Organic acid silver acylthiourea complex as well as preparation method and application thereof

Abstract

The invention provides an organic acid silver acylthiourea complex as well as a preparation method and application thereof, and belongs to the technical field of organic high-molecular compounds. The chemical formula of the organic acid silver acylthiourea complex is R2COOAg [NH2SNHNHCOR1] n, in the chemical formula, R1 is a normal or isomeric alkyl group of C5-C17, and R2 is an alkyl group of C5-C17. R2 is alkyl of C6-C18, or unsaturated aliphatic alkyl, or benzoic acid substituted by long-chain alkyl; and n is 1 or 2. The organic acid silver acylthiourea complex provided by the invention has a good miscible effect in oil paint and a remarkable antibacterial effect.

Description

Technical Field

[0001] The invention belongs to the technical field of organic polymer compounds, and in particular relates to an organic acid silver acyl thiourea complex and a preparation method and application thereof. Background Art

[0002] Elemental silver and silver ion antimicrobial agents have the characteristics of broad antimicrobial spectrum, high antimicrobial efficiency, safety and long action time, and are widely used in the preparation of antimicrobial materials. However, elemental silver and silver ions have poor dispersibility in oily coating systems, which affects their antimicrobial properties. Oil-soluble silver has special advantages in solvent-based coating binders and sealants when used as an antimicrobial agent, such as high-end wooden furniture, epoxy flooring, silicone binders and sealants, etc.

[0003] In the prior art, patent document CN107855540A discloses a method for preparing oil-soluble silver nanoparticles, comprising the following steps: (1) dissolving β-cyclodextrin in N-methylpyrrolidone, adding 2-bromoisobutyryl bromide at 0°C, reacting at room temperature to obtain a star-shaped macromolecular initiator 21Br-β-CD; (2) initiating polymerization of tert-butyl acrylate monomers with the star-shaped macromolecular initiator 21Br-β-CD through an ATRP polymerization reaction to obtain a multi-arm star-shaped β-CD-g-PtBA; (3) using the multi-arm star-shaped β-CD-g-PtBA as a macromolecular initiator. The polymerization of styrene monomer is initiated by ATRP polymerization reaction to obtain a multi-arm star-shaped block copolymer β-CD-g-[PtBA-b-Ps]; (4) the multi-arm star-shaped block copolymer β-CD-g-[PtBA-b-Ps] is dissolved in dichloromethane, trifluoroacetic acid is added, and hydrolyzed at room temperature to obtain a multi-arm star-shaped block copolymer β-CD-g-[PAA-b-Ps]; (5) the multi-arm star-shaped block copolymer β-CD-g-[PAA-b-Ps] is used as a single-molecule micelle template, and a soluble silver-containing compound is used as a precursor to obtain oil-soluble silver nanoparticles. This invention modifies the surface of Ag nanoparticles so that they can be evenly dispersed in an oily solvent to avoid agglomeration effects. However, the preparation process of the product in this invention is complicated, and the antibacterial effect is still uncertain, which needs further study. Summary of the invention

[0004] In order to solve the above technical problems, the technical solution adopted by the present invention is:

[0005] An organic acid silver acylthiourea complex, the chemical formula of which is:

[0006] R 2 COOAg[NH2SNHNHCOR 1 ] n ,

[0007] Among them, R 1C5~C 17 The normal or isomeric alkyl group; R 2 C6~C 18 An alkyl group, or an unsaturated aliphatic hydrocarbon group, or a long-chain alkyl-substituted benzoic acid; n is 1 or 2.

[0008] A method for preparing an organic acid silver acylthiourea complex comprises the following steps:

[0009] 1) Acylate the organic acid chloride and thiosemicarbazide to generate fatty acyl semicarbazide R at 20-30°C 1 CONHNHSNH2,R 1 C5~C 17 normal or isomeric alkyl groups;

[0010] 2) Reacting organic acid salt with silver nitrate to generate fatty acid silver R 2 COOAg, the chemical formula of the organic acid salt is R 2 COOM, R 2 C6~C 18 An alkyl group, or an unsaturated aliphatic hydrocarbon group, or a benzoic acid substituted with a long-chain alkyl group, and M is a sodium or potassium atom;

[0011] 3) The above product R 1 CONHNHSNH2 and R 2 COOAg reacts in an organic solvent to form an organic acid silver acylthiourea complex R 2 COOAg[NH2SNHNHCOR 1 ] n , n is 1 or 2.

[0012] Optionally, the organic acid chloride is hexanoyl chloride, octanoyl chloride, isooctanoyl chloride, dodecanoyl chloride, hexadecanoyl chloride or octadecanoyl chloride.

[0013] Optionally, the organic acid salt is a sodium salt or potassium salt of caproic acid, caprylic acid, isooctanoic acid, dodecanoic acid, hexadecanoic acid, octadecanoic acid, ricinoleic acid, oleic acid, linoleic acid or alkylbenzoic acid.

[0014] Optionally, the organic solvent is acetone and toluene.

[0015] The present invention also provides an application of the organic acid silver acylthiourea complex in the preparation of oily antibacterial coatings.

[0016] Optionally, the organic acid silver acylthiourea complex is dissolved in an oily antibacterial coating, and the mass percentage of the silver element is greater than 0.01%.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] Based on the above technical scheme, the present invention provides an organic acid silver acyl thiourea complex. Since the silver ions are surrounded by long hydrocarbon chains and have a strong affinity for organic matter, they have good miscibility with organic solvents and film-forming agents, and can therefore exert a good antibacterial effect.

[0019] The synthesis principle of the organic acid silver acyl thiourea complex of the present invention is as follows:

[0020] R 1 COCl + NH2NHSNH2 → R 1 CONHNHSNH2(1)R 2 COOH+AgNO3→R 2 COOAg(2)nR 1 CONHNHSNH2+R 2 COOAg→R 2 COOAg[NH2SNHNHCOR 1 ] n (3)

[0021] The organic acid silver acylthiourea complex obtained by the invention can be used to prepare oily antibacterial coatings, antibacterial adhesives and antibacterial sealants, and overcomes the shortcomings of poor miscibility or incompatibility of elemental silver or inorganic silver ions in oily coatings, so that the antibacterial products have good uniformity and stability, and have antibacterial functions while maintaining the original properties of the antibacterial products such as adhesion, hardness and durability, and the antibacterial performance can reach level I, thereby broadening the application range of silver. DETAILED DESCRIPTION

[0022] In order to better understand the present invention, the content of the present invention is further clearly set forth in conjunction with the embodiments below, but the protection content of the present invention is not limited to the following embodiments. In the following description, a large number of specific details are provided in order to provide a more thorough understanding of the present invention. However, it is obvious to those skilled in the art that the present invention can be implemented without one or more of these details.

[0023] Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in the field without making any creative work shall fall within the scope of protection of the present invention.

[0024] In all examples shown and discussed herein, any specific values ​​should be interpreted as merely exemplary and not as limiting. Therefore, other examples of the exemplary embodiments may have different values.

[0025] Unless otherwise specified, all raw materials are from commercially available products and do not contain other unspecified components except inevitable impurities unless otherwise specified.

[0026] Example 1

[0027] A straight condenser and a dropping funnel connected to an alkali solution absorption device are installed on the reaction vessel, and 10°C cooling water is passed into the vessel. An appropriate amount of acetone is added to the container, and thiosemicarbazide is added under stirring. After dissolution, an equimolar amount of hexanoyl chloride acetone solution is slowly added dropwise at 20°C. After the addition is completed, the reaction is continued for 40 minutes. The alkali solution absorption device is removed and a vacuum system is connected. After the system is heated to 60°C, the solvent is distilled off under pressure, and then toluene is added to dissolve the hexanoyl thiosemicarbazide (C5H 11 CONHNHSNH2) solution;

[0028] The sodium hexanoate aqueous solution and the equimolar silver nitrate aqueous solution are reacted at 30°C to generate a silver hexanoate precipitate, which is filtered, washed and dried to obtain silver hexanoate;

[0029] At 30°C, add dried silver hexanoate to a toluene solution of hexanoylthiosemicarbazide and stir to dissolve, the molar ratio of silver hexanoate to hexanoylthiosemicarbazide being 1:1, and dilute the formed solution to an organic silver solution having a silver concentration of 5%, i.e., an organic silver antibacterial agent.

[0030] C5H 11 COCl + NH2NHSNH2 → C5H 11 CONHNHSNH2+HCl

[0031] C5H 11 COONa + AgNO3 → C5H 11 COO

[0032] C5H 11 CONHNHSNH2+C5H 11 COOAg→C5H 11 COOAgNH2SNHNHCOC5H 11

[0033] Example 2

[0034] A straight condenser and a dropping funnel connected to an alkali solution absorption device are installed on the reaction vessel, and 10°C cooling water is passed into the vessel. An appropriate amount of acetone is added to the container, and thiosemicarbazide is added under stirring. After dissolution, an equimolar amount of octanoyl chloride acetone solution is slowly added dropwise at 20°C. After the addition is completed, the reaction is continued for 40 minutes. The alkali solution absorption device is removed and a vacuum system is connected. After the system is heated to 60°C, the solvent is distilled off under pressure, and then toluene is added to dissolve to obtain octanoyl thiosemicarbazide (C7H 13 CONHNHSNH2) solution;

[0035] The sodium hexanoate aqueous solution and the equimolar silver nitrate aqueous solution are reacted at 30°C to generate a silver hexanoate precipitate, which is filtered, washed and dried to obtain silver hexanoate;

[0036] At 30°C, add dried silver hexanoate to a toluene solution of octanoylthiosemicarbazide and stir to dissolve, the molar ratio of silver hexanoate to octanoylthiosemicarbazide being 1:2, and dilute the formed solution to an organic silver solution having a silver concentration of 5%, i.e., an organic silver antibacterial agent.

[0037] C7H 13 COCl + NH2NHSNH2 → C7H 13 CONHNHSNH2+HCl C5H 11 COONa + AgNO3 → C5H 11 7H 13 CONHNHSNH2+C5H 11 COOAg→

[0038] C5H 11 COOAg[NH2SNHNHCOC7H 13 ]2

[0039] Example 3

[0040] A straight condenser and a dropping funnel connected with an alkali solution absorption device are installed on the reaction container, and 10°C cooling water is passed into the container. An appropriate amount of acetone is added to the container, and thiosemicarbazide is added under stirring. After dissolution, an equimolar amount of acetone solution of dodecanoyl chloride is slowly added dropwise at 30°C. After the addition is completed, the reaction is continued for 40 minutes. The alkali solution absorption device is removed and a vacuum system is connected. After the system is heated to 60°C, the solvent is distilled off under pressure, and then toluene is added to dissolve to obtain dodecanoyl thiosemicarbazide (C 11 H 23 CONHNHSNH2) solution;

[0041] reacting an aqueous solution of sodium octylbenzoate with an equimolar aqueous solution of silver nitrate at 30° C. to generate a silver octylbenzoate precipitate, which is then filtered, washed, and dried to obtain silver octylbenzoate;

[0042] At 40°C, add dried silver octylbenzoate to a toluene solution of dodecanoylaminothiourea and stir to dissolve, the molar ratio of silver octylbenzoate to dodecanoylaminothiourea being 1:1, and dilute the formed solution to an organic silver solution having a silver concentration of 5%, i.e., an organic silver antibacterial agent.

[0043] C 11 H 23 COCl + NH2NHSNH2 → C 11 H 23 CONHNHSNH2+HCl C8H 17 PhCOONa+AgNO3→C8H 17 PhCOOAgC 11 H 23CONHNHSNH2+C8H 17 PhCOOAg→

[0044] 8H 17 PhCOOAg NH2SNHNHCOC 11 H 23

[0045] Example 4

[0046] A straight condenser and a dropping funnel connected with an alkali solution absorption device are installed on the reaction container, and 10°C cooling water is passed into the container. An appropriate amount of acetone is added to the container, and semicarbazide is added under stirring. After dissolution, an equimolar amount of acetone solution of octadecanoyl chloride is slowly added dropwise at 30°C. After the addition is completed, the reaction is continued for 40 minutes. The alkali solution absorption device is removed and a vacuum system is connected. After the system is heated to 60°C, the solvent is distilled off under pressure, and then toluene is added to dissolve to obtain octadecanoyl semicarbazide (C 17 H 35 CONHNHSNH2) solution;

[0047] reacting an aqueous sodium dodecylbenzoate solution with an equimolar aqueous silver nitrate solution at 30° C. to generate a silver dodecylbenzoate precipitate, which is then filtered, washed, and dried to obtain silver dodecylbenzoate;

[0048] At 50°C, add dried silver dodecylbenzoate to a toluene solution of octadecanoylthiocarbamide and stir to dissolve. The molar ratio of silver dodecylbenzoate to octadecanoylthiocarbamide is 1:2. Dilute the resulting solution to an organic silver solution with a silver concentration of 5%, i.e., an organic silver antibacterial agent. 17 H 35 COCl + NH2NHSNH2 → C 17 H 35 CONHNHSNH2+HCl

[0049] C 11 H 23 COONa+AgNO3→C 11 H 23 COOAg 11 H 23 COOAg+2C 17 H 35 CONHNHSNH2 →

[0050] C 11 H 23 COOAg[NH2SNHNHCOC 17 H 35 ]2

[0051] Example 5

[0052] A straight condenser and a dropping funnel connected with an alkali solution absorption device are installed on the reaction container, and 10°C cooling water is passed into the container. An appropriate amount of acetone is added to the container, and thiosemicarbazide is added under stirring. After dissolution, an equimolar amount of oleic acid chloride acetone solution is slowly added dropwise at 30°C. After the addition is completed, the reaction is continued for 40 minutes. The alkali solution absorption device is removed and a vacuum system is connected. After the system is heated to 60°C, the solvent is distilled off under pressure, and then toluene is added to dissolve to obtain oleic acid thiosemicarbazide (C 17 H 33 CONHNHSNH2) solution;

[0053] The sodium linoleate aqueous solution and an equimolar silver nitrate aqueous solution are reacted at 40°C to generate a silver linoleate precipitate, which is then filtered, washed and dried to obtain silver linoleate.

[0054] At 50°C, add dried silver linoleate to a toluene solution of oleic acid acylaminothiourea and stir to dissolve, the molar ratio of silver linoleate to oleic acid acylaminothiourea being 1:2, and dilute the formed solution to an organic silver solution having a silver concentration of 5%, i.e., an organic silver antibacterial agent.

[0055] C 17 H 33 COCl + NH2NHSNH2 → C 17 H 33 CONHNHSNH2+HCl

[0056] C 17 H 31 COONa+AgNO3→C 17 H 32 COOAg 17 H 31 COOAg+2C 17 H 33 CONHNHSNH2 →

[0057] C 17 H 31 COOAg[NH2SNHNHCOC 17 H 33 ]2

[0058] Example 6

[0059] A straight condenser and a dropping funnel connected with an alkali solution absorption device are installed on the reaction container, and 10°C cooling water is passed into the container. An appropriate amount of acetone is added to the container, and thiosemicarbazide is added under stirring. After dissolution, an equimolar amount of acetone solution of hexadecanoyl chloride is slowly added dropwise at 30°C. After the addition is completed, the reaction is continued for 40 minutes. The alkali solution absorption device is removed and a vacuum system is connected. After the system is heated to 60°C, the solvent is distilled off under pressure, and then toluene is added to dissolve to obtain hexadecanoyl thiosemicarbazide (C 15 H31 CONHNHSNH2) solution;

[0060] The sodium ricinoleate aqueous solution and an equimolar silver nitrate aqueous solution are reacted at 40°C to generate a ricinoleate silver precipitate, which is filtered, washed and dried to obtain ricinoleate silver;

[0061] At 50°C, add dried silver ricinoleate to a toluene solution of hexadecanoylaminothiourea and stir to dissolve, the molar ratio of silver ricinoleate to hexadecanoylaminothiourea being 1:2, and dilute the formed solution to an organic silver solution having a silver concentration of 5%, i.e., an organic silver antibacterial agent.

[0062] C 15 H 31 COCl + NH2NHSNH2 → C 15 H 31 CONHNHSNH2+HCl

[0063] C 17 H 33 COONa+AgNO3→C 17 H 33 COOAg 17 H 33 COOAg+2C 15 H 31 CONHNHSNH2 →

[0064] C 17 H 33 COOAg[NH2SNHNHCOC 15 H 31 ]2

[0065] Next, the contents of the evaluation test will be described.

[0066] Take 0.2 g, 0.4 g and 0.6 g of the organic silver antibacterial agent prepared in Example 1, Example 3 and Example 6, respectively, add them to 100 g of commercially available oily polyester paint and 100 g of commercially available two-component epoxy resin floor paint, mix them to form antibacterial samples, and perform the following performance tests.

[0067] 1. Antibacterial performance test

[0068] The antibacterial samples were applied on smooth wood pieces (100 mm×100 mm×18 mm) and dried to a film thickness of 50±5 μm to obtain a coating.

[0069] Referring to HG / T 3950-2007, the antibacterial performance of the coating was determined, and the results are shown in the following table:

[0070]

[0071] The above results show that when the organic silver antibacterial agent prepared by the present invention is added to commercially available oily polyester paint and two-component epoxy resin floor paint, the antibacterial rate of the oily polyester paint containing 100ppm silver and the epoxy floor paint containing 100ppm and 200ppm silver is ≥90%, and the antibacterial performance reaches Class II; the antibacterial rate of the oily polyester paint containing 200ppm and 300ppm silver and the epoxy floor paint containing 300ppm silver is ≥99%, and the antibacterial performance reaches Class I. This shows that the organic silver antibacterial agent of the present invention has good antibacterial performance.

[0072] 2. Compatibility test of organic silver antimicrobial agent in oil-based coatings

[0073] Static state test: Visually observe the state of the antibacterial sample in the container and record whether stratification, precipitation, crusting, etc. occur.

[0074] Coating status test: Visually observe the state of the antibacterial sample after it is coated on the wood chips and dried, and record whether there are abnormal surface texture, bubbling, peeling, peeling, cracking, etc.

[0075] Leveling test: According to the brush coating method in GB1750-79 (89) coating leveling test method, observe and record whether the antibacterial sample has flow marks, sagging and other phenomena.

[0076] In each of the above tests, if the above phenomenon is not observed, the corresponding test result is judged to be qualified; if any of the above phenomena is observed, the corresponding test result is judged to be unqualified.

[0077] The test results are shown in the following table:

[0078]

[0079] The results show that the organic silver antibacterial agent prepared by the present invention is applied to commercially available oily polyester paint and epoxy floor paint, respectively. The obtained paint products have no delamination, precipitation, crusting and other phenomena in the static state, no abnormal surface texture, bubbling, peeling, peeling, cracking and other phenomena in the brushing state, no flow marks, sagging and other phenomena in the leveling test, and all tests are qualified. The above results show that the organic silver antibacterial agent prepared by the present invention can be well dissolved in oily paint, has good miscibility, and will not affect the appearance and brushing performance of oily paint.

[0080] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Other modifications or equivalent substitutions made to the technical solution of the present invention by ordinary technicians in the field should be included in the scope of the claims of the present invention as long as they do not depart from the spirit and scope of the technical solution of the present invention.

Claims

1. An organic acid silver acylthiourea complex, characterized in that: Its chemical formula is: R 2 COOAg[NH2SNNHHCOR 1 ] n , Among them, R 1 C5~C 17 The normal or isomeric alkyl group; R 2 C6~C 18 An alkyl group, or an unsaturated aliphatic hydrocarbon group, or a long-chain alkyl-substituted benzoic acid; n is 1 or 2.

2. A method for preparing an organic acid silver acylthiourea complex, comprising the following steps: 1) Acylate organic acyl chloride and thiosemicarbazide to generate fatty acylsemicarbazide R at 20-30℃ 1 CONHNHSNH2,R 1 C5~C 17 normal or isomeric alkyl groups; 2) React the organic acid salt with silver nitrate to generate fatty acid silver R 2 COOAg, the chemical formula of the organic acid salt is R 2 COOM, R 2 C6~C 18 An alkyl group, or an unsaturated aliphatic hydrocarbon group, or a benzoic acid substituted with a long-chain alkyl group, and M is a sodium or potassium atom; 3) The above product R 1 CONHNHSNH2 and R 2 COOAg reacts in an organic solvent to form an organic acid silver acylthiourea complex R 2 COOAg [NH2SNHNHCOR 1 ] n , n is 1 or 2.

3. The method for preparing an organic acid silver acylthiourea complex as claimed in claim 2, characterized in that: The organic acid chloride is hexanoyl chloride, octanoyl chloride, isooctanoyl chloride, dodecanoyl chloride, hexadecanoyl chloride or octadecanoyl chloride.

4. The method for preparing an organic acid silver acylthiourea complex as claimed in claim 3, characterized in that: The organic acid salt is a sodium salt or potassium salt of caproic acid, caprylic acid, isooctanoic acid, dodecanoic acid, hexadecanoic acid, octadecanoic acid, ricinoleic acid, oleic acid, linoleic acid or alkylbenzoic acid.

5. The method for preparing an organic acid silver acylthiourea complex as claimed in claim 4, characterized in that: The organic solvents are acetone and toluene.

6. Use of an organic acid silver acyl thiourea complex as claimed in claim 5 or an organic acid silver acyl thiourea complex obtained by the preparation method of an organic acid silver acyl thiourea complex as claimed in any one of claims 2 to 4 in the preparation of an oily antibacterial coating.

7. Use of an organic acid silver acylthiourea complex as claimed in claim 6 in the preparation of an oily antibacterial coating, characterized in that: The organic acid silver acylthiourea complex is dissolved in the oily antibacterial coating, and the mass percentage of the silver element is above 0.01%.

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