Antibacterial agent as well as preparation method and application thereof

Abstract

The invention provides an antibacterial agent as well as a preparation method and application thereof. The structural formula of the antibacterial agent is as shown in a formula (I): # imgabs0 # formula (I); wherein n is an integer of 40-60, R is residues of hexamethylenediamine, m-xylylenediamine, p-xylylenediamine, 4, 4 '-diaminodicyclohexylmethane and the like, and X is any one of a benzene ring, a furan ring or # imgabs 1 #; wherein a is an integer from 4 to 6; the antibacterial agent provided by the invention not only has an excellent antibacterial effect, but also has good hydrophobic performance and high temperature resistance, meanwhile, the preparation process is good in controllability and high in yield, and the antibacterial agent has good long-acting antibacterial property, has the advantages of wide antibacterial range, safety, reliability, no peculiar smell and the like, is low in harm and pollution degree to human bodies and the environment, and is suitable for industrial production. Wide application prospects are realized.

Description

Technical Field

[0001] The present invention relates to the technical field of antimicrobial agents, and in particular to an antimicrobial agent and a preparation method and application thereof. Background Art

[0002] Antimicrobial agents are chemical substances that can keep the growth or reproduction of certain microorganisms (bacteria, fungi, yeasts, algae and viruses, etc.) below the necessary level for a certain period of time.

[0003] Antimicrobial agents are one of the core components of antimicrobial materials. The performance of antimicrobial agents plays a decisive role in the antimicrobial effect and action time of products. At present, general antimicrobial agents include three categories: organic, inorganic and composite antimicrobial agents; among them, organic antimicrobial agents are mainly represented by quaternary ammonium salts, chitosan, guanidine salts, etc., inorganic antimicrobial agents are represented by zinc oxide, silver, etc., and composite antimicrobial agents are mainly prepared by organic loading, organic complexation, etc.; organic antimicrobial agents have fast efficacy, but their biological toxicity is relatively large, and they are not resistant to high temperatures and are easy to decompose and discolor when used in industries such as plastics and textiles. In particular, about 1,000 components with bactericidal activity, including traditional fungicides such as triclosan, triclocarban, benzethonium chloride and chloroxylenol, have withdrawn from the market, and the safer and more environmentally friendly fungicide polyhexamethyleneguanidine hydrochloride (PHMG) has therefore received more attention, and is widely used in the fields of medicine, plant protection, industrial products and daily necessities for sterilization and mildew prevention.

[0004] Although polyhexamethyleneguanidine hydrochloride (PHMG) antimicrobial agents have many advantages, they still have obvious shortcomings in the fields of plastics, textiles, etc. For example, the high water solubility of polyhexamethyleneguanidine hydrochloride leads to rapid dissolution of the antimicrobial agent in related antibacterial plastics, textiles and other products due to frequent contact with water, resulting in rapid attenuation of the antibacterial effect of the products, thus limiting the application field and antibacterial effectiveness of this type of antimicrobial agent; at the same time, when the currently common polyhexamethyleneguanidine hydrochloride (PHMG) is heated to 160°C, PHMB will decompose and release nitrogen to form aminocyanide, thereby affecting its antibacterial performance. ; The processing temperature of thermoplastics is usually 260~300℃, so PHMB cannot be used as an additive in thermoplastics, which makes PHMB have obvious limitations in the field of plastic processing, resulting in restrictions on the selection of antibacterial additives for certain plastic products with high processing temperatures or long processing times, such as polyamide, polyethylene terephthalate, etc.; and according to the existing production process, to increase the thermal decomposition temperature of the antibacterial agent, it is necessary to increase the polymerization degree of the antibacterial agent, which requires extending the reaction time or optimizing the polymerization process, which will lead to an increase in preparation costs.

[0005] Based on the problems existing in the prior art, the present invention provides an antibacterial agent, which has a simple preparation process, can have a good fusion effect with thermoplastic resins, and will not undergo thermal decomposition within the processing temperature range. In particular, its excellent hydrophobicity can impart long-lasting antibacterial properties to a variety of plastic products, and the antibacterial time is far superior to the polyhexamethylene guanidine hydrochloride antibacterial agent products in the prior art. Summary of the invention

[0006] In order to overcome the deficiencies of the above-mentioned prior art, the purpose of the present invention is to provide an antibacterial agent and a preparation method and application thereof, so as to overcome the deficiencies of the prior art such as decomposition of the antibacterial agent due to high water solubility and limited use and low antibacterial effectiveness due to low thermal decomposition temperature, and have a higher thermal decomposition temperature, a simple production method, low cost, and flexible and diverse application forms.

[0007] To achieve the above objectives, the present invention provides the following technical solutions.

[0008] One aspect of the present invention provides the use of a compound represented by formula (I) in the preparation of an antibacterial agent. Formula (I); wherein n is an integer of 40-60, R is a residue of any one of hexamethylenediamine, m-phenylenediamine, p-phenylenediamine or 4,4'-diaminodicyclohexylmethane, and X is a benzene ring, a furan ring or Any one of the above, wherein a is an integer of 4-6; the compound is a hydrophobic organic salt.

[0009] Another aspect of the present invention provides an antibacterial agent, which includes a compound represented by formula (I): Formula (I); wherein n is an integer of 40 to 60, R is a residue of any one of hexamethylenediamine, m-phenylenediamine, p-phenylenediamine or 4,4'-diaminodicyclohexylmethane, and X is a benzene ring, a furan ring or Any one of , a is an integer from 4 to 6.

[0010] Another aspect of the present invention provides a method for preparing an antibacterial agent, the specific steps comprising: S1. After the guanidine hydrochloride and the diamine are completely dissolved and mixed at a temperature raised to completely dissolve, they are heated in an inert gas atmosphere to react the guanidine hydrochloride and the diamine to obtain an antibacterial agent intermediate as shown in formula (II); Formula (II); wherein n is an integer of 40-60, and R is a residue of any one of hexamethylenediamine, m-phenylenediamine, p-phenylenediamine, or 4,4'-diaminodicyclohexylmethane; S2. Dissolve the antibacterial agent intermediate and sodium salt obtained in S1 in a water / alcohol mixed system, stir and react to obtain the antibacterial agent.

[0011] Preferably, in S1, the heating treatment adopts a staged heating method; the staged heating method includes a first stage, a second stage, and a third stage, the heating temperature increases sequentially, and each stage is heated to the reaction temperature and then subjected to a heat preservation treatment.

[0012] More preferably, the first stage comprises raising the temperature to 130-140° C. and maintaining the temperature for 0.5-1.5 h.

[0013] More preferably, the second stage comprises raising the temperature to 150-160° C. and maintaining the temperature for 0.5-1.5 h.

[0014] More preferably, the third stage comprises raising the temperature to 170-180° C., removing ammonia generated by the reaction by vacuuming, and maintaining the temperature for 0.5 h.

[0015] Preferably, the diamine includes at least one of hexamethylenediamine, p-xylylenediamine, m-xylylenediamine and 4,4'-diaminodicyclohexylmethane.

[0016] Preferably, the molar ratio of guanidine hydrochloride to the diamine is (1:1) to (1.1:1).

[0017] Preferably, in S2, the sodium salt includes sodium furandicarboxylate, sodium terephthalate, sodium succinate, sodium glutarate or sodium adipic acid.

[0018] Preferably, the molar ratio of the antibacterial agent intermediate to the sodium salt is 1:0.1 to 1:1.

[0019] The reaction solvent of the antibacterial agent intermediate and the sodium salt is water / ethanol, water / isopropanol, water / glycerol, water / n-butanol, and water / isobutanol.

[0020] Preferably, the temperature for reacting the antibacterial agent intermediate with the sodium salt ranges from room temperature to 60°C.

[0021] Preferably, in S1 and S2, the reaction of guanidine hydrochloride and diamine, and the reaction of the antibacterial agent intermediate and the sodium salt are both carried out under the protection of an inert gas.

[0022] Another aspect of the present invention provides use of the antibacterial agent in preparing a product with antibacterial function.

[0023] Another aspect of the present invention provides an antibacterial material, wherein the antibacterial agent can be added as an antibacterial additive into a thermoplastic resin for melt extrusion, and then injection molded into a variety of antibacterial plastic products. Since the antibacterial agent therein has hydrophobic properties, it can work for a long time in an environment where water exists while maintaining the antibacterial effect, thereby extending the antibacterial performance and antibacterial time of the antibacterial material, and can even extend the antibacterial effect to a time similar to the service life of the plastic product.

[0024] The preparation of the antibacterial plastic product comprises at least uniformly mixing the antibacterial agent with the thermoplastic resin, and then performing melt extrusion at 220-260°C and injection molding to obtain the product.

[0025] The technical effects of the technical solution of the present invention are as follows: 1. By adopting the technical solution of the present invention, a salt antibacterial product with hydrophobic properties is provided. On the one hand, due to its hydrophobic property, it can be used as an antibacterial additive in products that need to be in contact with water for a long time, and can maintain a long-term antibacterial effect; on the other hand, the antibacterial agent provided by the present invention is an environmentally friendly antibacterial agent with excellent antibacterial properties and thermal stability, and can meet the requirements of the product for the long-term antibacterial performance of the antibacterial agent while effectively ensuring the antibacterial properties and mechanical properties of the formed antibacterial material.

[0026] 2. The antibacterial agent provided by the technical solution of the present invention has a simple preparation method, high yield, safety, environmental protection, and low cost.

[0027] 3. The antibacterial agent provided by the technical solution of the present invention has broad-spectrum antibacterial properties, high antibacterial efficiency, good mechanical properties, safety and reliability, no odor, and low harm and pollution to the human body and the environment.

[0028] 4. The antibacterial agent provided by the technical solution of the present invention is applied to the plastic antibacterial material prepared from thermoplastic plastics. The method is simple to operate, easy to control, and suitable for industrial production.

[0029] 5. The antibacterial material provided by the present invention has long-lasting antibacterial properties, and its effective antibacterial time is substantially the same as the service life of the antibacterial material. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 The antibacterial ring test results of the antibacterial agent prepared in Example 1 of the present invention are shown.

[0031] Figure 2 The antibacterial ring test results of the antibacterial agent prepared in Example 2 of the present invention are shown.

[0032] Figure 3The antibacterial ring test results of the antibacterial agent prepared in Example 3 of the present invention are shown.

[0033] Figure 4 The antibacterial ring test results of the antibacterial agent prepared in Example 4 of the present invention are shown.

[0034] Figure 5 The antibacterial ring test results of the antibacterial agent prepared in Example 5 of the present invention are shown.

[0035] Figure 6 The antibacterial ring test results of the antibacterial agent prepared in Example 6 of the present invention are shown.

[0036] Figure 7 The antibacterial ring test results of the antibacterial agent prepared in Example 7 of the present invention are shown.

[0037] Figure 8 The antibacterial ring test results of the antibacterial agent prepared in Example 8 of the present invention are shown.

[0038] Fig. 9 The antibacterial ring test results of the antibacterial agent prepared in Example 14 of the present invention.

[0039] Fig.10 These are the antibacterial ring test results of the antibacterial agents prepared in some comparative examples 1-3 of the present invention.

[0040] Fig.11 This is the infrared spectrum of the antibacterial agent prepared in Example 1 of the present invention.

[0041] Fig.12 This is the infrared spectrum of the antibacterial agent prepared in Example 9 of the present invention. DETAILED DESCRIPTION

[0042] To make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the protection scope of the present invention.

[0043] The disclosures of all patent and non-patent literature cited herein are incorporated herein by reference in their entirety.

[0044] As used in the invention, the terms "comprise", "include", "contain", "cover", "have", "with" or any other variation thereof are intended to cover non-exclusive inclusions. For example, a process, method, article or device that includes a list of elements is not necessarily limited to those elements, but may include other elements that are not explicitly listed or inherent to the process, method, article or device. In addition, unless expressly indicated to the contrary, "or" refers to an inclusive "or" rather than an exclusive "or". For example, conditions A or B meet any of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist). The phrase "one or more" is intended to cover non-exclusive inclusions. For example, one or more A, B and C, means any of the following: A alone, B alone, C alone, a combination of A and B, a combination of B and C, a combination of A and C, or a combination of A, B and C.

[0045] In addition, "a" or "an" is used to describe the elements and components described herein. This is done only for convenience and to provide a general sense of the scope of the invention. This description should be understood to include one or at least one, one or at least one, and the singular also includes the plural, unless it is obvious that it is intended otherwise.

[0046] Some embodiments of the present invention provide a method for preparing an antibacterial agent, comprising the following steps: S1. After the guanidine hydrochloride and the diamine are heated to completely dissolved and fully mixed, they are heated in an inert gas atmosphere to react with the guanidine hydrochloride and the diamine to obtain an antibacterial agent intermediate as shown in formula (II); Formula (II); wherein n is an integer of 40-60, and R is a residue of any one of hexamethylenediamine, m-phenylenediamine, p-phenylenediamine, or 4,4'-diaminodicyclohexylmethane; S2. Dissolve the antibacterial agent intermediate and sodium salt in a water / alcohol mixture, stir and react at room temperature to 60°C to obtain an antibacterial agent; the antibacterial agent includes a compound represented by formula (I): Formula (I); wherein n is an integer of 40 to 60, R is a residue of any one of hexamethylenediamine, m-phenylenediamine, p-phenylenediamine or 4,4'-diaminodicyclohexylmethane, and X is a benzene ring, a furan ring or Any one of , a is an integer from 4 to 6.

[0047] In some embodiments, in S1, the heating treatment adopts a staged heating method; the staged heating method includes a first stage-a second stage-a third stage, the heating temperature increases sequentially, and each stage is heated to the reaction temperature and then subjected to insulation treatment.

[0048] More specifically, the first stage includes raising the temperature to 130-140°C and keeping it warm for 0.5-1.5 hours; the second stage includes raising the temperature to 150-160°C and keeping it warm for 0.5-1.5 hours; the third stage includes raising the temperature to 170-180°C, vacuuming to remove ammonia generated by the reaction, and keeping it warm for 0.5 hours.

[0049] In some embodiments, the diamine includes at least one of hexamethylenediamine, p-xylylenediamine, m-xylylenediamine, and 4,4′-diaminodicyclohexylmethane.

[0050] In some embodiments, the molar ratio of guanidine hydrochloride to the diamine is 1:1 to 1.1:1.

[0051] In some embodiments, the sodium salt comprises sodium furandicarboxylate, sodium terephthalic acid, sodium succinate, sodium glutarate, or sodium adipate.

[0052] In other embodiments, the molar ratio of the antibacterial agent intermediate to the sodium salt is 1:0.2 to 1:2.

[0053] In other embodiments, the reaction of guanidine hydrochloride and diamine, and the reaction of the antibacterial agent intermediate and the sodium salt are both carried out under the protection of an inert gas.

[0054] The antibacterial agent provided by the above technical solution can be applied to thermoplastic plastics.

[0055] In the process of co-processing the antimicrobial agent with the thermoplastic, processing aids and modifiers conventional in the art are also used, such as plasticizers, flame retardants, lubricants, UV absorbers, antioxidants, fillers, etc.

[0056] Unless otherwise defined, the meaning of all technical and scientific terms used herein is the same as that generally understood by those of ordinary skill in the art to which the present disclosure belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the disclosed composition embodiments, suitable methods and materials are described below. Unless citing a specific paragraph, all publications, patent applications, patents and other references mentioned herein are incorporated herein by reference in their entirety. If a conflict occurs, this specification and the definitions included therein shall prevail. In addition, materials, methods and examples are illustrative only, and not restrictive.

[0057] The technical scheme of the present invention, its implementation process and principle, etc. will be further explained through specific embodiments as follows. It should be noted that the following detailed descriptions are exemplary and are intended to provide further explanation of the present invention. The described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the field without creative work are within the scope of protection of the present invention. Unless otherwise specified, the reagents and raw materials used in the following examples are commercially available, and the test methods for which specific conditions are not specified are usually carried out under conventional conditions or according to the conditions recommended by the manufacturers. In addition, unless otherwise specified, the experimental methods, detection methods, and preparation methods disclosed in the present invention all adopt conventional techniques in the art. These technologies have been fully described in the existing literature.

[0058] The test items, standards or methods involved in the embodiments and / or comparative examples are as follows: 1. Molecular weight test The number average molecular weight and weight average molecular weight of the product were determined using a GPC column.

[0059] Specifically, the size exclusion chromatography system Alliance 2695™ (Waters Corporation, Milford, MA) was equipped with a Waters 414™ differential refractive index detector, a multi-angle light scattering photometer DAWN Heleos II (Wyatt Technologies, Santa Barbara, CA), and a ViscoStar™ differential capillary viscometer detector (Wyatt). The software used for data acquisition and simplification was version 5.4 from Wyatt. The columns used were 2×10 7 and two Shodex GPC HFIP-806M™ styrene-divinylbenzene columns with a theoretical plate of 8,000 / 30 cm; and an exclusion limit of 2×10 5 And a Shodex GPC HFIP-804M™ styrene-divinylbenzene column with a theoretical plate of 10,000 / 30 cm.

[0060] The sample was dissolved in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) containing 0.01 M sodium trifluoroacetate, mixed with moderate stirring at 50° C. for four hours, and then filtered using a 0.45 μm PTFE filter. The concentration of the solution was approximately 2 mg / mL.

[0061] The chromatograph was set at 35°C; the flow rate was 0.5 mL / min and the data was collected; the injection volume was 100 μL; and the run time was 80 min. Data were imported from all three detectors mentioned above and data reduction was performed. The light scattering detector used eight scattering angles. No column calibration benchmark was involved in the data processing.

[0062] 2. Antibacterial test The present invention adopts the antibacterial ring method to test the antibacterial activity of Escherichia coli.

[0063] 3. Thermal decomposition test.

[0064] Thermogravimetric analysis (TGA) was used for testing.

[0065] The technical solution of the present invention is described in detail below through specific embodiments.

[0066] Example 1 The preparation method of the antibacterial agent provided in this embodiment specifically comprises the following steps: First, guanidine hydrochloride ( ) and hexamethylenediamine are fully mixed in a molar ratio of 1.1:1, and then stepwise heated under a nitrogen atmosphere. The heating steps include: In the first stage, the temperature was raised to 140°C and kept for 1 h; In the second stage, the temperature was raised to 160°C and kept for 1 h; In the third stage, the temperature was raised to 180°C, and ammonia produced by the reaction was removed by vacuum, and the temperature was kept for 0.5 h.

[0067] Guanidine hydrochloride and hexamethylenediamine undergo polycondensation reaction to obtain an antibacterial agent intermediate as shown in formula (II). , formula (II), wherein R is the residue of hexamethylenediamine.

[0068] Then, the obtained antibacterial agent intermediate and furandicarboxylic acid sodium salt are dissolved in a mixed solution of water and ethanol at a molar ratio of 1:0.1, stirred, and reacted at room temperature to obtain an antibacterial agent as shown in formula (I). , formula (I), wherein X is a furan ring, R is a residue of hexamethylenediamine, and n=40~50.

[0069] The molecular weight of the above antibacterial agent is 12000-19000.

[0070] See also Figure 1 , is the antibacterial test result of this embodiment on Escherichia coli, and the antibacterial ring is 16.95mm.

[0071] See also Fig.11, is the infrared spectrum of the antibacterial agent prepared in this example. It can be seen from the figure that 3200cm -1 The characteristic absorption peak of -NH- near 2921cm -1 、2846cm -1 is the stretching vibration absorption peak of -CH2-, 1600cm -1 -C=O and 1500cm -1 The double bond stretching vibration absorption peak of -C=N near 1000cm -1 The nearby carboxyl salt absorption characteristic peak indicates that the structural formula of the present invention was successfully synthesized.

[0072] Example 2 The preparation method of the antibacterial agent provided in this embodiment specifically comprises the following steps: First, guanidine hydrochloride ( ) and hexamethylenediamine are fully mixed in a molar ratio of 1:1, and then stepwise heated under a nitrogen atmosphere. The heating steps include: In the first stage, the temperature was raised to 140°C and kept for 1 h; In the second stage, the temperature was raised to 160°C and kept for 1 h; In the third stage, the temperature was raised to 180°C, and ammonia produced by the reaction was removed by vacuum, and the temperature was kept for 0.5 h.

[0073] Guanidine hydrochloride and hexamethylenediamine undergo polycondensation reaction to obtain an antibacterial agent intermediate as shown in formula (II). , formula (II), wherein R is the residue of hexamethylenediamine.

[0074] Then, the obtained antibacterial agent intermediate and furandicarboxylic acid sodium salt are dissolved in a mixed solution of water and isopropanol at a molar ratio of 1:0.15, stirred, and reacted at room temperature to obtain an antibacterial agent as shown in formula (I). , formula (I), wherein X is a furan ring, R is a residue of hexamethylenediamine, n=40-50, and the molecular weight of the above antibacterial agent is 16000-18000.

[0075] See also Figure 2 , is the antibacterial test result of this embodiment on Escherichia coli, and the antibacterial ring is 16.77mm.

[0076] Example 3 The preparation method of the antibacterial agent provided in this embodiment specifically comprises the following steps: First, guanidine hydrochloride ( ) and hexamethylenediamine in a molar ratio of 1.1:1 are mixed, and stepwise heating is performed under a nitrogen atmosphere. The heating steps include: In the first stage, the temperature was raised to 140°C and kept for 1 h; In the second stage, the temperature was raised to 160°C and kept for 1 h; In the third stage, the temperature was raised to 180°C, and ammonia produced by the reaction was removed by vacuum, and the temperature was kept for 0.5 h.

[0077] Guanidine hydrochloride and hexamethylenediamine undergo polycondensation reaction to obtain an antibacterial agent intermediate as shown in formula (II). , formula (II), wherein R is the residue of hexamethylenediamine.

[0078] Then, the obtained antibacterial agent intermediate and furandicarboxylic acid sodium salt are dissolved in a mixed solution of water and n-butanol at a molar ratio of 1:0.2, stirred, and reacted at room temperature to obtain an antibacterial agent as shown in formula (I). , formula (I), wherein X is a furan ring, R is a residue of hexamethylenediamine, and n=30~40.

[0079] The molecular weight of the above antibacterial agent is 11000-15000.

[0080] See also Figure 3 , is the antibacterial test result of this embodiment on Escherichia coli, and the antibacterial ring is 16.42mm.

[0081] Example 4 The preparation method of the antibacterial agent provided in this embodiment specifically comprises the following steps: First, guanidine hydrochloride ( ) and hexamethylenediamine are fully mixed in a molar ratio of 1:1, and then stepwise heated under a nitrogen atmosphere. The heating steps include: In the first stage, the temperature was raised to 140°C and kept for 1 h; In the second stage, the temperature was raised to 160°C and kept for 1 h; In the third stage, the temperature was raised to 180°C, and ammonia produced by the reaction was removed by vacuum, and the temperature was kept for 0.5 h.

[0082] Guanidine hydrochloride and hexamethylenediamine undergo polycondensation reaction to obtain an antibacterial agent intermediate as shown in formula (II). , formula (II), wherein R is the residue of hexamethylenediamine.

[0083] Then, the obtained antibacterial agent intermediate and furandicarboxylic acid sodium salt are dissolved in a mixed solution of water and ethanol at a molar ratio of 1:0.25, stirred, and reacted at room temperature to obtain an antibacterial agent as shown in formula (I). , formula (I), wherein X is a furan ring, R is a residue of hexamethylenediamine, and n=40-50; The molecular weight of the above antibacterial agent is 16000-19000.

[0084] See also Figure 4 , is the antibacterial test result of this embodiment on Escherichia coli, and the antibacterial ring is 16.72mm.

[0085] Example 5 The preparation method of the antibacterial agent provided in this embodiment specifically comprises the following steps: First, guanidine hydrochloride ( ) and hexamethylenediamine are fully mixed in a molar ratio of 1.1:1, and then stepwise heated under a nitrogen atmosphere. The heating steps include: In the first stage, the temperature was raised to 140°C and kept for 1 h; In the second stage, the temperature was raised to 160°C and kept for 1 h; In the third stage, the temperature was raised to 180°C, and ammonia produced by the reaction was removed by vacuum, and the temperature was kept for 0.5 h.

[0086] Guanidine hydrochloride and hexamethylenediamine undergo polycondensation reaction to obtain an antibacterial agent intermediate as shown in formula (II). , formula (II), wherein R is the residue of hexamethylenediamine.

[0087] Then, the obtained antibacterial agent intermediate and sodium furandicarboxylate are dissolved in water and isobutyl alcohol at a molar ratio of 1:0.4, stirred, and reacted at room temperature to obtain an antibacterial agent as shown in formula (I). , formula (I), wherein X is a furan ring, R is a residue of hexamethylenediamine, and n=30-40; the molecular weight of the above antibacterial agent is 12000-16000.

[0088] See also Figure 5 , is the antibacterial test result of this embodiment on Escherichia coli, and the antibacterial ring is 16.59mm.

[0089] Example 6 The preparation method of the antibacterial agent provided in this embodiment specifically comprises the following steps: First, guanidine hydrochloride ( ) and hexamethylenediamine are fully mixed in a molar ratio of 1.1:1, and then stepwise heated under a nitrogen atmosphere. The heating steps include: In the first stage, the temperature was raised to 140°C and kept for 1 h; In the second stage, the temperature was raised to 160°C and kept for 1 h; In the third stage, the temperature was raised to 180°C, and ammonia produced by the reaction was removed by vacuum, and the temperature was kept for 0.5 h.

[0090] Guanidine hydrochloride and hexamethylenediamine undergo polycondensation reaction to obtain an antibacterial agent intermediate as shown in formula (II). Formula (II), wherein R is the residue of hexamethylenediamine.

[0091] Then, the obtained antibacterial agent intermediate and furandicarboxylic acid sodium salt are dissolved in water and ethanol at a molar ratio of 1:0.5, stirred, and reacted at room temperature to obtain an antibacterial agent as shown in formula (I). Formula (I), wherein X is a furan ring, R is a residue of hexamethylenediamine, and n=30-40; the molecular weight of the antibacterial agent is 13000-16000.

[0092] See also Figure 6 , is the antibacterial test result of Escherichia coli in this embodiment, and the antibacterial ring of Escherichia coli is 15.72 mm.

[0093] Example 7 The preparation method of the antibacterial agent provided in this embodiment specifically comprises the following steps: First, guanidine hydrochloride ( ) and hexamethylenediamine are fully mixed in a molar ratio of 1.1:1, and then stepwise heated under a nitrogen atmosphere. The heating steps include: In the first stage, the temperature was raised to 140°C and kept for 1 h; In the second stage, the temperature was raised to 160°C and kept for 1 h; In the third stage, the temperature was raised to 180°C, and ammonia produced by the reaction was removed by vacuum, and the temperature was kept for 0.5 h.

[0094] Thus, guanidine hydrochloride and hexamethylenediamine undergo polycondensation reaction to obtain an antibacterial agent intermediate as shown in formula (II). Formula (II), wherein R is the residue of hexamethylenediamine.

[0095] Then, the obtained antibacterial agent intermediate and furandicarboxylic acid sodium salt are dissolved in a mixed solution of water and isobutyl alcohol at a molar ratio of 1:0.8, stirred, and reacted at room temperature to obtain an antibacterial agent as shown in formula (I). Formula (I), wherein X is a furan ring, R is a residue of hexamethylenediamine, and n=30-40.

[0096] The molecular weight of the above antibacterial agent is 12000-16000, see Figure 7, is the antibacterial test result of Escherichia coli in this embodiment, and the antibacterial ring of Escherichia coli is 15.68 mm.

[0097] Example 8 The preparation method of the antibacterial agent provided in this embodiment specifically comprises the following steps: First, guanidine hydrochloride ( ) and hexamethylenediamine are fully mixed in a molar ratio of 1.1:1, and then stepwise heated under a nitrogen atmosphere. The heating steps include: In the first stage, the temperature was raised to 140°C and kept for 1 h; In the second stage, the temperature was raised to 160°C and kept for 1 h; In the third stage, the temperature was raised to 180°C, and ammonia produced by the reaction was removed by vacuum, and the temperature was kept for 0.5 h.

[0098] Thus, guanidine hydrochloride and hexamethylenediamine undergo polycondensation reaction to obtain an antibacterial agent intermediate as shown in formula (II). Formula (II), wherein R is the residue of hexamethylenediamine.

[0099] Then, the obtained antibacterial agent intermediate and furandicarboxylic acid sodium salt are dissolved in a mixed solution of water and butanol at a molar ratio of 1:1, stirred, and reacted at room temperature to obtain an antibacterial agent as shown in formula (I). Formula (I), wherein X is a furan ring, R is a residue of hexamethylenediamine, and n=30-40; the molecular weight of the antibacterial agent is 12000-16000.

[0100] See also Figure 8 , is the antibacterial test result of Escherichia coli in this embodiment, and the antibacterial ring of Escherichia coli is 15.62 mm.

[0101] Example 9 The preparation method of the antibacterial agent provided in this embodiment specifically comprises the following steps: First, guanidine hydrochloride ( ) and hexamethylenediamine are fully mixed in a molar ratio of 1.1:1, and then stepwise heated under a nitrogen atmosphere. The heating steps include: In the first stage, the temperature was raised to 140°C and kept for 1 h; In the second stage, the temperature was raised to 160°C and kept for 1 h; In the third stage, the temperature was raised to 180°C, and ammonia produced by the reaction was removed by vacuum, and the temperature was kept for 0.5 h.

[0102] Thus, guanidine hydrochloride and hexamethylenediamine undergo polycondensation reaction to obtain an antibacterial agent intermediate as shown in formula (II). Formula (II), wherein R is the residue of hexamethylenediamine.

[0103] Then, the obtained antibacterial agent intermediate and sodium terephthalate are dissolved in a mixed solution of water and isopropanol at a molar ratio of 1:0.25, stirred, and reacted at room temperature to obtain an antibacterial agent as shown in formula (I). Formula (I), wherein X is a benzene ring, R is a residue of hexamethylenediamine, and n=30-40.

[0104] The molecular weight of the antibacterial agent is 12000-16000, and the inhibition zone of Escherichia coli is 14.59 mm.

[0105] See also Fig.12 , is the infrared spectrum of the antibacterial agent of this embodiment, and the spectrum analysis is shown in Fig.12 As can be seen from the figure, the antibacterial agent can be successfully synthesized using the technical solution of this embodiment.

[0106] Example 10 The preparation method of the antibacterial agent provided in this embodiment specifically comprises the following steps: First, guanidine hydrochloride ( ) and hexamethylenediamine are fully mixed in a molar ratio of 1.1:1, and then stepwise heated under a nitrogen atmosphere. The heating steps include: In the first stage, the temperature was raised to 140°C and kept for 1 h; In the second stage, the temperature was raised to 160°C and kept for 1 h; In the third stage, the temperature was raised to 180°C, and ammonia produced by the reaction was removed by vacuum, and the temperature was kept for 0.5 h.

[0107] Thus, guanidine hydrochloride and hexamethylenediamine undergo polycondensation reaction to obtain an antibacterial agent intermediate as shown in formula (II). Formula (II), wherein R is a residue of hexamethylenediamine.

[0108] Then, the obtained antibacterial agent intermediate and sodium glutarate are dissolved in a mixed solution of water and ethanol at a molar ratio of 1:0.4, stirred, and reacted at room temperature to obtain an antibacterial agent as shown in formula (I). Formula (I), wherein X is CH2CH2CH2CH2CH2, R is the residue of hexamethylenediamine, and n=30~40.

[0109] The molecular weight of the antibacterial agent is 12000-16000, and the inhibition zone of Escherichia coli is 14.08 mm.

[0110] Embodiment 11 The preparation method of the antibacterial agent provided in this embodiment specifically comprises the following steps: First, guanidine hydrochloride ( ) and m-phenylenediamine are fully mixed in a molar ratio of 1:1, and then stepwise heated under a nitrogen atmosphere. The heating steps include: In the first stage, the temperature was raised to 140°C and kept for 1 h; In the second stage, the temperature was raised to 160°C and kept for 1 h; In the third stage, the temperature was raised to 180°C, and ammonia produced by the reaction was removed by vacuum, and the temperature was kept for 0.5 h.

[0111] Thus, guanidine hydrochloride and m-xylylenediamine undergo polycondensation reaction to obtain an antibacterial agent intermediate as shown in formula (II). Formula (II) Wherein R is the residue of m-xylylenediamine.

[0112] Then, the obtained antibacterial agent intermediate and sodium terephthalate are dissolved in a mixed solution of water and ethanol at a molar ratio of 1:0.25, stirred, and reacted at room temperature to obtain an antibacterial agent as shown in formula (I). Formula (I), wherein X is a benzene ring, R is a residue of m-xylylenediamine, and n=30-40.

[0113] The molecular weight of the antibacterial agent is 11000-15000, and the inhibition zone of Escherichia coli is 15.27 mm.

[0114] Example 12 The preparation method of the antibacterial agent provided in this embodiment specifically comprises the following steps: First, guanidine hydrochloride ( ) and m-phenylenediamine are fully mixed in a molar ratio of 1:1, and then stepwise heated under a nitrogen atmosphere. The heating steps include: In the first stage, the temperature was raised to 140°C and kept for 1 h; In the second stage, the temperature was raised to 160°C and kept for 1 h; In the third stage, the temperature was raised to 180°C, and ammonia produced by the reaction was removed by vacuum, and the temperature was kept for 0.5 h.

[0115] Thus, guanidine hydrochloride and m-xylylenediamine undergo polycondensation reaction to obtain an antibacterial agent intermediate as shown in formula (II). , formula (II), wherein R is the residue of meta-xylylenediamine.

[0116] Then, the obtained antibacterial agent intermediate and sodium adipic acid salt are dissolved in a mixed solution of water and ethanol at a molar ratio of 1:0.15, stirred, and reacted at room temperature to obtain an antibacterial agent as shown in formula (I). Formula (I), wherein X is CH2CH2CH2CH2CH2CH2CH2, R is the residue of m-phenylenediamine, and n=30~40.

[0117] The molecular weight of the antibacterial agent is 12000-13000, and the inhibition zone of Escherichia coli is 15.97 mm.

[0118] Example 13 The preparation method of the antibacterial agent provided in this embodiment specifically comprises the following steps: First, guanidine hydrochloride ( ) and p-phenylenediamine are fully mixed in a molar ratio of 1:1.1, and then stepwise heated under a nitrogen atmosphere. The heating steps include: In the first stage, the temperature was raised to 140°C and kept for 1 h; In the second stage, the temperature was raised to 160°C and kept for 1 h; In the third stage, the temperature was raised to 180°C, and ammonia produced by the reaction was removed by vacuum, and the temperature was kept for 0.5 h.

[0119] Thus, guanidine hydrochloride and p-phenylenediamine undergo polycondensation reaction to obtain an antibacterial agent intermediate as shown in formula (II). Formula (II), wherein R is the residue of p-phenylenediamine.

[0120] Then, the obtained antibacterial agent intermediate and furandicarboxylic acid sodium salt are dissolved in a mixed solution of water and ethanol at a molar ratio of 1:0.25, stirred, and reacted at room temperature to obtain an antibacterial agent as shown in formula (I). , formula (I), wherein X is a furan ring, R is a residue of p-phenylenediamine, and n=30-40; the molecular weight of the above antibacterial agent is 13000-17000; the inhibition ring of Escherichia coli is 11.52 mm.

[0121] Embodiment 14 The preparation method of the antibacterial agent provided in this embodiment specifically comprises the following steps: First, guanidine hydrochloride ( ) and p-phenylenediamine are fully mixed in a molar ratio of 1:1.1, and then stepwise heated under a nitrogen atmosphere. The heating steps include: In the first stage, the temperature was raised to 140°C and kept for 1 h; In the second stage, the temperature was raised to 160°C and kept for 1 h; In the third stage, the temperature was raised to 180°C, and ammonia produced by the reaction was removed by vacuum, and the temperature was kept for 0.5 h.

[0122] Thus, guanidine hydrochloride and p-phenylenediamine undergo polycondensation reaction to obtain an antibacterial agent intermediate as shown in formula (II). , formula (II), wherein R is the residue of p-phenylenediamine.

[0123] Then, the obtained antibacterial agent intermediate and sodium adipic acid salt are dissolved in a mixed solution of water and ethanol at a molar ratio of 1:0.15, stirred, and reacted at room temperature to obtain an antibacterial agent as shown in formula (I). Formula (I) Wherein, X is CH2CH2CH2CH2CH2CH2, R is the residue of p-phenylenediamine, n=30-40; and the molecular weight of the above antibacterial agent is 12000-17000.

[0124] See also Fig. 9 , is the antibacterial test result of Escherichia coli in this embodiment, and the antibacterial ring of Escherichia coli is 11.59 mm.

[0125] Embodiment 15 The preparation method of the antibacterial agent provided in this embodiment specifically comprises the following steps: First, guanidine hydrochloride ( ) and 4,4'-diaminodicyclohexylmethane are fully mixed in a molar ratio of 1:1.1, and then stepwise heated under a nitrogen atmosphere. The heating steps include: In the first stage, the temperature was raised to 140°C and kept for 1 h; In the second stage, the temperature was raised to 160°C and kept for 1 h; In the third stage, the temperature was raised to 180°C, and ammonia produced by the reaction was removed by vacuum, and the temperature was kept for 0.5 h.

[0126] Thus, guanidine hydrochloride and 4,4'-diaminodicyclohexylmethane undergo polycondensation reaction to obtain an antibacterial agent intermediate as shown in formula (II). Formula (II), wherein R is the residue of 4,4'-diaminodicyclohexylmethane.

[0127] Then, the obtained antibacterial agent intermediate and furandicarboxylic acid sodium salt are dissolved in a mixed solution of water and ethanol at a molar ratio of 1:0.25, stirred, and reacted at room temperature to obtain an antibacterial agent as shown in formula (I). Formula (I), wherein X is a furan ring, R is a residue of 4,4'-diaminodicyclohexylmethane, and n=30-40.

[0128] The molecular weight of the above antibacterial agent is 16000-22000, and the inhibition zone of Escherichia coli is 16.35 mm.

[0129] Example 16 The preparation method of the antibacterial agent provided in this embodiment specifically comprises the following steps: First, guanidine hydrochloride ( ) and 4,4'-diaminodicyclohexylmethane are fully mixed in a molar ratio of 1:1.1, and then stepwise heated under a nitrogen atmosphere. The heating steps include: In the first stage, the temperature was raised to 140°C and kept for 1 h; In the second stage, the temperature was raised to 160°C and kept for 1 h; In the third stage, the temperature was raised to 180°C, and ammonia produced by the reaction was removed by vacuum, and the temperature was kept for 0.5 h.

[0130] Thus, guanidine hydrochloride and 4,4'-diaminodicyclohexylmethane undergo polycondensation reaction to obtain an antibacterial agent intermediate as shown in formula (II). Formula (II), wherein R is the residue of 4,4'-diaminodicyclohexylmethane.

[0131] Then, the obtained antibacterial agent intermediate and sodium malonate are dissolved in a mixed solution of water and ethanol at a molar ratio of 1:0.15, stirred, and reacted at room temperature to obtain an antibacterial agent as shown in formula (I). , formula (I), wherein X is CH2CH2CH2, R is the residue of 4,4'-diaminodicyclohexylmethane, and n=30~40.

[0132] The molecular weight of the above antibacterial agent is 15000-21000, and the inhibition zone of Escherichia coli is 16.21 mm.

[0133] Comparative Example 1 The preparation method of the antibacterial agent provided in this comparative example specifically comprises the following steps: First, guanidine hydrochloride ( ) and hexamethylenediamine are fully mixed in a molar ratio of 1:1, and then stepwise heated under a nitrogen atmosphere. The heating steps include: In the first stage, the temperature was raised to 140°C and kept for 1 h; In the second stage, the temperature was raised to 160°C and kept for 1 h; In the third stage, the temperature was raised to 180°C, and ammonia produced by the reaction was removed by vacuum, and the temperature was kept for 0.5 h.

[0134] Thus, guanidine hydrochloride and hexamethylenediamine undergo polycondensation reaction to obtain an antibacterial agent as shown in formula (II). , formula (II), wherein R is the residue of hexamethylenediamine, and the molecular weight of the structural formula is 12000-13000.

[0135] Comparative Example 2 The preparation method of the antibacterial agent provided in this embodiment specifically comprises the following steps: First, guanidine hydrochloride ( ) and m-phenylenediamine are fully mixed in a molar ratio of 1:1, and then stepwise heated under a nitrogen atmosphere. The heating steps include: In the first stage, the temperature was raised to 140°C and kept for 1 h; In the second stage, the temperature was raised to 160°C and kept for 1 h; In the third stage, the temperature was raised to 180°C, and ammonia produced by the reaction was removed by vacuum, and the temperature was kept for 0.5 h.

[0136] Thus, guanidine hydrochloride and m-xylylenediamine undergo polycondensation reaction to obtain an antibacterial agent as shown in formula (II). , formula (II), wherein R is the residue of meta-phenylenediamine, and the molecular weight of the structural formula is 8000-10000.

[0137] Comparative Example 3 The preparation method of the antibacterial agent provided in this embodiment specifically comprises the following steps: First, guanidine hydrochloride ( ) and 4,4'-diaminodicyclohexylmethane are fully mixed in a molar ratio of 1:1.1, and then stepwise heated under a nitrogen atmosphere. The heating steps include: In the first stage, the temperature was raised to 140°C and kept for 1 h; In the second stage, the temperature was raised to 160°C and kept for 1 h; In the third stage, the temperature was raised to 180°C, and ammonia produced by the reaction was removed by vacuum, and the temperature was kept for 0.5 h.

[0138] Thus, guanidine hydrochloride and 4,4'-diaminodicyclohexylmethane undergo polycondensation reaction to obtain an antibacterial agent as shown in formula (II): Formula (II), wherein R is the residue of 4,4'-diaminodicyclohexylmethane, and the molecular weight of the structural formula is 10000-12000.

[0139] See also Fig.10, respectively, are the antibacterial test results of comparative examples 1-3, and from left to right are the antibacterial conditions of comparative example 1, comparative example 2 and comparative example 3. The results show that: since the antibacterial agent provided in the comparative example is a water-soluble antibacterial agent, the antibacterial agent has dissolved after the antibacterial test, indicating that the antibacterial property of the antibacterial agent provided in the comparative example fails when used in the resin system, and therefore the antibacterial property of the resin cannot be guaranteed, especially in a humid environment, which will greatly shorten the antibacterial effectiveness of the antibacterial material.

[0140] Furthermore, thermogravimetric analysis (TGA) tests were performed on Examples 1 to 16, and the results showed that no decomposition occurred when the temperature was heated to 300°C.

[0141] By comparing the results of the antibacterial ring test of the embodiment and the comparative example, it can be found that the antibacterial agent provided in the comparative example has a higher water solubility. When it is used as an antibacterial agent, it will be quickly precipitated in a humid environment, especially in a solution environment. The antibacterial effect of the antibacterial agent is rapidly precipitated, which leads to the rapid attenuation or even loss of the antibacterial effect of the antibacterial product. The antibacterial agent provided by the present invention has significantly improved hydrophobicity. It can be seen from the antibacterial ring diameter formed by the antibacterial ring test that the antibacterial effect of the antibacterial agent obtained by the technical solution of the present invention is stable, and the antibacterial sheet can still maintain a complete form after the experiment, thereby expanding the scope of use of guanidine hydrochloride antibacterial agents and antibacterial time.

[0142] The above are only preferred embodiments of the present invention, which do not limit the protection scope of the present invention. For those skilled in the art, the present invention may have various modifications and changes. Within the spirit and principle of the present invention, changes, modifications, replacements, integrations and parameter changes to these embodiments by conventional substitutions or by being able to achieve the same functions without departing from the principles and spirit of the present invention all fall within the protection scope of the present invention.

Claims

1. Use of the compound represented by formula (I) in the preparation of an antibacterial agent, Formula (I); in, n is an integer of 40-60, R is a residue of any one of hexamethylenediamine, m-phenylenediamine, p-phenylenediamine or 4,4'-diaminodicyclohexylmethane, X is a benzene ring, a furan ring or Any one of , a is an integer from 4 to 6.

2. An antibacterial agent, characterized in that The antibacterial agent includes a compound represented by formula (I): Formula (I); wherein n is an integer of 40 to 60, R is a residue of any one of hexamethylenediamine, m-phenylenediamine, p-phenylenediamine or 4,4'-diaminodicyclohexylmethane, and X is a benzene ring, a furan ring or Any one of , a is an integer from 4 to 6.

3. A method for preparing the antibacterial agent according to claim 2, characterized in that: The following steps are involved: S1. After the guanidine hydrochloride and the diamine are heated to be completely dissolved and fully mixed, they are heated in an inert gas atmosphere to react with the guanidine hydrochloride and the diamine to obtain an antibacterial agent intermediate as shown in formula (II); Formula (II); wherein n is an integer of 40-60, and R is a residue of any one of hexamethylenediamine, m-phenylenediamine, p-phenylenediamine, or 4,4'-diaminodicyclohexylmethane; S2. dissolving the antibacterial agent intermediate and sodium salt obtained in S1 in a reaction solvent, stirring and reacting to obtain the antibacterial agent.

4. The method for preparing the antibacterial agent according to claim 3, characterized in that: In S1, the heating treatment adopts a staged heating method; the staged heating method includes a first stage, a second stage, and a third stage, and each stage is heated to a reaction temperature and then subjected to a heat preservation treatment.

5. The method for preparing the antibacterial agent according to claim 4, characterized in that: The first stage includes raising the temperature to 130-140°C and keeping it warm for 0.5-1.5h; The second stage includes raising the temperature to 150-160°C and keeping it at that temperature for 0.5-1.5h; The third stage includes raising the temperature to 170-180° C., removing the ammonia generated by the reaction by vacuuming, and maintaining the temperature for 0.5 h.

6. The method for preparing the antibacterial agent according to claim 4, characterized in that: In the stage heating method, the heating temperatures of the first stage, the second stage, and the third stage are increased sequentially, and the temperature increase gradient of each stage is 20°C.

7. The method for preparing the antibacterial agent according to claim 3, characterized in that: The diamine includes at least one of hexamethylenediamine, p-phenylenediamine, m-phenylenediamine, and 4,4'-diaminodicyclohexylmethane; And / or, the molar ratio of guanidine hydrochloride to the diamine is 1:1 to 1.1:

1.

8. The method for preparing the antibacterial agent according to claim 3, characterized in that: In S2, the sodium salt includes sodium furandicarboxylate, sodium terephthalate, sodium succinate, sodium glutarate or sodium adipic acid; and / or, the molar ratio of the antimicrobial agent intermediate to the sodium salt is 1:0.1 to 1:1; And / or, the temperature at which the antibacterial agent intermediate reacts with the sodium salt ranges from room temperature to 60°C; And / or, the reaction solvent is a water / alcohol mixed system; And / or, the water / alcohol mixed system is any one of water / ethanol, water / isopropanol, water / glycerol, water / n-butanol or water / isobutanol; And / or, the volume ratio of water to alcohol in the water / alcohol mixed system is any ratio.

9. The method for preparing the antibacterial agent according to claim 3, characterized in that: In S1 and S2, the reaction between guanidine hydrochloride and diamine, and the reaction between the antibacterial agent intermediate and the sodium salt are both carried out under the protection of inert gas.

10. Use of the antibacterial agent according to claim 2 as an antibacterial additive in the preparation of thermoplastic resin antibacterial functional products.

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