CN110313488B - 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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- CN110313488B CN110313488B CN201910544738.7A CN201910544738A CN110313488B CN 110313488 B CN110313488 B CN 110313488B CN 201910544738 A CN201910544738 A CN 201910544738A CN 110313488 B CN110313488 B CN 110313488B
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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 mildewproof 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
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 generally include industrial adhesives (e.g., metal part glues, 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 adhesive glues, 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 liable to be deteriorated and mildewed by microorganisms or to be inactivated by water and sunlight over time, thereby affecting the use effect.
Therefore, it is a hot research on adhesives to reduce the effects of microbial molding 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, defoaming agent, etc. to prepare a natural mildew-proof adhesive, which has the advantages of good mildew-proof performance and long service life.
Lauroyl arginine Ethyl ester (LAE) is an organic substance formed by condensing fatty acid and dibasic amino acid, is a white hygroscopic solid, is chemically stable 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, and has a distribution coefficient of more than 10 in water and oil, namely is mainly in the water phase. Researches find that the lauroyl arginine ethyl ester LAE has the characteristics of strong antibacterial capability, low biological toxicity, 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 generated in the metabolism process of lauroyl arginine ethyl ester are nontoxic and harmless, and are the same as the metabolites of foods ingested daily by human beings and animals in vivo.
In 2005, LAE was approved by FDA as a GRAS (generally recognized as safe) food additive in the united states, approved by European Food Safety Administration (EFSA) for safe food certification in 2007, and listed as a standard of food additive general law by 2011 international committee on food code, and is approved 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, the LAE is further improved to obtain a novel derivative, namely LAE and organic acid salt are subjected to condensation reaction, so that the 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 structural formula shown in the following 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 orthopedic use, a pressure sensitive adhesive for skin, an adhesive for skin, etc.).
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 heating and dissolving temperature 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 is as follows: 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 mildew-resistant adhesive refers to a composition comprising the above LAE or its ion pair derivative in a matrix of a conventional mildew-resistant 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 range of pH 3-7, has a melting point of 50-58 ℃, can be dispersed in 1kg of water at the temperature of 247g, and has a distribution coefficient of more than 10 in water and oil, namely is mainly in the water phase. Researches find that the lauroyl arginine ethyl ester LAE has the characteristics of strong antibacterial capability, low biological toxicity, 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 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 existing dietary components of 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 derivatives 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 to replace a bacteriostatic agent and a preservative in the mildew-proof adhesive, and the traditional mildew-proof adhesive has the advantages of low cost, simple preparation process and good stability, and simultaneously has the advantages of obvious bacteriostatic effect, single component, simple preparation, no harm to human bodies, easy biological catabolism, easy long-term storage and the like.
Drawings
FIG. 1: cation B of the 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 LAE1Peak shape and chemical shift diagram of H-NMR;
FIG. 4: process for preparing nicotinic acid1Peak shape and chemical shift diagram of H-NMR;
FIG. 5: of the LAE nicotinic acid ion pair1Peak shape and chemical shift diagram of 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 from lauroyl arginine ethyl ester hydrochloride and nicotinic acid
2.0g of sodium nicotinate (purchased from Taishiai (Shanghai) chemical industry development Co., Ltd.) is dissolved in 50mL of water to prepare a sodium nicotinate aqueous solution (A); dissolving 6.8g 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 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 drying the precipitate at 60 ℃ in vacuum to obtain 7.6g of the nicotinic acid ion pair compound.
Example analysis of molecular formula and molecular weight of compound by dilauroyl arginine ethyl ester nicotinic acid ion pair
By mass spectrometry,1H-NMR、13The 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;
mass Spectrometry detection ESI + 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
Extracting lauroyl arginine ethyl ester hydrochloride (see FIG. 3), nicotinic acid1H-NMR (see FIG. 4) and of LAE Niacin ion-pair Compounds1H-NMR (see FIG. 5). Because the peak shape and chemical shift of the lauroyl arginine ethyl ester in the ion pair compound are not changed greatly in the salt forming process of the LAE ion pair compound, but all hydrogen on the nicotinic acid has shift change, the spectral characteristics of the acid and base part are closer to the space distance compared with the original inorganic acid salt (namely LAE hydrochloride), the influence is generated, and therefore, the corresponding change is generated compared with the original LAE and the hydrochloride thereof, the acid and base part is not simply superposed, for example, washing and precipitating in purified waterWhen the solubility is changed, it shows that all hydrogen nuclei of lauroyl arginine ethyl ester have strong interaction with nicotinic acid, and form a stable single compound structure 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 analysis of molecular weight of Compounds by Artocylarginine Ethyl ester tartrate ions
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 niacin ion for the cation in the compound was 534.3, and the observed value coincided with the theoretical value.
Example five: preparation method for synthesizing ion pair compound by using 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 a 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 research Co., Ltd.) was dissolved in 50mL of water to prepare an aqueous sodium carbonate solution (A); 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 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: according to the microbubult dilution method specified by CLSI, the minimum drug concentration at which bacterial growth is inhibited after 24h of co-incubation of the drug with bacteria in a 96-well plate is the minimum inhibitory concentration of the drug.
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 culture medium CK1 without bacteria, a culture medium CK2 added with LAE (1000. mu.g/ml) and a normal growth control culture 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 with blank control625Wells 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 of the compound 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 lauroyl arginine ethyl ester ion pair or sodium methyl paraben, a positive fruit preservative, were added to the wells at various concentrations, approximately 100. mu.l per well, covered with a lid, and incubated in an incubator at 37 ℃ for 48 h. 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 concentration of 256 μ g/ml or more, and LAE-nicotinic acid ion pair inhibits the growth of Microbacterium at concentration of 512 μ g/ml or more. Both LAE and LAE ion pair can inhibit the growth of Aspergillus, LAE-formate ion pair, LAE-salicylate ion pair have inhibitory effect at a concentration of 128 μ g/ml or more, and LAE-nicotinic acid ion pair inhibit the growth of Microbacterium at a concentration of 256 μ g/ml or more.
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 2LAE and its ion pair Compounds results for the zone of inhibition of Penicillium
TABLE 3LAE 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 the LAE and the derivatives thereof is increased, although the bacteriostatic rate is correspondingly increased, the excessively 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 derivatives thereof belong to natural environment-friendly and nontoxic components, the bacteriostatic agent has the advantage of being friendly to human bodies when being added and used in high dosage 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 (9)
- Use of a LAE ion pair compound for the preparation of a mildewproof adhesive, wherein the LAE ion pair compound has a structural formula shown in formula (III) below;
the RCOO-The organic acid salt of (a) is selected from salicylates, ammonium formates, calcium formates, nicotinates, oxalates having antibacterial activity;wherein the LAE ion pair compound is prepared by the condensation reaction of:(1) heating and dissolving the compound shown in the formula (II), and then adding an organic acid salt solution of RCOO-;
(2) fully stirring and uniformly mixing, and carrying out condensation reaction under the condition of heating to 90 ℃ to obtain the LAE ion pair compound, wherein the condensation reaction is shown as the following reaction formula:
reaction formula (A);(3) after sufficient reaction, the reaction mixture is cooled to room temperature, washed and purified with purified water and then dried in vacuum, thereby preparing a purified LAE ion pair compound. - 2. Use according to claim 1, wherein the organic acid salt is selected from nicotinates, oxalates.
- 3. Use according to claim 1, characterized in that the antimildew adhesive is chosen from industrial adhesives, household adhesives, medical adhesives.
- 4. The use of claim 3, 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.
- 5. The use according to claim 4, wherein the LAE ion pair compound is present in the matrix solution of the mildewproof adhesive in an amount of 0.001 to 2% by mass.
- 6. The use of claim 5, wherein the LAE ion pair compound is present in the mildewcide binder in an amount of 0.001 to 0.01, 0.01 to 0.1, 0.05 to 0.1, 0.1 to 0.2, 0.1 to 1, 1 to 2, or 1.5 to 2 percent by weight.
- 7. The preparation method of the mildew-proof adhesive is characterized by comprising the following steps of:(1) heating and dissolving the compound shown in the formula (II), and then adding an organic acid salt solution of RCOO-;(2) fully stirring and uniformly mixing, and generating an LAE ion pair compound through the following condensation reaction under the condition of heating to 90 ℃, wherein the reaction is shown as the following reaction formula:
reaction formula (A);wherein the organic acid salt of RCOO-is selected from salicylate, ammonium formate, calcium formate, nicotinate, oxalate with antibacterial activity;(3) after full reaction, cooling to room temperature, washing with purified water, purifying, and vacuum drying 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. The method of claim 7, wherein the organic acid salt of RCOO-is prepared by: 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.
- 9. A mildewproof adhesive prepared by the method according to claim 7 or 8.
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