, convenient operation and high product transparency, can see whether the casting material in the mold has the defects of air bubbles and the like, has the linear shrinkage rate of less than or equal to 0.1 percent, and can reproduce the product with precise size.
The liquid silica gel has no antibacterial function, and pathogenic microorganisms such as bacteria and the like can breed when the liquid silica gel is used, so that an antibacterial agent is usually added in the preparation process of the liquid silica gel to obtain the liquid silica gel with certain antibacterial performance.
Silver is often added into liquid silica gel as an antibacterial agent because of its excellent bactericidal ability and broad-spectrum antibacterial property; however, with the existing drug resistance and resistance of many bacteria, a single antibacterial agent has a common antibacterial effect, and the affinity of silver ions and silica gel is not high, so that the silver ions are directly added into the silica gel, the dispersibility is not uniform, and the overall antibacterial property is reduced.
Disclosure of Invention
In order to further improve the antibacterial property of the liquid silica gel, the application provides the antibacterial and anti-allergy liquid silica gel and the preparation method thereof.
In a first aspect, the application provides an antibacterial and antiallergic liquid silica gel, which adopts the following technical scheme:
the antibacterial and antiallergic liquid silica gel comprises, by mass, 100-120 parts of hydroxyl-terminated polysiloxane, 20-30 parts of histidine, 15-25 parts of silver nitrate, 20-30 parts of an amino-containing silane coupling agent, 15-25 parts of cinnamaldehyde, 10-15 parts of tetraethoxysilane and 3-5 parts of a vulcanizing agent.
Preferably, the antibacterial and antiallergic liquid silica gel comprises, by mass, 110-112 parts of hydroxyl-terminated polysiloxane, 24-26 parts of histidine, 18-20 parts of silver nitrate, 24-26 parts of amino-containing silane coupling agent, 18-22 parts of cinnamaldehyde, 12-14 parts of ethyl orthosilicate and 3-5 parts of vulcanizing agent.
By adopting the technical scheme, the terminal hydroxyl of the hydroxyl-terminated polysiloxane and the carboxyl of the histidine can be subjected to esterification reaction so as to graft the histidine onto the polysiloxane, and the histidine can complex silver ions, so that the silver ions can be uniformly dispersed in the liquid silica gel; the introduction of histidine can improve the biocompatibility of the liquid silica gel and reduce the generation of anaphylactic reaction. The amino-containing silane coupling agent can react with aldehyde groups on cinnamaldehyde, and the silane coupling agent and silicate ester can be further subjected to cross-linking polymerization with polysiloxane in the vulcanization process, so that cinnamaldehyde antibacterial groups are introduced into liquid silica gel. Therefore, the liquid silica gel contains the silver ion antibacterial agent and the cinnamaldehyde antibacterial group, and the combination of the two antibacterial agents can realize a synergistic effect and increase the antibacterial property of the liquid silica gel.
Preferably, the antibacterial and antiallergic liquid silica gel further comprises: 5-8 parts of gas-phase nano titanium dioxide.
By adopting the technical scheme, the gas phase nano titanium dioxide as an inorganic antibacterial agent has the advantages of excellent broad-spectrum antibacterial property, no drug resistance, good heat resistance and lasting antibacterial property, and free radicals on the surface of the gas phase nano titanium dioxide have high reactivity and can destroy bonds such as C-C, C-H, C-N, C-O, O-H, N-H and the like in bacteria, so that most organic pollutants and part of inorganic pollutants can be oxidized and finally degraded into harmless substances such as carbon dioxide, water and the like, thereby achieving the bactericidal effect. And the nano titanium dioxide has good anti-aging effect and can prolong the service life of the liquid silica gel.
Further preferably, the gas phase nano titanium dioxide is a mixed crystal type gas phase nano titanium dioxide P25.
By adopting the technical scheme, two structures of anatase nano titanium dioxide and rutile nano titanium dioxide in the mixed crystal type gas phase nano titanium dioxide P25 are mixed, so that the defect density in titanium dioxide crystal lattices is increased, the capturing capability of the gas phase nano titanium dioxide on bacteria is improved, the sterilization effect, the weather resistance and the ageing resistance of the gas phase nano titanium dioxide are improved, and the antibacterial property and the antibacterial durability of the liquid silica gel are improved.
Preferably, the silane coupling agent containing amino is one of 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane; the silicate is one of methyl orthosilicate, ethyl orthosilicate and isopropyl orthosilicate; the vulcanizing agent is one of dibenzoyl peroxide and 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane.
By adopting the technical scheme, the grafting effect of the cinnamaldehyde can be improved by controlling the type of the silane coupling agent through a better aldehyde group reaction; the silane coupling agent and the polysiloxane can be combined together by means of a vulcanizing agent and a silicate to form a liquid silica gel.
In a second aspect, the application provides a preparation method of an antibacterial and antiallergic liquid silica gel, which comprises the following steps:
s1: mixing hydroxyl-terminated polysiloxane with histidine, adding a sodium hydroxide solution to adjust the pH = 10-12, heating to react, and after the reaction is finished, separating out a water phase to obtain polysiloxane grafted with histidine; adding silver nitrate into polysiloxane grafted with histidine, heating for a complexing reaction, and obtaining Ag-histidine-polysiloxane after the reaction is finished;
s2: mixing an amino-containing silane coupling agent, cinnamaldehyde and methanol, adding an alkali to adjust the pH of a solution to 10-12, reacting at normal temperature, and after the reaction is finished, heating and evaporating to recover a methanol solvent to obtain silane coupling agent modified cinnamaldehyde;
s3: and (2) stirring and mixing the Ag-histidine-polysiloxane, the silane coupling agent modified cinnamaldehyde and other components in the step (S1) to obtain a mixture, and pouring the mixture into a mold to sequentially perform vulcanization treatment, cooling treatment and demoulding treatment to obtain the antibacterial and antiallergic liquid silica gel.
According to the technical scheme, in the preparation method, firstly, hydroxyl on hydroxyl-terminated polysiloxane and carboxyl on histidine are subjected to esterification reaction to be grafted on polysiloxane, and then, silver ions are uniformly loaded in a polysiloxane structure through the complexation of histidine on the silver ions. According to the preparation method, amino groups on the amino-containing silane coupling agent react with aldehyde groups on cinnamaldehyde, so that cinnamaldehyde groups are grafted to the silane coupling agent, and finally the silane coupling agent and polysiloxane are combined together under the vulcanization action through silicate ester to form liquid silica gel.
Preferably, in the step S1, the heating temperature is 60-80 ℃, the reaction time is 4-6 h, and the concentration of ammonium hydroxide is 1-2 mol/L.
By adopting the technical scheme, histidine can better react with hydroxyl-terminated polysiloxane by controlling the reaction temperature and the reaction time, so that the biocompatibility of the liquid silica gel is better improved.
Preferably, in the step S2, the volume ratio of the amino-containing silane coupling agent to the formaldehyde is 1 (1-2), and the reaction time is 2-4 h.
By adopting the technical scheme, the silane coupling agent with better cinnamaldehyde can be reacted by controlling the volume and the reaction time of the methanol.
Preferably, in the step S3, the vulcanization temperature is 60-80 ℃ and the vulcanization time is 2-4 h.
By adopting the technical scheme, the mixed components can fully react by controlling the vulcanization temperature and the vulcanization time, so that the liquid silica gel with stable performance is formed.
In summary, the present application includes at least one of the following beneficial technical effects:
1. histidine and silver ions are introduced through the terminal hydroxyl of polysiloxane, and then cinnamaldehyde is introduced through the silane coupling agent, so that the introduction of two-component antibacterial agents can be realized, the antibacterial property of the liquid silica gel can be improved under the synergistic effect of the two antibacterial agents, and the drug resistance of a strain is reduced.
2. Further introduce gaseous phase nanometer titanium dioxide in this application not only can assist reinforcing antibacterial effect, can improve the ageing resistance of silica gel moreover, prolong liquid silica gel's life.
3. In the preparation method, the polysiloxane terminal hydroxyl and the carboxyl of histidine are subjected to esterification reaction so as to be introduced into the structure of polysiloxane, and then silver ions are complexed by the histidine, so that the dispersion uniformity of the silver ions can be improved; introducing a cinnamaldehyde antibacterial group through the action of amino on a silane coupling agent and aldehyde group of cinnamaldehyde; finally, a vulcanizing agent and silicate ester are used for enabling the polysilane and the silane coupling agent to generate a chain growth reaction to form the liquid silica gel. The method has the advantages of simple reaction process, temperature conditioning and easy realization of industrialized production.
Detailed Description
Example 1
110g of hydroxyl-terminated polysiloxane, 24g of histidine, 20g of silver nitrate, 25g of 3-aminopropyltriethoxysilane, 20g of cinnamaldehyde, 12g of ethyl orthosilicate and 4g of dibenzoyl peroxide.
The preparation method comprises the following steps:
s1: mixing hydroxyl-terminated polysiloxane and histidine, adding 1.0mol/L sodium hydroxide solution to adjust the pH to be 10-11, heating to 70 ℃ to react for 5 hours, and after the reaction is finished, separating out a water phase to obtain polysiloxane grafted with histidine; adding silver nitrate into polysiloxane grafted with histidine, heating to 70 ℃ for complexation reaction for 3h, and obtaining Ag-histidine-polysiloxane after the reaction is finished.
S2: mixing 3-aminopropyltriethoxysilane, cinnamaldehyde and 39mL of methanol, adding 1.0mol/L of strong sodium oxide to adjust the pH of the solution to 10-11, reacting for 3 hours at normal temperature, and after the reaction is finished, heating and evaporating to recover the methanol solvent to obtain the silane coupling agent modified cinnamaldehyde.
S3: stirring and mixing the Ag-histidine-polysiloxane, silane coupling agent modified cinnamaldehyde, ethyl orthosilicate and dibenzoyl peroxide in the step S1 to obtain a mixture, pouring the mixture into a mold, placing the mold on a vulcanizing machine, vulcanizing at 70 ℃ for 3 hours, and after vulcanization, cooling and demoulding to obtain the antibacterial and antiallergic liquid silica gel.
Comparative example 1
In substantial agreement with example 1, with the difference that silver nitrate was added directly without introducing histidine, i.e. without carrying out step S1, silver nitrate was added directly in step S3.
Comparative example 2
In substantial agreement with example 1, with the difference that silver nitrate was added directly in step S3 without addition of silver nitrate, step S1.
Comparative example 3
In substantial agreement with example 1, with the difference that no cinnamaldehyde was introduced, step S2 was eliminated in the process.
Testing the antibacterial property of the prepared liquid silica gel, wherein the testing method adopts a filter paper method, and the strain adopts escherichia coli and staphylococcus aureus; the testing steps are as follows:
cutting the liquid silica gel into a circular sheet with the diameter of 6mm and the thickness of 0.2mm by a puncher.
Respectively activating the two strains, and culturing to about 5 × 10 8 Cfu/mL to respectively obtain corresponding strain culture solutions; preparing a solid culture medium solution, pouring the solid culture medium solution into a flat plate, after solidification, sucking 50uL of strain culture solution, placing the strain culture solution on the solid culture medium, after a coating rod is uniformly coated, placing a liquid silica gel wafer in the center of the flat plate, then respectively culturing for 24h and 15 days, testing the diameter of a bacteriostatic circle, testing each sample for 3 times, and calculating an average value; and a blank filter paper sheet was used as a blank control. The results are shown in Table 1.
Example 1 compared with comparative examples 2 and 3, no silver ion was added in comparative example 2, no cinnamaldehyde was added in comparative example 3, and the antibacterial performance in comparative examples 2 and 3 was significantly reduced, indicating that silver ion and cinnamaldehyde can act synergistically to improve the antibacterial performance of liquid silica gel.
From the comparison of the antibacterial performance after 15 days in example 1 and comparative examples 1 to 3, the antibacterial performance after 15 days in comparative examples 1 to 3 is relatively more remarkably reduced, probably because the two antibacterial agents have better synergistic antibacterial effects and can realize longer antibacterial performance.
Example 2
100g of hydroxyl-terminated polysiloxane, 20g of histidine, 15g of silver nitrate, 30g of 3-aminopropyltrimethoxysilane, 25g of cinnamaldehyde, 15g of methyl orthosilicate and 5g of dibenzoyl peroxide.
The preparation method comprises the following steps:
s1: mixing hydroxyl-terminated polysiloxane with histidine, adding 1.0mol/L sodium hydroxide solution to adjust the pH value to be 11-12, heating to 60 ℃ to react for 6 hours, and after the reaction is finished, separating out a water phase to obtain polysiloxane grafted with histidine; adding silver nitrate into polysiloxane grafted with histidine, heating to 80 ℃ for complexation reaction for 2h,
after the reaction is finished, ag-histidine-polysiloxane is obtained;
s2: mixing 3-aminopropyltrimethoxysilane and 30mL of methanol of cinnamaldehyde, adding 1.0mol/L of strong sodium oxide to adjust the pH value of the solution to 10-11, reacting for 2h at normal temperature, and after the reaction is finished, heating and evaporating to recover the methanol solvent to obtain silane coupling agent modified cinnamaldehyde;
s3: stirring and mixing the Ag-histidine-polysiloxane, silane coupling agent modified cinnamaldehyde, methyl orthosilicate and dibenzoyl peroxide in the step S1 to obtain a mixture, pouring the mixture into a mold, placing the mold on a vulcanizing machine, vulcanizing at 60 ℃ for 4 hours, and after vulcanizing, cooling and demoulding to obtain the antibacterial and antiallergic liquid silica gel.
Example 3
120g of hydroxyl-terminated polysiloxane, 28g of histidine, 23g of silver nitrate, 22g of N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, 18g of cinnamaldehyde, 14g of isopropyl n-silicate, and 4g of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane.
The preparation method comprises the following steps:
s1: mixing hydroxyl-terminated polysiloxane with histidine, adding 1.0mol/L sodium hydroxide solution to adjust the pH value to be 11-12, heating to 80 ℃ to react for 4 hours, and after the reaction is finished, separating out a water phase to obtain polysiloxane grafted with histidine; adding silver nitrate into polysiloxane grafted with histidine, heating to 60 deg.C for complexation reaction for 4h,
after the reaction is finished, ag-histidine-polysiloxane is obtained;
s2: mixing N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, cinnamaldehyde and 42mL of methanol, adding 1.0mol/L of strong sodium oxide to adjust the pH of the solution to 10-11, reacting for 3h at normal temperature, and after the reaction is finished, heating and evaporating to recover the methanol solvent to obtain silane coupling agent modified cinnamaldehyde;
s3: stirring and mixing the Ag-histidine-polysiloxane, silane coupling agent modified cinnamaldehyde, methyl orthosilicate and 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane in the step S1 to obtain a mixture, pouring the mixture into a mold, placing the mold on a vulcanizing machine, vulcanizing at 80 ℃ for 2 hours, and after the vulcanization is finished, cooling and demoulding to obtain the antibacterial and antiallergic liquid silica gel.
Example 4
112g of hydroxyl polysiloxane, 26g of histidine, 19g of silver nitrate, 26g of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 22g of cinnamaldehyde, 13g of isopropyl n-silicate and 4g of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane.
The preparation method comprises the following steps:
s1: mixing hydroxyl-terminated polysiloxane and histidine, adding 1.0mol/L sodium hydroxide solution to adjust the pH to be 11-12, heating to 70 ℃ to react for 4 hours, and after the reaction is finished, separating out a water phase to obtain polysiloxane grafted with histidine; adding silver nitrate into polysiloxane grafted with histidine, heating to 70 ℃ for complexation reaction for 3h,
after the reaction is finished, ag-histidine-polysiloxane is obtained;
s2: mixing N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, cinnamaldehyde and 38mL of methanol, adding 1.0mol/L of strong sodium oxide to adjust the pH of the solution to 10-11, reacting for 3h at normal temperature, and after the reaction is finished, heating and evaporating to recover the methanol solvent to obtain silane coupling agent modified cinnamaldehyde;
s3: stirring and mixing the Ag-histidine-polysiloxane, silane coupling agent modified cinnamaldehyde, methyl orthosilicate and 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane obtained in the step S1 to obtain a mixture, pouring the mixture into a mold, placing the mold on a vulcanizing machine, vulcanizing at 70 ℃ for 3 hours, and after vulcanization, cooling and demoulding to obtain the antibacterial and antiallergic liquid silica gel.
The liquid silica gels prepared in examples 2 to 4 were subjected to an antibacterial property test, and the results thereof are shown in table 2.
As can be seen from the data in Table 2, with the change of the component ratio and the change of the preparation process parameters, the appearance of the prepared liquid silica gel has no obvious change, the antibacterial performance of the liquid silica gel has certain fluctuation, but the whole antibacterial performance is better. It can also be seen from the data in table 2 that the antibacterial property of the antibacterial liquid silica gel in the present application is not significantly reduced with the increase of the antibacterial time, which indicates that the liquid silica gel in the present application has long-lasting antibacterial performance.
Example 5
The method is basically consistent with the embodiment 1, and is characterized in that 5g of vapor-phase nano titanium dioxide P25 is added on the basis of the embodiment 1.
Example 6
The difference from the example 2 is that 6g of vapor phase nano titanium dioxide P25 is added on the basis of the example 1.
Example 7
The method is basically consistent with the method in example 3, and is characterized in that 8g of vapor-phase nano titanium dioxide P25 is added on the basis of the method in example 1.
The liquid silica gels prepared in examples 5 to 7 were subjected to antibacterial property tests, and the results are shown in Table 3.
As can be seen from the data in table 3, the antibacterial performance of example 5 is slightly improved compared with that of example 1, the antibacterial performance of example 6 is also slightly improved compared with that of example 2, and the antibacterial performance of example 7 is obviously improved compared with that of example 3; and from the antibacterial effect after 15 days, the antibacterial effect is reduced very little, which shows that the antibacterial effect of the liquid silica gel can be improved to a certain extent by heating the gas phase nano titanium dioxide. However, in example 7, too much gas phase nano titanium dioxide is added, which causes uneven dispersion and small amount of white spots, and affects the appearance of the liquid gel.
The liquid silica gels of examples 1 to 3 and examples 5 to 7 were subjected to aging resistance tests, the liquid silica gels were placed in an aging oven at 150 ℃ for 1500 hours, and the conditions of the liquid silica gels were observed. The results are shown in Table 4.
As can be seen from the data in table 4, after the gas-phase nano titanium dioxide is introduced into the liquid silica gel, the anti-aging effect is obviously enhanced, which indicates that the anti-aging effect of the liquid silica gel can be obviously enhanced by adding the gas-phase nano titanium dioxide, and the service life of the liquid silica gel is prolonged.
The above embodiments are preferred embodiments of the present application, and the protection scope of the present application is not limited by the above embodiments, so: equivalent changes in structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (9)
1. The antibacterial and antiallergic liquid silica gel is characterized by comprising, by mass, 100-120 parts of hydroxyl-terminated polysiloxane, 20-30 parts of histidine, 15-25 parts of silver nitrate, 20-30 parts of amino-containing silane coupling agent, 15-25 parts of cinnamaldehyde, 10-15 parts of ethyl orthosilicate and 3-5 parts of a vulcanizing agent.
2. The antibacterial and antiallergic liquid silica gel according to claim 1, which is characterized by comprising, by mass, 110 to 112 parts of hydroxyl-terminated polysiloxane, 24 to 26 parts of histidine, 18 to 20 parts of silver nitrate, 24 to 26 parts of amino-containing silane coupling agent, 18 to 22 parts of cinnamaldehyde, 12 to 14 parts of ethyl orthosilicate and 3 to 5 parts of vulcanizing agent.
3. The antibacterial and antiallergic liquid silicone rubber according to claim 1, wherein the antibacterial and antiallergic liquid silicone rubber further comprises: 5 to 8 portions of gas phase nano titanium dioxide.
4. The antibacterial and antiallergic liquid silica gel according to claim 1, wherein the gas-phase nano titanium dioxide is a mixed-crystal type gas-phase nano titanium dioxide P25.
5. The antibacterial and antiallergic liquid silica gel according to claim 1, wherein the amino-containing silane coupling agent is one of 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane; the silicate is one of methyl orthosilicate, ethyl orthosilicate and isopropyl orthosilicate; the vulcanizing agent is one of dibenzoyl peroxide and dibenzoyl peroxide.
6. A preparation method of the antibacterial and antiallergic liquid silica gel according to any one of claims 1 to 5, comprising the following steps:
s1: mixing hydroxyl-terminated polysiloxane and histidine, adding a sodium hydroxide solution to adjust the pH to be 10-12, heating to react, and separating a water phase after the reaction is finished to obtain polysiloxane grafted with histidine; adding silver nitrate into polysiloxane grafted with histidine, heating for a complexing reaction, and obtaining Ag-histidine-polysiloxane after the reaction is finished;
s2: mixing an amino-containing silane coupling agent, cinnamaldehyde and methanol, adding an alkali to adjust the pH of a solution to 10 to 12, reacting at normal temperature, and after the reaction is finished, heating and evaporating to recover a methanol solvent to obtain silane coupling agent modified cinnamaldehyde;
s3: and (2) stirring and mixing the Ag-histidine-polysiloxane, the silane coupling agent modified cinnamaldehyde and other components in the step (S1) to obtain a mixture, and pouring the mixture into a mold to sequentially perform vulcanization treatment, cooling treatment and demoulding treatment to obtain the antibacterial and antiallergic liquid silica gel.
7. The method for preparing the antibacterial and antiallergic liquid silica gel according to claim 6, wherein in the step S1, the heating temperature is 60 to 80 ℃, the reaction time is 4 to 6h, and the concentration of ammonium hydroxide is 1 to 2mol/L.
8. The preparation method of the antibacterial and antiallergic liquid silica gel according to claim 6, wherein in the step S2, the volume ratio of the amino-containing silane coupling agent to formaldehyde is 1 (1 to 2), and the reaction time is 2 to 4h.
9. The preparation method of the antibacterial and antiallergic liquid silica gel according to claim 6, wherein in the step S3, the vulcanization temperature is 60 to 80 ℃ and the vulcanization time is 2 to 4h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112795195A (en) * | 2021-02-02 | 2021-05-14 | 深圳深凯硅胶制品有限公司 | Wear-resistant antibacterial silica gel and preparation method thereof |
| CN113355047A (en) * | 2021-06-25 | 2021-09-07 | 上海珏晟新材料科技有限公司 | Flame-retardant liquid silica gel for bonding electrical elements and preparation method thereof |
| CN113402889A (en) * | 2021-08-13 | 2021-09-17 | 深圳精灿材料技术有限公司 | Preparation method of durable liquid silica gel |
| CN113480851A (en) * | 2021-07-08 | 2021-10-08 | 深圳精灿材料技术有限公司 | Preparation process of antibacterial liquid silica gel |
| CN113861697A (en) * | 2021-10-15 | 2021-12-31 | 东莞天绘新材料有限公司 | Liquid silica gel with excellent dispersibility and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112795195A (en) * | 2021-02-02 | 2021-05-14 | 深圳深凯硅胶制品有限公司 | Wear-resistant antibacterial silica gel and preparation method thereof |
| CN113355047A (en) * | 2021-06-25 | 2021-09-07 | 上海珏晟新材料科技有限公司 | Flame-retardant liquid silica gel for bonding electrical elements and preparation method thereof |
| CN113480851A (en) * | 2021-07-08 | 2021-10-08 | 深圳精灿材料技术有限公司 | Preparation process of antibacterial liquid silica gel |
| CN113402889A (en) * | 2021-08-13 | 2021-09-17 | 深圳精灿材料技术有限公司 | Preparation method of durable liquid silica gel |
| CN113861697A (en) * | 2021-10-15 | 2021-12-31 | 东莞天绘新材料有限公司 | Liquid silica gel with excellent dispersibility and preparation method thereof |
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