An organic acid silver acyl thiourea complex and a preparation method and application thereof

Abstract

The application provides an organic acid silver acyl thiourea complex and a preparation method and application thereof, and belongs to the technical field of organic polymer compounds. The organic acid silver acyl thiourea complex has a chemical formula of R 2 COOAg[NH2CSNHNHCOR 1 ] n , wherein R 1 is normal or isomeric alkyl with C5-C 17 ; R 2 is alkyl with C6-C 18 , or an unsaturated aliphatic hydrocarbon group, or a long-chain alkyl-substituted benzoic acid; and n is 1 or 2. The organic acid silver acyl thiourea complex provided by the application has good miscibility in oil-based paint and remarkable antibacterial effect.

Description

Technical Field

[0001] This invention belongs to the field of organic polymer compound technology, specifically relating to an organic acid silver acyl thiourea complex, its preparation method, and its application. Background Technology

[0002] Elemental silver and silver ion antibacterial agents possess broad antibacterial spectrum, high antibacterial efficiency, safety, and long-lasting action, making them widely used in the preparation of antibacterial materials. However, elemental silver and silver ions exhibit poor dispersibility in oil-based coating systems, affecting their antibacterial performance. Oil-soluble silver, when used as an antibacterial agent, offers unique advantages in solvent-based coatings, adhesives, and sealants, such as in high-end wooden furniture, epoxy flooring, and silicone adhesives and sealants.

[0003] In the prior art, patent document CN107855540A discloses a method for preparing oil-soluble silver nanoparticles, including the following steps: (1) dissolving β-cyclodextrin in N-methylpyrrolidone, adding 2-bromoisobutyryl bromide at 0°C, and reacting at room temperature to obtain the star-shaped macromolecular initiator 21Br-β-CD; (2) initiating the polymerization of tert-butyl acrylate monomers by ATRP polymerization of the star-shaped macromolecular initiator 21Br-β-CD to obtain multi-armed star-shaped β-CD-g-PtBA; (3) using multi-armed star-shaped β-CD-g-PtBA as a macromolecular initiator. (3) A multi-armed star-shaped block copolymer β-CD-g-[PtBA-b-Ps] was prepared by ATRP polymerization to initiate the polymerization of styrene monomers; (4) The multi-armed star-shaped block copolymer β-CD-g-[PtBA-b-Ps] was dissolved in dichloromethane, trifluoroacetic acid was added, and hydrolysis was carried out at room temperature to obtain the multi-armed star-shaped block copolymer β-CD-g-[PAA-b-Ps]; (5) The multi-armed star-shaped block copolymer β-CD-g-[PAA-b-Ps] was used as a monomolecular micelle template, and a soluble silver-containing compound was used as a precursor to prepare oil-soluble silver nanoparticles. This invention modifies the surface of Ag nanoparticles, enabling them to be uniformly dispersed in oily solvents and avoiding agglomeration. However, the preparation process of the product in this invention is complex, and the antibacterial effect is still uncertain and needs further research. Summary of the Invention

[0004] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows: An organic acid silver acyl thiourea complex, the chemical formula of which is: R 2 COOAg[NH2CSNHNHCOR 1 ] n , Among them, R 1 C5~C 17 n- or iso-alkyl groups; R2 C6~C 18 The alkyl group, or unsaturated aliphatic hydrocarbon group, or long-chain alkyl-substituted benzoic acid; n is 1 or 2.

[0005] A method for preparing an organic acid silver acyl thiourea complex includes the following steps: 1) Acylation of organic acyl chloride and aminothiourea at 20-30℃ produces fatty acylaminourea R. 1 CONHNHCSNH2, R 1 C5~C 17 Ortho- or iso-alkyl groups; 2) React organic acid salts with silver nitrate to produce silver fatty acid R. 2 COOAg, the chemical formula of the organic acid salt is R 2 COOM, R 2 C6~C 18 The alkyl group, or unsaturated aliphatic hydrocarbon group, or benzoic acid substituted with a long-chain alkyl group, where M is a sodium or potassium atom; 3) The above product R 1 CONHNHCSNH2 and R 2 COOAg reacts in an organic solvent to form the organic acid silver acyl thiourea complex R. 2 COOAg [NH2CSNHNHCOR 1 ] n n is 1 or 2.

[0006] Optionally, the organic acyl chloride is hexanoyl chloride, octanoyl chloride, isooctanoyl chloride, dodecanoyl chloride, hexadecanoyl chloride, or octadecanoyl chloride.

[0007] Optionally, the organic acid salt is a sodium or potassium salt of hexanoic acid, octanoic acid, isooctanoic acid, dodecanoic acid, hexadecanoic acid, octadecanoic acid, ricinoleic acid, oleic acid, linoleic acid, or alkylbenzoic acid.

[0008] Optionally, the organic solvent is acetone or toluene.

[0009] The present invention also provides an application of the above-mentioned organic acid silver acyl thiourea complex in the preparation of oil-based antibacterial coatings.

[0010] Optionally, the organic acid silver acyl thiourea complex is dissolved in an oil-based antibacterial coating, wherein the mass percentage of silver is 0.01% or more.

[0011] Compared with the prior art, the beneficial effects of the present invention are as follows: Based on the above technical solution, the present invention provides an organic acid silver acyl thiourea complex. Since the silver ions are surrounded by long-chain hydrocarbon chains, they have a strong affinity for organic matter. Therefore, they have good miscibility with organic solvents and film-forming agents, and thus can exert a good antibacterial effect.

[0012] The synthesis principle of the organic acid silver acyl thiourea complex of the present invention is as follows:

[0013] The organic acid silver acyl thiourea complex obtained by this invention can be used to prepare oil-based antibacterial coatings, antibacterial adhesives, and antibacterial sealants. It overcomes the shortcomings of poor miscibility or immiscibility of elemental silver or inorganic silver ions in oil-based coatings, making the antibacterial products more uniform and stable. While maintaining the original properties of the antibacterial products such as adhesion, hardness, and durability, it also has antibacterial function, and the antibacterial performance can reach Grade I, thereby broadening the application range of silver. Detailed Implementation

[0014] To better understand the present invention, the following embodiments further illustrate the content of the invention, but the scope of protection of the present invention is not limited to the following embodiments. Numerous specific details are set forth in the following description to provide a more thorough understanding of the invention. However, it will be apparent to those skilled in the art that the present invention can be practiced without one or more of these details.

[0015] Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without inventive effort are within the scope of protection of this invention.

[0016] In all examples shown and discussed herein, any specific values ​​should be interpreted as merely exemplary and not as limitations. Therefore, other examples of exemplary embodiments may have different values.

[0017] Unless otherwise specified, all raw materials are derived from commercially available products and do not contain any unspecified components other than unavoidable impurities.

[0018] Example 1 A straight condenser connected to an alkali absorption device and a dropping funnel were installed on a reaction vessel. Cooling water at 10°C was introduced, and an appropriate amount of acetone was added to the vessel. Aminothiourea was added with stirring, and after dissolution, an equimolar amount of hexanoyl chloride in acetone was slowly added dropwise at 20°C. After the addition was complete, the reaction was continued for 40 minutes. The alkali absorption device was then removed and a vacuum system was connected. The system was heated to 60°C, and the solvent was distilled off under pressure. Then, toluene was added to dissolve the solvent to obtain hexanoylaminothiourea (C5H). 11 CONHNHCSNH2) solution; A sodium hexanoate aqueous solution is reacted with an equimolar silver nitrate aqueous solution at 30°C to form a silver hexanoate precipitate. The precipitate is then filtered, washed, and dried to obtain silver hexanoate. At 30°C, dry silver hexanoate is added to a toluene solution of hexanothiourea and stirred until dissolved. The molar ratio of silver hexanoate to hexanothiourea is 1:1. The resulting solution is then diluted to an organic silver solution with a silver concentration of 5%, which is the organic silver antibacterial agent.

[0019]

[0020] Example 2 A straight condenser connected to an alkali absorption device and a dropping funnel were installed on a reaction vessel. Cooling water at 10°C was introduced, and an appropriate amount of acetone was added to the vessel. Aminothiourea was added with stirring, and after dissolution, an equimolar amount of octanoyl chloride in acetone was slowly added dropwise at 20°C. After the addition was complete, the reaction was continued for 40 minutes. The alkali absorption device was then removed and a vacuum system was connected. The system was heated to 60°C, and the solvent was distilled off under pressure. Toluene was then added to dissolve the solvent to obtain octanoyl aminothiourea (C7H). 15 CONHNHCSNH2) solution; A sodium hexanoate aqueous solution is reacted with an equimolar silver nitrate aqueous solution at 30°C to form a silver hexanoate precipitate. The precipitate is then filtered, washed, and dried to obtain silver hexanoate. At 30°C, dry silver hexanoate is added to a toluene solution of octanoaminothiourea and stirred until dissolved. The molar ratio of silver hexanoate to octanoaminothiourea is 1:2. The resulting solution is then diluted to an organic silver solution with a silver concentration of 5%, which is the organic silver antibacterial agent.

[0021]

[0022] Example 3 A straight condenser and dropping funnel connected to an alkali absorption device were installed on a reaction vessel. Cooling water at 10°C was introduced, and an appropriate amount of acetone was added to the vessel. Aminothiourea was added with stirring, and after dissolution, an equimolar amount of dodecyl chloride in acetone was slowly added dropwise at 30°C. After the addition was complete, the reaction was continued for 40 minutes. The alkali absorption device was then removed and a vacuum system was connected. The system was heated to 60°C, and the solvent was distilled off under pressure. Toluene was then added to dissolve the solvent to obtain dodecyl aminothiourea (C). 11 H 23 CONHNHCSNH2) solution; An aqueous solution of sodium octylbenzoate was reacted with an equimolar aqueous solution of silver nitrate at 30°C to produce a precipitate of silver octylbenzoate. The precipitate was then filtered, washed, and dried to obtain silver octylbenzoate. At 40°C, dry silver octylbenzoate is added to a toluene solution of dodecylaminothiourea and stirred until dissolved. The molar ratio of silver octylbenzoate to dodecylaminothiourea is 1:1. The resulting solution is diluted to an organic silver solution with a silver concentration of 5%, which is an organic silver antibacterial agent.

[0023]

[0024] Example 4 A straight condenser and dropping funnel connected to an alkali absorption device were installed on a reaction vessel. Cooling water at 10°C was introduced, and an appropriate amount of acetone was added to the vessel. Aminothiourea was added with stirring, and after dissolution, an equimolar amount of octadecyl chloride in acetone was slowly added dropwise at 30°C. After the addition was complete, the reaction was continued for 40 minutes. The alkali absorption device was then removed and a vacuum system was connected. The system was heated to 60°C, and the solvent was distilled off under pressure. Toluene was then added to dissolve the solvent to obtain octadecyl aminothiourea (C...). 17 H 35 CONHNHCSNH2) solution; An aqueous solution of sodium dodecylbenzoate was reacted with an equimolar aqueous solution of silver nitrate at 30°C to produce a precipitate of silver dodecylbenzoate. The precipitate was then filtered, washed, and dried to obtain silver dodecylbenzoate. At 50°C, dry silver dodecylbenzoate is added to a toluene solution of octadecylaminothiourea and stirred until dissolved. The molar ratio of silver dodecylbenzoate to octadecylaminothiourea is 1:2. The resulting solution is diluted to an organic silver solution with a silver concentration of 5%, which is an organic silver antibacterial agent.

[0025] Example 5

[0026] A straight condenser connected to an alkali absorption device and a dropping funnel were installed on a reaction vessel. Cooling water at 10°C was introduced, and an appropriate amount of acetone was added to the vessel. Aminothiourea was added with stirring, and after dissolution, an equimolar amount of oleic acid acyl chloride in acetone was slowly added dropwise at 30°C. After the addition was complete, the reaction was continued for 40 minutes. The alkali absorption device was then removed, and a vacuum system was connected. The system was heated to 60°C, and the solvent was distilled off under pressure. Toluene was then added to dissolve the solvent to obtain oleic acid acyl aminothiourea (C...). 17 H 33 CONHNHCSNH2) solution; An aqueous solution of sodium linoleate is reacted with an equimolar aqueous solution of silver nitrate at 40°C to form a precipitate of silver linoleate. The precipitate is then filtered, washed, and dried to obtain silver linoleate.

[0027] At 50°C, dry silver linoleate is added to a toluene solution of oleic acid thiourea and stirred until dissolved. The molar ratio of silver linoleate to oleic acid thiourea is 1:2. The resulting solution is then diluted to an organic silver solution with a silver concentration of 5%, which is the organic silver antibacterial agent.

[0028]

[0029] Example 6 A straight condenser and dropping funnel connected to an alkali absorption device were installed on a reaction vessel. Cooling water at 10°C was introduced, and an appropriate amount of acetone was added to the vessel. Aminothiourea was added with stirring, and after dissolution, an equimolar amount of hexadecyl chloride in acetone was slowly added dropwise at 30°C. After the addition was complete, the reaction was continued for 40 minutes. The alkali absorption device was then removed and a vacuum system was connected. The system was heated to 60°C, and the solvent was distilled off under pressure. Toluene was then added to dissolve the solvent to obtain hexadecyl aminothiourea (C...). 15 H 31 CONHNHCSNH2) solution; An aqueous solution of sodium ricinoleate was reacted with an equimolar aqueous solution of silver nitrate at 40°C to form a precipitate of silver ricinoleate. The precipitate was then filtered, washed, and dried to obtain silver ricinoleate. At 50°C, dry silver ricinoleate is added to a toluene solution of hexadecylaminothiourea and stirred until dissolved. The molar ratio of silver ricinoleate to hexadecylaminothiourea is 1:2. The resulting solution is then diluted to an organic silver solution with a silver concentration of 5%, which is the organic silver antibacterial agent.

[0030]

[0031] Next, the content of the evaluation experiment will be explained.

[0032] Take 0.2g, 0.4g and 0.6g of the organic silver antibacterial agent prepared in Examples 1, 3 and 6 respectively, and add them to 100g of oil-based polyester paint (commercially available) and 100g of two-component epoxy resin floor paint (commercially available), respectively. After mixing, antibacterial samples are formed and the following performance tests are performed.

[0033] 1. Antibacterial performance test Antibacterial samples were coated onto smooth wood chips (100mm×100mm×18mm), dried, and the film thickness was 50±5μm to obtain the coating.

[0034] The antibacterial properties of the coating were determined according to HG / T 3950-2007, and the results are shown in the table below:

[0035] The above results show that when the organic silver antibacterial agent prepared by the present invention is added to commercially available oil-based polyester paint and two-component epoxy resin floor paint respectively, the oil-based polyester paint with a silver content of 100 ppm and the epoxy floor paint with a silver content of 100 ppm and 200 ppm have a bacterial inhibition rate of ≥90%, reaching Class II antibacterial performance; the oil-based polyester paint with a silver content of 200 ppm and 300 ppm and the epoxy floor paint with a silver content of 300 ppm have a bacterial inhibition rate of ≥99%, reaching Class I antibacterial performance. This indicates that the organic silver antibacterial agent of the present invention has good antibacterial properties.

[0036] 2. Compatibility effect test of organic silver antibacterial agent in oil-based coatings Static state test: Visually observe the state of the antibacterial sample in the container, and record whether phenomena such as delamination, precipitation, and skinning occur.

[0037] Brushing state test: Visually observe the state of the antibacterial sample after being brushed on a wood piece and dried, and record whether phenomena such as abnormal surface texture, bubbling, peeling, flaking, and cracking occur.

[0038] Leveling property test: According to the brushing method in GB1750-79(89) Test Method for Leveling Property of Coatings, observe and record whether phenomena such as flow marks and sagging occur in the antibacterial sample.

[0039] In each of the above tests, if none of the above phenomena are observed, the corresponding test result is judged as qualified; if any of the above phenomena is observed, the corresponding test result is judged as unqualified.

[0040] The test results are shown in the following table:

[0041] The results show that when the organic silver antibacterial agent prepared by the present invention is applied to commercially available oil-based polyester paint and epoxy floor paint respectively, the obtained paint products have no phenomena such as delamination, precipitation and skinning under the static state, no phenomena such as abnormal surface texture, bubbling, peeling, flaking and cracking under the brushing state, and no phenomena such as flow marks and sagging in the leveling property test, and all tests are qualified. The above results indicate that the organic silver antibacterial agent prepared by the present invention can be well dissolved in oil-based coatings, has excellent miscibility, and will not affect the appearance and brushing performance of the oil-based coatings.

[0042] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present invention rather than to limit them. Other modifications or equivalent substitutions made by those of ordinary skill in the art to the technical solutions of the present invention shall fall within the scope of the claims of the present invention as long as they do not depart from the spirit and scope of the technical solutions of the present invention.

Claims

1. An organic acid silver acyl thiourea complex, characterized in that: The preparation is carried out using the following method: 1) Acylation of organic acyl chloride and aminothiourea, using acetone as a solvent, at 20-30℃ produces fatty acylaminourea R. 1 CONHNHCSNH2, R 1 C5~C 17 The organic acyl chloride is a normal or isoalkyl group; wherein the organic acyl chloride is hexanoyl chloride, octanoyl chloride, isooctanoyl chloride, dodecanoyl chloride, hexadecanoyl chloride or octadecanoyl chloride; 2) React organic acid salts with silver nitrate to produce silver fatty acid R. 2 COOAg; wherein the organic acid salt is a sodium or potassium salt of hexanoic acid, octanoic acid, isooctanoic acid, dodecanoic acid, hexadecanoic acid, octadecanoic acid, ricinoleic acid, oleic acid, linoleic acid or alkylbenzoic acid, R 2 Corresponding to the organic acid salt portion; 3) Add fatty amide R 1 CONHNHCSNH2 and Fatty Acid Silver R 2 COOAg reacts in an organic solvent to form the organic acid silver acyl thiourea complex R. 2 COOAg [NH2CSNHNHCOR 1 ] n n is 1 or 2.

2. The organic acid silver acyl thiourea complex as described in claim 1, characterized in that: The organic solvents are acetone and toluene.

3. The application of the organic acid silver acyl thiourea complex as described in claim 1 or 2 in the preparation of oil-based antibacterial coatings.

4. The application of the organic acid silver acyl thiourea complex as described in claim 3 in the preparation of oil-based antibacterial coatings, characterized in that: The organic acid silver acyl thiourea complex is soluble in oil-based antibacterial coatings, and its silver content is greater than 0.01% by mass.

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