CN115124563A - Heptamethyl siloxane polyoxyethylene ether gallate and preparation method and application thereof - Google Patents
Heptamethyl siloxane polyoxyethylene ether gallate and preparation method and application thereof Download PDFInfo
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- CN115124563A CN115124563A CN202210897646.9A CN202210897646A CN115124563A CN 115124563 A CN115124563 A CN 115124563A CN 202210897646 A CN202210897646 A CN 202210897646A CN 115124563 A CN115124563 A CN 115124563A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0889—Reactions not involving the Si atom of the Si-O-Si sequence
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- C—CHEMISTRY; METALLURGY
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/54—Silicon compounds
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
The invention discloses heptamethyl siloxane polyoxyethylene ether gallate and a preparation method and application thereof, wherein the preparation method comprises the following steps: dissolving heptamethyltrisiloxane polyoxyethylene ether and sodium methoxide in an organic solvent to obtain a mixed solution; dissolving gallic acid methyl ester in an organic solvent, heating, and then adding the mixed solution for reaction; cooling after the reaction is finished, carrying out solid-liquid separation, and taking out a liquid part for rotary evaporation to obtain the catalyst. According to the invention, heptamethyl trisiloxane polyoxyethylene ether and methyl gallate are subjected to ester exchange reaction to prepare heptamethyl trisiloxane polyoxyethylene ether gallate, and the heptamethyl trisiloxane polyoxyethylene ether gallate has good surfactant function and sterilization effect.
Description
Technical Field
The invention belongs to the fields of surfactants, emulsifiers and antibacterial agents, and relates to heptamethylsiloxane polyoxyethylene ether gallate and a preparation method and application thereof.
Background
The surfactant consists of a hydrophilic end and a hydrophobic end, the hydrophobic end of the water solution of the surfactant is contacted with air in an air-water interface due to the amphipathic structural property of the surfactant, the hydrophilic end extends into the liquid and is closely distributed in the air-liquid interface, the interfacial tension is obviously reduced, and the surfactant has the functions of emulsification, wetting, lotion and the like. Due to its specific amphiphilic structure, surfactants have found widespread use in both industry and civilian industries, and are closely related to our lives.
The surfactant has a certain bactericidal function, particularly the bactericidal function of the cationic surfactant is more remarkable, and the widely used cationic surfactant benzalkonium chloride is one of the famous representative varieties which are both surfactants and widely used for sterilization. However, such biocides have a positive charge and limit the range of applications to some extent, for example in the presence of anionic surfactants. Anionic and nonionic surfactants are widely used as detergents, emulsifiers, wetting and spreading agents and the like in the fields of people's life and industry, and in order to guarantee a long storage and quality guarantee period of finished products such as detergents, emulsions and the like, antibacterial and bacteriostatic agents need to be added to prevent the products from breeding bacteria and being decayed in the processes of storage and use.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art, and provides heptamethyl siloxane polyoxyethylene ether gallate which is prepared from heptamethyl trisiloxane polyoxyethylene ether and methyl gallate, and has the functions of remarkably reducing surface tension and emulsifying, and simultaneously has good antibacterial and bactericidal functions.
In order to solve the technical problems, the invention discloses heptamethylsiloxane polyoxyethylene ether gallate and a preparation method and application thereof.
Specifically, the heptamethyl siloxane polyoxyethylene ether gallate has a structure shown in a formula I,
wherein n is 5-7.
The chemical reaction equation for preparing the compound of formula I is as follows:
wherein n is 5-7.
Specifically, the preparation method of the heptamethyl siloxane polyoxyethylene ether gallate comprises the steps of dissolving heptamethyl trisiloxane polyoxyethylene ether and sodium methoxide in an organic solvent (preferably, the mass ratio of the heptamethyl trisiloxane polyoxyethylene ether to the organic solvent is 1: 2-4) to obtain a mixed solution; dissolving methyl gallate in an organic solvent, heating (preferably, the mass ratio of the methyl gallate to the organic solvent is 1: 4-6), and then adding the mixed solution for reaction; and after the reaction is finished, cooling, carrying out solid-liquid separation, and taking out a liquid part for rotary evaporation to obtain the catalyst.
Specifically, the organic solvent is any one or a combination of two of dioxane and tetrahydrofuran, and dioxane is preferred.
Specifically, the molar ratio of the heptamethyltrisiloxane polyoxyethylene ether to the methyl gallate is 1: 1.05 to 1.20.
Specifically, the molar ratio of the sodium methoxide to the methyl gallate is 0.0001-0.3: 1.
specifically, the heating temperature is 60-90 ℃, and the heating time is 0.1-2 h.
Specifically, the reaction temperature is 60-90 ℃, and the reaction time is 3-12 h.
Specifically, the rotary evaporation temperature is 50-100 ℃, and the rotary evaporation vacuum degree is 650-700 mmHg.
The application of the heptamethyl siloxane polyoxyethylene ether gallate as the surfactant is also in the protection scope of the invention.
The application of the heptamethyl siloxane polyoxyethylene ether gallate as the bactericide is also within the protection scope of the invention.
Has the beneficial effects that:
according to the invention, methyl gallate is subjected to ester exchange reaction by virtue of polyoxyethylene ether modified heptamethyltrisiloxane to prepare the heptamethylsiloxane polyoxyethylene ether gallate bactericide, the polyoxyethylene ether modified heptamethyltrisiloxane is combined with gallic acid, and organic silicon is introduced by virtue of an ester group, so that the prepared bactericide has good surface spreadability, and has good surface tension reducing capability and bactericidal effect.
Drawings
The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is a graph showing the surface tension test of heptamethylsiloxane polyoxyethylene ether gallate in example 1;
FIG. 2 is a graph showing the surface tension test of heptamethylsiloxane polyoxyethylene ether gallate in example 2;
FIG. 3 is an infrared spectrum of gallic acid methyl ester, heptamethyltrisiloxane polyoxyethylene ether, and heptamethyltrisiloxane polyoxyethylene ether gallate of example 2;
FIG. 4 is a graph showing the test of emulsifying power of heptamethylsiloxane polyoxyethylene ether gallate in example 2;
FIG. 5 is a graph showing the surface tension test of heptamethylsiloxane polyoxyethylene ether gallate in example 3;
FIG. 6 is a graph showing the surface tension test of heptamethylsiloxane polyoxyethylene ether gallate in example 4.
Detailed Description
The invention will be better understood from the following examples.
Example 1
Dissolving 2.024g (0.011mol) of gallic acid methyl ester in 10g of dioxane, preheating for 0.5h to 60 ℃, then dissolving 0.0054g (0.0001mol) of sodium methoxide and 5.44g of heptamethyltrisiloxane polyoxyethylene ether (n ═ 5) in 15g of dioxane, slowly and dropwise adding the solution into the gallic acid methyl ester dioxane solution, heating to 90 ℃ for reaction for 5h, after the solution is cooled, removing solids by suction filtration, and performing rotary evaporation at 80 ℃ and 700mmHg to obtain the product, wherein the yield is 68.5%.
Surface tension test: the surface tension test of heptamethylsiloxane polyoxyethylene ether gallate in example 1 is shown in FIG. 1. As the concentration of surfactant in water increases, the surface tension of the solution begins to drop sharply, at a concentration of 5X 10 -5 When the percentage (mass fraction) is higher, the surface tension of the solution is reduced to 20.718mN/m, and the fact that the heptamethylsiloxane polyoxyethylene ether gallate has good capability of reducing the surface tension is proved.
Example 2
19.32g (0.105mol) of methyl gallate is dissolved in 100g of dioxane, preheated for 0.5h to 65 ℃, 0.054g (0.001mol) of sodium methoxide and 58.8g (0.1mol) of heptamethyltrisiloxane polyoxyethylene ether (n ═ 6) are dissolved in 150g of dioxane and slowly dripped into the solution of methyl gallate dioxane, heated to 80 ℃ for reaction for 6h, the solution is cooled and filtered to remove solids, and rotary evaporation is carried out at 85 ℃ and vacuum degree of 680mmHg to obtain the product, wherein the yield is 66.5%.
Surface tension test: the surface tension test of heptamethylsiloxane polyoxyethylene ether gallate in example 2 is shown in FIG. 2. As the concentration of surfactant in water increases, the surface tension of the solution begins to drop sharply, at a concentration of 5X 10 -5 When the percentage (mass fraction) is higher, the surface tension of the solution is reduced to 22.242mN/m, which proves that the heptamethylsiloxane polyoxyethylene ether gallate has good capability of reducing the surface tension.
Infrared spectrum analysis: the infrared spectra of methyl gallate, heptamethyltrisiloxane polyoxyethylene ether and heptamethyltrisiloxane polyoxyethylene ether gallate in example 2 are shown in FIG. 3, for methyl gallate, at 1716cm -1 An infrared characteristic absorption peak of the carbon-oxygen double bond appears at 1254cm -1 An infrared characteristic absorption peak at which ether bonds appear, in the case of heptamethyltrisiloxane polyoxyethylene ether, at 1254cm -1 Has an infrared characteristic absorption peak of 1200cm at which ether bond appears -1 The infrared characteristic absorption peak of silicon-carbon bond appears at 950cm -1 Infrared characteristic of occuring silicaThe absorption peak is 1716cm for heptamethyltrisiloxane polyoxyethylene ether gallate -1 The characteristic absorption peak of carbon-oxygen double bond appears at 1254cm -1 An infrared characteristic absorption peak of ether bond at 950cm -1 The infrared characteristic absorption peak of the siloxane bond appears, which proves the successful synthesis of the heptamethyl trisiloxane polyoxyethylene ether gallate.
And (3) testing the emulsifying capacity: the emulsifying ability of heptamethylsiloxane polyoxyethylene ether gallate in example 2 is tested as shown in FIG. 4. The emulsifying capacity of the solution is enhanced along with the increase of the concentration of the surfactant in water, 20mL of surfactant with different concentrations is emulsified for three minutes by a homogenizer at 10000rad/s of speed for 20mL of oil phase, then timing is started, timing is stopped when 10mL of water phase is separated out, and the longer the time for separating out water is, the stronger the emulsifying capacity is. The heptamethyl siloxane polyoxyethylene ether gallate is proved to have good emulsifying property.
Example 3
19.32g (0.115mol) of methyl gallate is dissolved in 100g of dioxane, the solution is preheated for 0.5h to 75 ℃, then 0.054g (0.001mol) of sodium methoxide and 63.2g (0.1mol) of heptamethyltrisiloxane polyoxyethylene ether (n ═ 7) are dissolved in 150g of dioxane and slowly dripped into the solution of methyl gallate dioxane, the solution is heated to 85 ℃ for reaction for 8h, the solution is cooled and filtered to remove solids, the product is obtained by rotary evaporation at 90 ℃ and the vacuum degree of 660mmHg, and the yield is 65.9%.
Surface tension test: the surface tension test of heptamethylsiloxane polyoxyethylene ether gallate in example 3 is shown in FIG. 5. As the concentration of surfactant in water increases, the surface tension of the solution begins to drop sharply, at a concentration of 5X 10 -5 When the percentage (mass fraction) is higher, the surface tension of the solution is reduced to 23.455mN/m, and the fact that the heptamethylsiloxane polyoxyethylene ether gallate has good capability of reducing the surface tension is proved.
And (3) testing the sterilizing capability: the bactericidal performance of the heptamethylsiloxane polyoxyethylene ether gallate bactericide is shown in table 1, a certain amount of bacteria culture solution is added into a sample, and the microorganism detection is carried out on the sample after a certain time. Sucking a proper amount of sample by using a sterile pipette, uniformly mixing the sample in a tryptone agar culture medium, then culturing the tryptone agar culture medium for 48 hours at 35 ℃, taking out the culture medium, observing the growth condition of the microorganism on an agar plate, and reading. The bactericidal rate of the heptamethyl siloxane polyoxyethylene ether gallate bactericide on escherichia coli, staphylococcus aureus and candida albicans is more than or equal to 90 percent, and the fact that the heptamethyl siloxane polyoxyethylene ether gallate bactericide has a bactericidal effect is proved.
TABLE 1 Heptamethylsiloxane polyoxyethylene ether gallate bactericidal Properties
Example 4
22.08g (0.12mol) of gallic acid methyl ester is dissolved in 100g of dioxane, preheated for 1h to 70 ℃, then 0.054g (0.001mol) of sodium methoxide and 58.8g (0.1mol) of heptamethyltrisiloxane polyoxyethylene ether (n ═ 6) are dissolved in 150g of dioxane and slowly dripped into the gallic acid methyl ester dioxane solution, heated to 90 ℃ for reaction for 9h, the solution is cooled and filtered to remove solids, and rotary evaporation is carried out at 85 ℃ and vacuum degree of 680mmHg to obtain the product, wherein the yield is 68.7%.
Surface tension test: the surface tension test of heptamethylsiloxane polyoxyethylene ether gallate in example 4 is shown in FIG. 6. As the concentration of surfactant in water increases, the surface tension of the solution begins to drop sharply, at a concentration of 5X 10 -5 When the percentage (mass fraction) is higher, the surface tension of the solution is reduced to 21.325mN/m, and the fact that the heptamethylsiloxane polyoxyethylene ether gallate has good capability of reducing the surface tension is proved.
And (3) testing the foam performance: 4 surfactant samples (prepared in example 1, example 2, example 3 and example 4) were prepared into 0.1% surfactant solutions, and equilibrated in a thermostatic water bath at 25 + -0.2 deg.C for 12h (to eliminate the effect of temperature on foam properties). Adding 10mL of sample water solution with the mass fraction of 0.1% to be detected into a 100mL measuring cylinder with a plug, largely oscillating for 30 times at 25 ℃, horizontally standing, and recording the foam volume after oscillation is finished for 0min and 5 min.
TABLE 2 foam Properties
The invention provides a heptamethyl siloxane polyoxyethylene ether gallate and a preparation method and application thereof, and a method and a way for realizing the technical scheme are many, the above description is only a preferred embodiment of the invention, it should be noted that for a person skilled in the art, a plurality of improvements and decorations can be made without departing from the principle of the invention, and the improvements and decorations should also be regarded as the protection scope of the invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (10)
1. A heptamethyl siloxane polyoxyethylene ether gallate is characterized in that the heptamethyl siloxane polyoxyethylene ether gallate has a structure shown in a formula I,
wherein n is 5-7.
2. The method of claim 1, wherein heptamethyl trisiloxane polyoxyethylene ether and sodium methoxide are dissolved in an organic solvent to obtain a mixed solution; dissolving gallic acid methyl ester in an organic solvent, heating, and then adding the mixed solution for reaction; cooling after the reaction is finished, carrying out solid-liquid separation, and taking out a liquid part for rotary evaporation to obtain the catalyst.
3. The method according to claim 2, wherein the organic solvent is any one or a combination of two of dioxane and tetrahydrofuran.
4. The method according to claim 2, wherein the molar ratio of the heptamethyltrisiloxane polyoxyethylene ether to the methyl gallate is 1: 1.05 to 1.20.
5. The method according to claim 2, wherein the molar ratio of sodium methoxide to methyl gallate is 0.0001 to 0.3: 1.
6. the preparation method according to claim 2, wherein the heating is carried out at a temperature of 60 to 90 ℃ for 0.1 to 2 hours.
7. The preparation method according to claim 2, wherein the reaction is carried out at a temperature of 60-90 ℃ for 3-12 h.
8. The preparation method according to claim 2, wherein the rotary evaporation temperature is 50-100 ℃, and the rotary evaporation vacuum degree is 650-700 mmHg.
9. Use of heptamethylsiloxane polyoxyethylene ether gallate as claimed in claim 1 as a surfactant.
10. Use of heptamethylsiloxane polyoxyethylene ether gallate as claimed in claim 1 as a fungicide.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936333A (en) * | 2012-11-02 | 2013-02-20 | 陕西科技大学 | Aromatic hyperbranched polymer surfactant and preparation method thereof |
| CN103638872A (en) * | 2013-12-16 | 2014-03-19 | 南京美思德新材料有限公司 | Trisiloxane polyether-ester surfactant as well as preparation method thereof |
| CN105669968A (en) * | 2015-12-30 | 2016-06-15 | 中山大学惠州研究院 | Preparation method of polyether grafted trisiloxane surfactant |
| CN107501531A (en) * | 2017-08-23 | 2017-12-22 | 大连大学 | A kind of double block stabilizer HMTS PCL synthetic method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936333A (en) * | 2012-11-02 | 2013-02-20 | 陕西科技大学 | Aromatic hyperbranched polymer surfactant and preparation method thereof |
| CN103638872A (en) * | 2013-12-16 | 2014-03-19 | 南京美思德新材料有限公司 | Trisiloxane polyether-ester surfactant as well as preparation method thereof |
| CN105669968A (en) * | 2015-12-30 | 2016-06-15 | 中山大学惠州研究院 | Preparation method of polyether grafted trisiloxane surfactant |
| CN107501531A (en) * | 2017-08-23 | 2017-12-22 | 大连大学 | A kind of double block stabilizer HMTS PCL synthetic method |
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