Preparation method of intrinsic antibacterial material

Abstract

The present application relates to the field of intrinsic antibacterial technology, and particularly to a preparation method of intrinsic antibacterial material. The organic metal synergist prepared by the present application can change the electron cloud distribution and chemical bonding characteristics of the resin, so that the combination of the resin and nano zinc oxide is more stable and firm. The nano zinc oxide has a large specific surface area and high surface activity, can interact with various microorganisms, and destroy the cell wall or affect the physiological function of the microorganisms. The carboxylic acid copper and the tributyl tin jointly act on the interface between the resin and the nano zinc oxide, enhance the chemical bonding and physical adsorption between the two, and make the dispersion of the nano zinc oxide in the epoxy resin more uniform and stable. The above synergistic effect improves the antibacterial performance of the resin. The intrinsic antibacterial material prepared by the present application has excellent antibacterial performance on escherichia coli and staphylococcus aureus.

Description

Technical Field

[0001] This invention relates to the field of intrinsic antibacterial technology, and in particular to a method for preparing an intrinsic antibacterial material. Background Technology

[0002] In recent years, hygiene and safety in public places have become particularly important, and the development of protective coatings with antibacterial and bacteriostatic functions is an important means of inhibiting the rapid spread of bacteria and viruses. At present, there are many types of antibacterial products, including inorganic, organic, and natural antibacterial materials. Their addition gives the materials the function of killing molds, fungi, and viruses or inhibiting their growth and reproduction.

[0003] Chinese Patent CN116135907A discloses an intrinsically antibacterial nylon prepared by homopolymerization. The structural formula is as follows: [Structure formula would be inserted here], where R1 is a C1-C10 straight-chain hydrocarbon group; R2 is a furan ring, benzene ring, pyrazine ring, or a C1-C3 straight-chain hydrocarbon group; and n is 50-200. This technical solution achieves broad-spectrum antibacterial properties in nylon materials by designing a Schiff base structure with antibacterial activity in the polyamide material backbone. It also solves problems such as decreased antibacterial performance due to antibacterial agent precipitation and antibacterial agent contamination. The production method is simple, low-cost, and allows for flexible and diverse applications.

[0004] Chinese patent CN116284758A also provides an intrinsic antibacterial nylon, which is prepared by copolymerization reaction. It can obtain nylon material with excellent antibacterial properties and long-term antibacterial stability without adding antibacterial agent to nylon material. It avoids problems such as the precipitation of antibacterial agent during the use of material and can effectively ensure the antibacterial properties and antibacterial time of the formed intrinsic antibacterial nylon material.

[0005] Chinese Patent CN117004056A discloses an antibacterial masterbatch and its preparation method. The preparation method includes: preparing a diol containing polyhexamethylene guanidine hydrochloride: reacting polyhexamethylene guanidine hydrochloride with dihydroxy fatty acids to obtain a diol containing polyhexamethylene guanidine hydrochloride; and preparing the antibacterial masterbatch: adding the polyol, isocyanate, and the diol containing polyhexamethylene guanidine hydrochloride obtained in the above steps into a twin-screw extruder, extruding and granulating to obtain the antibacterial masterbatch. The antibacterial masterbatch obtained by this invention is a high-molecular-weight polyurethane material with intrinsic antibacterial properties prepared using polyhexamethylene guanidine hydrochloride-type polyol as a chain extender. This results in a polyurethane material with excellent antibacterial properties. The antibacterial masterbatch has good compatibility with existing polyurethane matrices, and the prepared TPU antibacterial material does not precipitate, has long-lasting antibacterial ability, and differs from small-molecule quaternary ammonium salts and guanidines in that it is easy to store and has low toxicity.

[0006] However, in the use of common commercially available antibacterial materials, antibacterial agents generally still have compatibility issues with different resin matrices, which leads to easy migration and short-lasting antibacterial effects. Summary of the Invention

[0007] The purpose of this invention is to provide a method for preparing intrinsic antibacterial materials, which exhibit excellent antibacterial properties against both Escherichia coli and Staphylococcus aureus.

[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0009] A method for preparing an intrinsic antibacterial material, comprising the following steps:

[0010] M1: By weight, add 0.05-0.5 parts of modified nano ZnO powder to 5-10 parts of cyclohexane-1,2-dicarboxylic acid diglycidyl ester, disperse by ultrasonication, and mix evenly;

[0011] M2: Continue to add 1-5 parts of organometallic synergist and 3-7 parts of bisphenol A epoxy resin (epoxy values ​​of 0.44, 0.51, 0.53 and 0.55 respectively). After mixing and stirring, pour into a mold, place in a vacuum oven for gradient heat preservation for a period of time, and then cool to room temperature to obtain the intrinsic antibacterial material.

[0012] In this invention, the ultrasonic dispersion time of M1 is 10-20 min.

[0013] In this invention, the mixing and stirring time of M1 is 10-30 min.

[0014] In this invention, the operation steps of the vacuum oven of M2 are as follows: keep warm at 60-70℃ for 30-50 minutes, keep warm at 80-90℃ for 30-50 minutes, keep warm at 110-120℃ for 20-40 minutes, and keep warm at 140-150℃ for 50-80 minutes.

[0015] The method for preparing the modified nano-ZnO powder in this invention is as follows:

[0016] H1: Weigh 100-120 parts by weight of nano ZnO powder, 5-10 parts by weight of KH560 (γ-glycidyl etheroxypropyltrimethoxysilane), 100-200 parts by weight of ethanol, and 5-10 parts by weight of deionized water. Disperse by ultrasonication for 10-20 min, mix and stir for 10-30 min, and then vacuum dry.

[0017] H2: After cooling to room temperature, grind to obtain modified nano ZnO powder.

[0018] In this invention, the vacuum drying temperature of H1 is 100-120℃, and the time is 1-3h.

[0019] In this invention, the method for synthesizing the organometallic synergist is as follows:

[0020] K1: By weight, add 10-20 parts of copper chloride, 18-36 parts of 4-aminopyridine-2,6-dicarboxylic acid, and 320-400 parts of N,N-dimethylformamide to a stirred tank and heat and stir to react;

[0021] K2: Add 12-24 parts of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and 1-4 parts of sodium hydroxide to the stirred tank, and heat and stir to react;

[0022] K3: Add 0.01-0.2 parts of allyltributyltin, heat and stir to react; remove N,N-dimethylformamide by vacuum distillation to obtain organometallic synergist.

[0023] In this invention, the reaction temperature of K1 is 30-40℃ and the reaction time is 50-100min.

[0024] In this invention, the reaction temperature of K2 is 40-50℃ and the reaction time is 30-100min.

[0025] In this invention, the reaction temperature of K3 is 70-80℃ and the reaction time is 60-150 min.

[0026] Mechanism of preparation of organometallic synergists:

[0027] Copper chloride reacts with 4-aminopyridine-2,6-dicarboxylic acid to generate copper 4-aminopyridine-2,6-dicarboxylic acid; copper 4-aminopyridine-2,6-dicarboxylic acid undergoes an amino-epoxy addition reaction with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate; copper 4-aminopyridine-2,6-dicarboxylic acid undergoes an amino-allyl addition reaction with allyltributyltin; thus, an organometallic synergist containing copper carboxylic acid and tributyltin is obtained.

[0028] The method for preparing an intrinsic antibacterial material according to the present invention has the following significant advantages compared with the prior art:

[0029] 1. The organometallic synergist prepared in this invention contains tributyltin, which can alter the electron cloud distribution and chemical bonding characteristics of the resin, making its bond with nano-zinc oxide more stable and robust. Nano-zinc oxide has a large specific surface area and high surface activity, and can interact with various microorganisms, destroying their cell walls or affecting their physiological functions. Copper carboxylate and tributyltin work together at the interface between the resin and nano-zinc oxide, enhancing the chemical bonding and physical adsorption between the two, making the dispersion of nano-zinc oxide in epoxy resin more uniform and stable. The above synergistic effects improve the antibacterial properties of the resin.

[0030] 2. The intrinsic antibacterial material prepared by this invention has excellent antibacterial properties against both Escherichia coli and Staphylococcus aureus. Detailed Implementation

[0031] The technical solution of the present invention will be further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited thereto.

[0032] Antibacterial performance test method: Diluted solutions of fourth-generation Escherichia coli and Staphylococcus aureus were selected as experimental bacterial solutions, and the test was performed according to the film-coating method of GB / T21510—2008.

[0033] Example 1

[0034] A method for preparing an intrinsic antibacterial material, comprising the following steps:

[0035] M1: Add 0.05g of modified nano ZnO powder to 5g of cyclohexane-1,2-dicarboxylic acid diglycidyl ester, disperse by ultrasonication, and mix thoroughly.

[0036] M2: Continue to add 1g of organometallic synergist and 3g of bisphenol A epoxy resin (epoxy value 0.44). Mix and stir for 10 minutes, pour into a mold, place in a vacuum oven for gradient heat preservation for a period of time, and then cool to room temperature to obtain the intrinsic antibacterial material.

[0037] The ultrasonic dispersion time of M1 is 10 min.

[0038] The mixing time for M1 is 10 minutes.

[0039] The operating steps of the vacuum oven of M2 are as follows: keep warm at 60℃ for 30 minutes, keep warm at 80℃ for 30 minutes, keep warm at 110℃ for 20 minutes, and keep warm at 140℃ for 50 minutes.

[0040] The method for preparing the modified nano-ZnO powder is as follows:

[0041] H1: Weigh 100g of nano ZnO powder, 5g of KH560 (γ-glycidyl etheroxypropyltrimethoxysilane), 100g of ethanol, and 5g of deionized water. Disperse the mixture by ultrasonication for 10min, mix and stir for 10min, and then vacuum dry.

[0042] H2: After cooling to room temperature, grind to obtain modified nano ZnO powder.

[0043] The vacuum drying temperature of H1 is 100℃ and the time is 1 hour.

[0044] The method for synthesizing the organometallic synergist is as follows:

[0045] K1: Add 10g of copper chloride, 18g of 4-aminopyridine-2,6-dicarboxylic acid, and 320g of N,N-dimethylformamide to a stirred tank and heat and stir to react;

[0046] K2: Add 12g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and 1g of sodium hydroxide to the stirred tank, and heat and stir to react;

[0047] K3: Add 0.01g of allyltributyltin, heat and stir to react; remove N,N-dimethylformamide by vacuum distillation to obtain organometallic synergist.

[0048] The reaction temperature of K1 is 30℃ and the reaction time is 50 min.

[0049] The reaction temperature of K2 is 40℃ and the reaction time is 30 min.

[0050] The reaction temperature of K3 is 70℃ and the reaction time is 60 min.

[0051] Example 2

[0052] A method for preparing an intrinsic antibacterial material, comprising the following steps:

[0053] M1: Add 0.2g of modified nano ZnO powder to 6g of cyclohexane-1,2-dicarboxylic acid diglycidyl ester, disperse by ultrasonication, and mix thoroughly.

[0054] M2: Continue to add 2g of organometallic synergist and 5g of bisphenol A epoxy resin with an epoxy value of 0.51. Mix and stir for 15 minutes, pour into a mold, place in a vacuum oven for gradient heat preservation for a period of time, and then cool to room temperature to obtain the intrinsic antibacterial material.

[0055] The ultrasonic dispersion time of M1 is 15 min.

[0056] The mixing time for M1 is 15 minutes.

[0057] The operating steps of the vacuum oven M2 are as follows: keep warm at 65℃ for 35 minutes, keep warm at 85℃ for 35 minutes, keep warm at 115℃ for 25 minutes, and keep warm at 145℃ for 60 minutes.

[0058] The method for preparing the modified nano-ZnO powder is as follows:

[0059] H1: Weigh 105g of nano ZnO powder, 6g of KH560 (γ-glycidyl etheroxypropyltrimethoxysilane), 130g of ethanol, and 6g of deionized water. Disperse the mixture by ultrasonication for 15min, mix and stir for 15min, and then vacuum dry.

[0060] H2: After cooling to room temperature, grind to obtain modified nano ZnO powder.

[0061] The vacuum drying temperature of H1 is 105℃ and the time is 2h.

[0062] The method for synthesizing the organometallic synergist is as follows:

[0063] K1: Add 13g of copper chloride, 24g of 4-aminopyridine-2,6-dicarboxylic acid, and 340g of N,N-dimethylformamide to a stirred tank and heat and stir to react;

[0064] K2: Add 16g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and 2g of sodium hydroxide to the stirred tank, and heat and stir to react;

[0065] K3: Add 0.1g of allyltributyltin, heat and stir to react; remove N,N-dimethylformamide by vacuum distillation to obtain organometallic synergist.

[0066] The reaction temperature of K1 is 35℃ and the reaction time is 60 min.

[0067] The reaction temperature of K2 is 45℃ and the reaction time is 50 min.

[0068] The reaction temperature of K3 is 75℃ and the reaction time is 80 min.

[0069] Example 3

[0070] A method for preparing an intrinsic antibacterial material, comprising the following steps:

[0071] M1: Add 0.4g of modified nano ZnO powder to 9g of cyclohexane-1,2-dicarboxylic acid diglycidyl ester, disperse by ultrasonication, and mix thoroughly.

[0072] M2: Continue to add 4g of organometallic synergist and 6g of bisphenol A epoxy resin (epoxy value 0.53), mix and stir for 25 minutes, pour into a mold, place in a vacuum oven for gradient heat preservation for a period of time, and then cool to room temperature to obtain the intrinsic antibacterial material.

[0073] The ultrasonic dispersion time of M1 is 15 min.

[0074] The mixing time for M1 is 25 minutes.

[0075] The operating steps of the vacuum oven M2 are as follows: keep warm at 65℃ for 45 minutes, keep warm at 85℃ for 45 minutes, keep warm at 115℃ for 35 minutes, and keep warm at 145℃ for 70 minutes.

[0076] The method for preparing the modified nano-ZnO powder is as follows:

[0077] H1: Weigh 115g of nano ZnO powder, 9g of KH560 (γ-glycidyl etheroxypropyltrimethoxysilane), 180g of ethanol, and 9g of deionized water. Disperse the mixture by ultrasonication for 15min, mix and stir for 25min, and then vacuum dry.

[0078] H2: After cooling to room temperature, grind to obtain modified nano ZnO powder.

[0079] The vacuum drying temperature of H1 is 115℃ and the time is 2h.

[0080] The method for synthesizing the organometallic synergist is as follows:

[0081] K1: Add 18g of copper chloride, 32g of 4-aminopyridine-2,6-dicarboxylic acid, and 380g of N,N-dimethylformamide to a stirred tank and heat and stir to react;

[0082] K2: Add 22g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and 3g of sodium hydroxide to the stirred tank, and heat and stir to react;

[0083] K3: Add 0.15g of allyltributyltin, heat and stir to react; remove N,N-dimethylformamide by vacuum distillation to obtain organometallic synergist.

[0084] The reaction temperature of K1 is 35℃ and the reaction time is 90 min.

[0085] The reaction temperature of K2 is 45℃ and the reaction time is 80 min.

[0086] The reaction temperature of K3 is 75℃ and the reaction time is 130 min.

[0087] Example 4

[0088] A method for preparing an intrinsic antibacterial material, comprising the following steps:

[0089] M1: Add 0.5g of modified nano ZnO powder to 10g of cyclohexane-1,2-dicarboxylic acid diglycidyl ester, disperse by ultrasonication, and mix thoroughly.

[0090] M2: Continue to add 5g of organometallic synergist and 7g of bisphenol A epoxy resin (epoxy value 0.55), mix and stir for 30 minutes, pour into a mold, place in a vacuum oven for gradient heat preservation for a period of time, and then cool to room temperature to obtain the intrinsic antibacterial material.

[0091] The ultrasonic dispersion time of M1 is 20 min.

[0092] The mixing time for M1 is 30 minutes.

[0093] The operating steps of the vacuum oven of M2 are as follows: keep warm at 70℃ for 50 minutes, keep warm at 90℃ for 50 minutes, keep warm at 120℃ for 40 minutes, and keep warm at 150℃ for 80 minutes.

[0094] The method for preparing the modified nano-ZnO powder is as follows:

[0095] H1: Weigh 120g of nano ZnO powder, 10g of KH560 (γ-glycidyl etheroxypropyltrimethoxysilane), 200g of ethanol, and 10g of deionized water. Disperse the mixture by ultrasonication for 20min, mix and stir for 30min, and then vacuum dry.

[0096] H2: After cooling to room temperature, grind to obtain modified nano ZnO powder.

[0097] The vacuum drying temperature of H1 is 120℃ and the time is 3h.

[0098] The method for synthesizing the organometallic synergist is as follows:

[0099] K1: Add 20g of copper chloride, 36g of 4-aminopyridine-2,6-dicarboxylic acid, and 400g of N,N-dimethylformamide to a stirred tank and heat and stir to react;

[0100] K2: Add 24g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and 4g of sodium hydroxide to the stirred tank, and heat and stir to react;

[0101] K3: Add 0.2g of allyltributyltin, heat and stir to react; remove N,N-dimethylformamide by vacuum distillation to obtain organometallic synergist.

[0102] The reaction temperature of K1 is 40℃ and the reaction time is 100min.

[0103] The reaction temperature of K2 is 50℃ and the reaction time is 100 min.

[0104] The reaction temperature of K3 is 80℃ and the reaction time is 150 min.

[0105] Comparative Example 1

[0106] Without the addition of organometallic synergists, otherwise the same as in Example 1.

[0107] Comparative Example 2

[0108] The 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate was not added, and the rest was the same as in Example 1.

[0109] Comparative Example 3

[0110] Allyltributyltin was not added; otherwise, it was the same as in Example 1.

[0111] Test results:

[0112]

[0113] Based on the data analysis of the above embodiments and comparative examples, the intrinsic antibacterial material prepared by the present invention has excellent antibacterial properties against both Escherichia coli and Staphylococcus aureus.

[0114] The embodiments described in this specification are merely examples of implementations of the inventive concept. The scope of protection of this invention should not be considered as limited to the specific forms stated in the embodiments. The scope of protection of this invention also includes equivalent technical means that can be conceived by those skilled in the art based on the inventive concept.

Claims

1. A method for preparing an intrinsic antibacterial material, comprising the following steps: M1: By weight, add 0.05-0.5 parts of modified nano ZnO powder to 5-10 parts of cyclohexane-1,2-dicarboxylic acid diglycidyl ester, disperse by ultrasonication, and mix evenly; M2: Continue to add 1-5 parts of organometallic synergist and 3-7 parts of bisphenol A epoxy resin, wherein the epoxy value of the bisphenol A epoxy resin is 0.44, 0.51, 0.53 or 0.55 respectively. After mixing and stirring, pour into a mold, place in a vacuum oven and keep warm in a gradient for a period of time, and then cool to room temperature to obtain the intrinsic antibacterial material. The method for synthesizing the organometallic synergist in M2 is as follows: K1: By weight, add 10-20 parts of copper chloride, 18-36 parts of 4-aminopyridine-2,6-dicarboxylic acid, and 320-400 parts of N,N-dimethylformamide to a stirred tank and heat and stir to react; K2: Add 12-24 parts of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarbamate and 1-4 parts of sodium hydroxide to the stirred tank, and heat and stir to react; K3: Add 0.01-0.2 parts of allyltributyltin, heat and stir to react; remove N,N-dimethylformamide by vacuum distillation to obtain organometallic synergist.

2. The method for preparing an intrinsic antibacterial material according to claim 1, characterized in that: The ultrasonic dispersion time of M1 is 10-20 min.

3. The method for preparing an intrinsic antibacterial material according to claim 1, characterized in that: The mixing time for M1 is 10-30 minutes.

4. The method for preparing an intrinsic antibacterial material according to claim 1, characterized in that: The operating steps of the vacuum oven of M2 are as follows: keep warm at 60-70℃ for 30-50 minutes, keep warm at 80-90℃ for 30-50 minutes, keep warm at 110-120℃ for 20-40 minutes, and keep warm at 140-150℃ for 50-80 minutes.

5. The method for preparing an intrinsic antibacterial material according to claim 1, characterized in that: The preparation method of the modified nano-ZnO powder in M1 is as follows: H1: Weigh 100-120 parts by weight of nano ZnO powder, 5-10 parts by weight of KH560 (γ-glycidoxypropyltrimethoxysilane), 100-200 parts by weight of ethanol, and 5-10 parts by weight of deionized water. Disperse by ultrasonication for 10-20 min, mix and stir for 10-30 min, and then vacuum dry. H2: After cooling to room temperature, grind to obtain modified nano ZnO powder.

6. The method for preparing an intrinsic antibacterial material according to claim 5, characterized in that: The vacuum drying temperature of H1 is 100-120℃, and the time is 1-3h.

7. The method for preparing an intrinsic antibacterial material according to claim 1, characterized in that: The reaction temperature of K1 is 30-40℃ and the reaction time is 50-100min.

8. The method for preparing an intrinsic antibacterial material according to claim 1, characterized in that: The reaction temperature of K2 is 40-50℃, and the reaction time is 30-100 min.

9. The method for preparing an intrinsic antibacterial material according to claim 1, characterized in that: The reaction temperature of K3 is 70-80℃, and the reaction time is 60-150 min.

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