CN112790195B - Mildew-proof adhesive and preparation method and application thereof - Google Patents
Mildew-proof adhesive and preparation method and application thereof Download PDFInfo
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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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
- A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
- A01N47/44—Guanidine; Derivatives thereof
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C277/08—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups of substituted guanidines
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- C07C279/00—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C279/04—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of guanidine groups bound to acyclic carbon atoms of a carbon skeleton
- C07C279/14—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of guanidine groups bound to acyclic carbon atoms of a carbon skeleton being further substituted by carboxyl groups
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
Abstract
The present invention provides a preservative for adhesives comprising lauroyl arginine ethyl ester (LAE) ion pair derivatives. The invention also provides a method for preparing the adhesive containing the preservative and the mildew-proof adhesive prepared by the method. The preservative of the adhesive has the characteristics of being natural, non-toxic, efficient and bacteriostatic, easy to degrade and environment-friendly.
Description
The application is a divisional application of Chinese invention patent application with the application date of 2019, 6 and 21 months and the application number of 201910544738.7, and the invention name of the invention is 'mildew-proof adhesive and a preparation method and application thereof'.
Technical Field
The invention relates to a mildew-proof adhesive, in particular to an adhesive containing lauroyl arginine ethyl ester derivatives (ion pair compounds), wherein the lauroyl arginine ethyl ester ion pair has an antibacterial effect, can help the adhesive to exert a bonding function, and can also keep the adhesive stable and exert an antibacterial and antiseptic effect.
Background
The adhesives typically include industrial adhesives (e.g., metal part adhesives, building material adhesives, or caulks), household adhesives (e.g., glues, glue sticks), medical adhesives (e.g., soft tissue adhesives, dental adhesives, orthopedic adhesives, skin pressure sensitive adhesives, skin adhesives, etc.). These adhesives exert their adhesive effect mainly by organic adhesive substances such as various organic celluloses (e.g., starches, polymeric celluloses), polyvinyl acetates, various organic resins (e.g., amino resins, silicone resins, acrylic modified resins), and bio-adhesive substances (e.g., biogel, gliadin, etc.), which are easily deteriorated and moldy by microorganisms over time or easily inactivated by water and sunlight, thereby affecting the use effect.
Therefore, it is a hot research on adhesives to reduce the effects of microbial mold and/or deterioration of external environmental factors as much as possible while maintaining the adhesive effect.
Chinese patent application 2017107142581, a "mildew-proof natural adhesive", discloses that borax and boric acid are used as preservative, and are matched with other adhesive components, stabilizer, defoamer and the like to prepare a natural mildew-proof adhesive, which has the advantages of good mildew-proof performance and long service time.
Lauroyl arginine Ethyl ester (LAE) is an organic matter formed by condensing fatty acid and dibasic amino acid, is a white hygroscopic solid, is stable in chemical property within the pH range of 3-7, has a melting point of 50-58 ℃, can be dispersed in 1kg of water at the temperature of 247g, has a distribution coefficient of more than 10 in water and oil, and mainly exists in a water phase. Researches find that the lauroyl arginine ethyl ester LAE has the characteristics of strong antibacterial ability, low biotoxicity, good in-vivo metabolism effect and high environmental compatibility. The most representative characteristic is that no residue is left in the metabolism of lauroyl arginine ethyl ester, and related researches show that the lauroyl arginine ethyl ester can be rapidly and naturally metabolized in human bodies and animal bodies to generate lauric acid and arginine which are further metabolized into ornithine, urea, carbon dioxide and water. All primary metabolites and final products produced during the metabolism of lauroyl arginine ethyl ester are non-toxic and harmless, and are the same as the metabolites of food which is ingested daily by human and animals in the body.
In 2005, the FDA approved LAE as a GRAS (generally recognized as safe) food additive in the united states, passed the safety food certification of the European Food Safety Authority (EFSA) in 2007, and the international commission on food code in 2011 included LAE as a standard of the general code for food additives, and approved LAE as a preservative for 20 kinds of foods and fresh agricultural products.
Chinese patent application 201610679678, a waterproof mildew-proof starch adhesive and a preparation method thereof, discloses that LAE and 5-chloro-2-methyl-4-isothiazoline-3-ketone are used as mildew inhibitors and are matched with other starch adhesive components to prepare the waterproof mildew-proof starch adhesive.
However, the research on adhesives inventions relating to LAE and its salts as mildewcides has been less appreciated and further improvements are needed. Facing the largest global markets for industrial, medical and daily adhesives, China needs a new high-efficiency, non-toxic and stable mildew-proof adhesive.
In view of the above, studies on LAE have been conducted in the prior art, but no reports on the use of LAE, or even LAE derivatives, for preparing mildewproof adhesives have been found.
Disclosure of Invention
One principle of the invention is that according to the characteristics that lauroyl arginine ethyl ester LAE has strong antibacterial ability, low biological toxicity, good in vivo metabolism effect, high environmental compatibility and no reaction with other compounds at normal temperature, LAE is further improved to obtain a novel derivative, namely LAE and organic acid salt are subjected to condensation reaction, so that an LAE ion pair compound is obtained. The ion pair compound is used as a bacteriostatic agent and a preservative component in the adhesive, and has the advantages of better bacteriostatic effect and lower using dosage compared with LAE, thereby being more beneficial to preparing natural, nontoxic and stable mildew-proof adhesive. Wherein the LAE ion pair compound component is used as the main or only bacteriostatic and preservative component.
Accordingly, a first object of the present invention is to provide the use of a LAE ion pair compound for preparing a mildewproof adhesive, wherein the LAE ion pair compound has a formula as shown in formula (III):
wherein, the RCOO - The organic acid or salt is selected from salicylic acid, formic acid, ammonium formate, calcium formate, acetic acid, sodium diacetate, propionic acid, ammonium propionate, sodium propionate, calcium propionate, butyric acid, sodium butyrate, lactic acid, benzoic acid, sodium benzoate, sorbic acid, sodium sorbate, potassium sorbate, fumaric acid, citric acid, potassium citrate, sodium citrate, calcium citrate, tartaric acid, malic acid, phosphoric acid, sodium carbonate, oxalic acid or carbonic acid having antibacterial activity; preferably, the organic acid salt is selected from nicotinic acid, tartaric acid, oxalic acid.
In any of the above embodiments, the mildewproof adhesive is an industrial adhesive (e.g., a metal part adhesive, a building material adhesive, or a caulking agent), a household adhesive (e.g., a glue stick), a medical adhesive (e.g., an adhesive for soft tissue, an adhesive for dental use, an adhesive for bone use, a pressure sensitive adhesive for skin use, an adhesive for skin use, or the like).
In one embodiment, the LAE ion pair compound is present in the mildewcide binder in an amount of 0.001 to 2 percent by weight; preferably, 0.001-0.01%, 0.01-0.1%, 0.05-0.1%, 0.1-0.2%, 0.1-1%, 1-2%, or 1.5-2%; further preferably, it is 0.1 to 1% or 0.1 to 0.2%.
It is a third object of the present invention to provide a method for preparing a mildewproof adhesive containing the above LAE ion pair compound, comprising the steps of:
(1) heating and dissolving the compound shown in the formula (II), and then adding an organic acid salt solution;
(2) fully stirring and uniformly mixing, and reacting to generate the LAE ionic compound under the condition of heating, wherein the reaction is shown as the following reaction formula:
wherein, the RCOO - The organic acid or salt is selected from salicylic acid, formic acid, ammonium formate, calcium formate, acetic acid, sodium diacetate, propionic acid, ammonium propionate, sodium propionate, calcium propionate, butyric acid, sodium butyrate, lactic acid, benzoic acid, sodium benzoate, sorbic acid, sodium sorbate, potassium sorbate, fumaric acid, citric acid, potassium citrate, sodium citrate, calcium citrate, tartaric acid, malic acid, phosphoric acid, sodium carbonate, oxalic acid or carbonic acid having antibacterial activity; preferably, the organic acid salt is selected from nicotinic acid, tartaric acid, oxalic acid.
(3) After full reaction, cooling to room temperature, purifying and then drying in vacuum to prepare the lauroyl arginine ethyl ester organic acid ion pair compound shown in the formula (III);
(4) dissolving the LAE ion pair compound in an organic solvent in a container to obtain an ion pair compound mother solution;
(5) and (3) adding the mother solution into a matrix of the mildew-proof adhesive at room temperature, and fully stirring to obtain the mildew-proof adhesive.
In the step (1), the temperature for heating and dissolving is 50-100 ℃; preferably, it is 90 ℃.
In the step (2), the reaction temperature is 50-100 ℃; preferably, it is 90 ℃.
In the step (2), the reaction time is 50-100 ℃; preferably, it is 90 ℃.
In the step (3), the vacuum drying condition is 50-100 ℃; preferably, it is 60 ℃.
In the step (4), the container is preferably made of stainless steel or inert material.
In the step (4), the organic solvent is methanol, ethanol or the like.
In another embodiment, the RCOO - The preparation method of the organic acid salt comprises the following steps: adding the organic acid into a methanol solution, adding a proper amount of NaOH, stirring at room temperature until a white solid is separated out, carrying out suction filtration, and washing with methanol to obtain the organic acid salt.
It is a fourth object of the present invention to provide a mold-resistant adhesive containing the above LAE ion-pair compound or prepared by the above method.
In any of the above embodiments, the mildewproof adhesive refers to a composition comprising the LAE or the ion pair derivative thereof described above in a matrix of a conventional mildewproof adhesive.
Terms and definitions:
lauroyl arginine Ethyl ester (LAE) is an organic matter formed by condensing fatty acid and dibasic amino acid, is a white hygroscopic solid, is stable in chemical property within the pH range of 3-7, has a melting point of 50-58 ℃, can be dispersed in 1kg of water at the temperature of 247g, has a distribution coefficient of more than 10 in water and oil, and mainly exists in a water phase. Researches find that the lauroyl arginine ethyl ester LAE has the characteristics of strong antibacterial ability, low biotoxicity, good in-vivo metabolism effect and high environmental compatibility. The most representative characteristic of lauroyl arginine ethyl ester is that no residue is left in metabolism, and related research shows that lauroyl arginine ethyl ester can be rapidly metabolized naturally in human bodies and animal bodies, is firstly hydrolyzed into Lauroyl Arginine (LAS) and ethanol, then LAS is hydrolyzed into naturally-occurring dietary components, namely lauric acid and arginine, the lauric acid is further metabolized into carbon dioxide and water, and the arginine is metabolized into ornithine, urea and carbon dioxide. All primary metabolites and final metabolites produced during the metabolism of lauroyl arginine ethyl ester are non-toxic and harmless, and are the same as the metabolites of food ingested daily by humans and animals in the body.
The invention improves the derivatives of the LAE, breaks through the traditional thought of the development of the derivatives, namely, the traditional thought is not limited to selecting the proper forms of acid, alkali and salt/ester which are traditionally suitable for the LAE, or the LEA is treated by acid, alkali, salt or esterification groups, but creatively selects an acid radical group which can enhance the bacteriostatic synergistic effect of the LAE, and combines the acid radical group and the acid radical group into a new derivative, namely an ion pair compound, through strong intermolecular ionic bonds, so that the application of the LAE derivative in the mildew-proof adhesive is remarkably improved.
Technical effects
The mildew-proof adhesive has the advantages that:
the LAE ion pair compound is creatively used for replacing bacteriostatic agents and preservatives in the mildew-proof adhesive, and the traditional mildew-proof adhesive has the advantages of low cost, simple manufacturing process and good stability, and meanwhile has the advantages of remarkable bacteriostatic effect, single component, simplicity in preparation, no harm to human bodies, easiness in biological catabolism, easiness in long-term storage and the like.
Drawings
FIG. 1: cation B of LAE ion pair compound + ESI mass spectra of molecular ion peaks;
FIG. 2: anion A of LAE nicotinic acid ion pair compound - ESI mass spectra of molecular ion peaks;
FIG. 3: of LAE 1 Peak shape and chemical shift pattern by H-NMR;
FIG. 4: process for preparing nicotinic acid 1 Peak shape and chemical shift diagram of H-NMR;
FIG. 5: of the LAE nicotinic acid ion pair 1 Peak shape and chemical shift pattern by H-NMR;
FIG. 6: anion A of LAE tartrate ion pair compound - ESI mass spectrum of molecular ion peak.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and drawings, and the present invention is not limited to the following examples. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is intended to be protected. The procedures, conditions, reagents, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art, except for the contents specifically mentioned below, and the present invention is not particularly limited.
The first embodiment is as follows: preparation method of ion pair compound synthesized by lauroyl arginine ethyl ester hydrochloride and nicotinic acid
Dissolving 2.0g of sodium nicotinate (purchased from Taishiai (Shanghai) chemical industry development Co., Ltd.) in 50mL of water to prepare a sodium nicotinate saline solution (A); dissolving lauroyl arginine ethyl ester hydrochloride 6.8g in 40mL of water, heating to 90 ℃ until the lauroyl arginine ethyl ester hydrochloride is completely dissolved to prepare lauroyl arginine ethyl ester hydrochloride aqueous solution (B); slowly adding the sodium nicotinate aqueous solution (A) into the lauroyl arginine ethyl ester hydrochloride aqueous solution (B) at 90 ℃, continuously stirring, reacting for 2 hours, cooling to room temperature, filtering, fully washing the precipitate with purified water, and performing vacuum drying on the precipitate at 60 ℃ to obtain 7.6g of the nicotinic acid ion pair compound.
The second embodiment: analysis of molecular formula and molecular weight of lauroyl arginine ethyl ester nicotinic acid ion pair compound
By mass spectrometry, 1 H-NMR、 13 The compound obtained by C-NMR spectroscopy has the formula:
1. mass Spectrometry (ESI) analysis
Cation B + The molecular ion peak has m/z 385.3, see fig. 1;
ESI + mass spectrometry was 124.2, see FIG. 2. The ESI-is 122.2, i.e. the m/z of the anion a-molecular ion peak is 122.2.
The theoretical calculation of the niacin ion for the cation in the compound was 507.4, and the observed value coincided with the theoretical value.
NMR analysis
Mixing lauroyl arginine ethyl ester hydrochloride (see figure 3), nicotinic acidIs/are as follows 1 H-NMR (see FIG. 4) and of LAE nicotinic acid ion-pair compounds 1 H-NMR (see FIG. 5). In the salt forming process of the LAE ion pair compound, the peak shape and chemical shift of lauroyl arginine ethyl ester in the ion pair compound are not changed greatly, but all hydrogen on nicotinic acid has shift change, and the spectral characteristics of the acid-base part are closer to the spatial distance of the original inorganic acid salt (namely LAE hydrochloride), so that the influence is generated, therefore, the corresponding change is generated compared with the original LAE and the hydrochloride thereof, the acid-base part is not simply superposed, for example, the solubility is changed when purified water is used for washing and precipitating, and the strong interaction is generated between all hydrogen nuclei of the lauroyl arginine ethyl ester and the nicotinic acid, and a stable single compound structure is formed through strong ionic bonds.
Example three: preparation method of ion pair compound synthesized by lauroyl arginine ethyl ester hydrochloride and tartaric acid
2.0g of tartaric acid (purchased from Chiese chemical industry Co., Ltd.) was dissolved in 50mL of methanol, and an equivalent amount of NaOH was added thereto, and the mixture was stirred at room temperature until a white solid was precipitated, and then the solution was filtered under suction and washed with 30mL of methanol three times to obtain a tartaric acid sodium salt. Dissolving sodium tartrate salt in 50mL of water to prepare a sodium tartrate salt aqueous solution (A); dissolving 5.6g of lauroyl arginine ethyl ester hydrochloride in 40mL of water, heating to 90 ℃ until the lauroyl arginine ethyl ester hydrochloride is completely dissolved to prepare lauroyl arginine ethyl ester hydrochloride aqueous solution (B); slowly adding the tartaric acid sodium salt aqueous solution (A) into the lauroyl arginine ethyl ester hydrochloride aqueous solution (B) at 90 ℃, continuously stirring, reacting for 2 hours, cooling to room temperature, filtering, fully washing the precipitate with purified water, and drying the precipitate in vacuum at 60 ℃ to obtain 6.3g of the tartaric acid ion pair compound.
Example four: analysis of molecular weight of Compound by lauroyl arginine Ethyl ester tartrate ion
Mass Spectrometry (ESI) analysis of cation B + Molecular ion peak m/z 385.3 (see fig. 1)
Anion A - Molecular ion peak m/z 149.0 (see FIG. 6)
The theoretical calculation of the nicotinic acid ion for the cation in the compound is 534.3, and the actual measurement value is consistent with the theoretical value.
Example five: preparation method for synthesizing ion pair compound by lauroyl arginine ethyl ester hydrochloride and oxalic acid
Oxalic acid (purchased from research Co., Ltd.) 1.0g was dissolved in 50mL of methanol, and an equivalent amount of NaOH was added thereto, and the mixture was stirred at room temperature until a white solid precipitated, filtered under suction and washed with 30mL of methanol three times to obtain an oxalic acid sodium salt. Dissolving sodium oxalate in 50mL of water to prepare sodium oxalate aqueous solution (A); dissolving 4.7g of lauroyl arginine ethyl ester hydrochloride in 40mL of water, heating to 90 ℃ until the lauroyl arginine ethyl ester hydrochloride is completely dissolved to prepare lauroyl arginine ethyl ester hydrochloride aqueous solution (B); slowly adding the sodium oxalate salt aqueous solution (A) into the lauroyl arginine ethyl ester hydrochloride aqueous solution (B) at 90 ℃, continuously stirring, reacting for 2 hours, cooling to room temperature, filtering, fully washing the precipitate with purified water, and drying the precipitate in vacuum at 60 ℃ to obtain 5.0g of the oxalate ion pair compound.
The results of NMR and ESI analyses performed according to the method of example two show that the ion pair compound is not a simple superposition of two acid and base portions, which are closely spaced and affect the spectral characteristics, and the spectral data of the ion pair compound is changed compared with the original LAE and its hydrochloride, for example, the solubility is changed when the precipitate is washed with purified water, which indicates that all hydrogen nuclei of lauroyl arginine ethyl ester have strong interactions with oxalic acid and form a stable single compound structure through strong ionic bonds.
Example six: preparation method of ion pair compound synthesized by lauroyl arginine ethyl ester hydrochloride and carbonic acid
1.0g of sodium carbonate (purchased from exploration Co., Ltd.) was dissolved in 50mL of water to prepare an aqueous solution (A) of sodium carbonate; dissolving 4.0g of lauroyl arginine ethyl ester hydrochloride in 40mL of water, heating to 90 ℃ until the lauroyl arginine ethyl ester hydrochloride is completely dissolved to prepare a lauroyl arginine ethyl ester hydrochloride aqueous solution (B); slowly adding the sodium carbonate aqueous solution (A) into the lauroyl arginine ethyl ester hydrochloride aqueous solution (B) at 90 ℃, continuously stirring, reacting for 2 hours, cooling to room temperature, filtering, fully washing the precipitate with purified water, and drying the precipitate in vacuum at 60 ℃ to obtain 4.0g of the carbonate ion pair compound.
The results of NMR and ESI analyses performed according to the method of example two show that the ion pair compound does not have a simple superposition of two acid and base portions, the two acid and base portions are close in space distance and have an influence, and the spectral data of the ion pair compound is changed correspondingly compared with the original LAE and hydrochloride thereof, which indicates that all hydrogen nuclei of the lauroyl arginine ethyl ester have strong interaction with carbonic acid and form a stable single compound structure through strong ionic bonds.
Example seven: determination of lauroyl arginine ethyl ester ion pair compound Minimum Inhibitory Concentration (MIC) in vitro
The principle and the purpose are as follows: the minimum drug concentration at which bacterial growth is inhibited after 24h incubation of the drug with bacteria in a 96-well plate is the minimum inhibitory concentration for the drug, according to the microbult dilution method specified by CLSI.
The method comprises the following steps: lauroyl arginine ethyl ester hydrochloride (LAE hydrochloride) and the pair of lauroyl arginine ethyl ester organic acid ions prepared above are respectively diluted to different concentrations by Trypticase Soy Broth (TSB), the drug and the bacteria are mixed and incubated in a 96-well plate, and a blank control medium CK1 without bacteria, a medium CK2 added with LAE (1000. mu.g/ml) and a normal growth control medium CK3 without the drug are additionally arranged. The absorbance at 625nm of each well was measured after incubating the 96-well plate in a 37 ℃ incubator for 24 hours. OD comparison with blank 625 Wells with consistent values were considered to have no significant growth of bacteria. The lowest concentration of drug at which bacteria do not significantly grow is the minimum Inhibitory concentration mic (minimum inhibition concentration) of LAE to bacteria.
The results of comparing the antibacterial activity of various LAE derivatives (ion pair compounds) prepared with respect to the original LAE compound are shown in table 1 below.
TABLE 1 in vitro antibacterial Effect of LAE and its ion-pair Compounds on two bacteria
Wherein the percentage value in the bracket () represents the mass percentage of each additive in the reaction system.
And (4) analyzing results:
(1) most of the LAE ion pair compound keeps the same antibacterial activity to escherichia coli, and especially the antibacterial activity of the oxalic acid ion pair compound is increased;
(2) most of LAE ion pair compounds keep the same antibacterial activity to staphylococcus aureus, the antibacterial activity of carbonic acid ion pair compounds is reduced, and the antibacterial activity of nicotinic acid ion pair compounds is obviously improved;
and (4) conclusion: ion pair compounds of LAE derivatives do not inhibit the antibacterial activity of the original LAE in a single component, but are beneficial to the antibacterial activity. Wherein, the nicotinic acid ion pair compound has obvious bacteriostatic effect on staphylococcus aureus.
Example eight: determination of inhibitory Activity of lauroyl arginine Ethyl ester ion on mildew-causing microorganisms
The principle and the purpose are as follows: the penicillium and aspergillus are main microorganisms causing the mildew of the adhesive, and the inhibition effect of lauroyl arginine ethyl ester (LAE) ions on the penicillium and aspergillus is detected by the bacteriostatic circle method for the experiment, so that the mildew-proof effect of the lauroyl arginine ethyl ester ions on the penicillium and aspergillus is evaluated.
The method comprises the following steps: respectively putting penicillium or aspergillus spores into an LB liquid culture medium, selecting fungi single colonies, putting the fungi single colonies into a PDB liquid culture medium, culturing for 24 hours at room temperature, and uniformly coating the amplified bacterial liquid on the surface of the LB solid culture medium. The medium was punched with a 0.8mm punch, and about 100. mu.l of each well of lauroyl arginine ethyl ester ion pair or sodium methyl paraben, a positive fruit preservative, was added to the wells, which were covered with a lid, and incubated in an incubator at 37 ℃ for 48 hours. And measuring and counting the diameter of the inhibition zone of each hole.
And (4) analyzing results: tables 2 and 3 show the inhibition zones of the LAE ion pair compounds for Penicillium and Aspergillus, respectively. Both LAE and LAE ion pair can inhibit the growth of Penicillium, LAE-formate ion pair, and LAE-salicylate ion pair have inhibitory effect at a concentration of 256 μ g/ml or more, and LAE-nicotinic acid ion pair has inhibitory effect at a concentration of 512 μ g/ml or more. Both LAE and LAE ion pair can inhibit the growth of Aspergillus, LAE-formate ion pair and LAE-salicylate ion pair have inhibition effect at a concentration of more than or equal to 128 mug/ml, and LAE-nicotinic acid ion pair inhibits the growth of Microbacterium at a concentration of more than or equal to 256 mug/ml.
And (4) conclusion: the LAE can inhibit the growth of mildew-causing microorganisms, the ability of the LAE ion pair to inhibit the decay-causing microorganisms is not lost, and the inhibition effect of the LAE-nicotinic acid ion pair compound on penicillium and aspergillus is strongest.
TABLE 2 results of inhibition zone of LAE and its ion pair compounds against Penicillium
TABLE 3 LAE and its results for zone of inhibition of Aspergillus by ion-pair compounds
Although the bacteriostatic effect of the 0.2% dose group was the highest among the above-mentioned several groups of experiments, and from the in vitro cell test data of the applicant's previously filed patent application (title of the invention: "use of lauroyl arginine ethyl ester derivative as an antibacterial agent for animals", application No. 201810648982.3, application date 2019, 6/22/h), the bacteriostatic effect was already produced at a concentration of 0.0032%, and the bacteriostatic effect was improved by increasing the dose of LAE and its derivative within a certain range, but the bacteriostatic effect was not significantly improved with respect to the 0.1% dose group, indicating that the dose range of 0.01% -0.2% has satisfied the production requirements.
If the addition amount of LAE and derivatives thereof is increased, although the bacteriostatic rate is correspondingly increased, too high bacteriostatic rate means more residues and is not beneficial to human health. Even so, because the bacteriostatic agent components of the LAE and the derivative thereof belong to natural, environment-friendly and nontoxic components, the addition of high dosage of the LAE and the derivative thereof has the advantage of being friendly to human body compared with the traditional chemical bacteriostatic agent.
Therefore, in consideration of production cost and actual production requirements, the LAE and ions thereof can effectively prevent mildew when the mass percentage concentration of the LAE and ions thereof to the active ingredients of the kitchen oil stain cleaning agent is 0.001-0.01% or 0.01-0.1% or 0.1-0.2%, preferably the effective concentration is 0.05-0.1%, and most preferably 0.1-0.2%, thereby meeting the production requirements.
Claims (8)
- Use of a LAE ion pair compound for the preparation of a mouldproof adhesive, characterised in that the LAE ion pair compound is prepared by the reaction:(1) dissolving the compound shown in the formula (II) in water, heating to 90 ℃ until the compound is completely dissolved, and then slowly adding a sodium tartrate solution at 90 ℃;
(2) fully stirring and uniformly mixing, and reacting under the condition of heating to 90 ℃ to obtain an LAE ion pair compound;(3) after sufficient reaction, the reaction mixture is cooled to room temperature, and is fully washed and purified by purified water and then dried in vacuum, thereby preparing the purified LAE ion pair compound. - 2. Use according to claim 1, characterized in that said antimildew adhesive is chosen from industrial adhesives, household adhesives, medical adhesives.
- 3. The use according to claim 2, wherein the industrial adhesive comprises a metal part adhesive, a building material adhesive or a caulk; the daily adhesive comprises glue and a glue stick; the medical adhesive comprises an adhesive for soft tissue, an adhesive for dentistry, an adhesive for orthopedics, a pressure-sensitive adhesive for skin and a skin adhesive.
- 4. The use according to claim 3, wherein the LAE ion pair is present in a matrix solution of the mildewproof adhesive in a concentration of 0.001 to 2% by mass.
- 5. The use of claim 4, wherein the LAE ion pair compound is present in the mildewproof adhesive in an amount from 0.001 to 0.01%, from 0.01 to 0.1%, from 0.1 to 1%, or from 1 to 2% by weight.
- 6. The use according to claim 5, wherein the LAE ion pair compound is present in the mould-proof binder in a concentration of 0.05-0.1%, 0.1-0.2% or 1.5-2% by weight.
- 7. The preparation method of the mildew-proof adhesive is characterized by comprising the following steps of:(1) dissolving a compound of formula (II) as defined in claim 1 in water, heating to 90 ℃ until complete dissolution, and then slowly adding a sodium tartrate solution at 90 ℃;(2) fully stirring and uniformly mixing, and generating an LAE ion pair compound through reaction under the condition of heating to 90 ℃;(3) after full reaction, cooling to room temperature, fully washing and purifying with purified water, and then drying in vacuum to prepare a purified LAE ion pair compound;(4) dissolving the LAE ion pair compound in an organic solvent in a container to obtain a mother solution of the LAE ion pair compound;(5) and (3) adding the LAE ion pair compound mother solution into a matrix of the mildew-proof adhesive at room temperature, and fully stirring to obtain the mildew-proof adhesive.
- 8. A mildewproof adhesive prepared by the method of claim 7.
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|---|---|---|---|---|
| CN101227884A (en) * | 2005-08-01 | 2008-07-23 | 米雷特实验室股份公司 | Corrosion protection system including cationic surfactant |
| CN106565546A (en) * | 2016-10-21 | 2017-04-19 | 武汉桀升生物科技有限公司 | Lauroyl arginine ethyl ester glycol acid salt and preparation method and application thereof |
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| MX2009001200A (en) * | 2006-08-03 | 2009-02-11 | Miret Lab | Antiviral use of cationic surfactant. |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101227884A (en) * | 2005-08-01 | 2008-07-23 | 米雷特实验室股份公司 | Corrosion protection system including cationic surfactant |
| CN106565546A (en) * | 2016-10-21 | 2017-04-19 | 武汉桀升生物科技有限公司 | Lauroyl arginine ethyl ester glycol acid salt and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Ionic coupling of hyaluronic acid with ethyl N-lauroyl L-arginate(LAE): Structure, properties and biocide activity of complexes;Ana Gamarra et al;《Carbohydrate Polymers》;20180518;第197卷;第9页第1段、图1，第19页倒数第1节 * |
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