Efficient bactericidal composition as well as preparation method and application thereof

Abstract

The invention relates to the technical field of bactericidal compositions, and discloses an efficient bactericidal composition and a preparation method and application thereof.The efficient bactericidal composition is prepared by taking diethylenetriamine, cinnamyl aldehyde, 1, 4-dibromobutane and the like as raw materials, performing aldehyde-amine condensation reaction and quaternization reaction to obtain cinnamyl dimeric quaternary ammonium salt, washing clove buds and mint leaves, and drying the clove buds and the mint leaves to obtain the efficient bactericidal composition. And sequentially carrying out supercritical CO2 extraction and ultrasonic-assisted extraction to obtain the essential oil extract. And finally, adding the cinnamyl dimeric quaternary ammonium salt and the essential oil extract into deionized water, and stirring and dispersing to obtain the efficient bactericidal composition. The high-efficiency bactericidal composition prepared by the invention has an excellent bactericidal effect and a green and environment-friendly effect.

Description

Technical Field

[0001] The present invention relates to the technical field of bactericidal compositions, in particular to a high-efficiency bactericidal composition and a preparation method and application thereof. Background Art

[0002] my country is a big agricultural country. With the development of agriculture, the occurrence of diseases, insects and weeds has also followed. Gray mold caused by Botrytis cinerea is an important disease that can cause rot of fruits and flowers, affecting yield and quality, and posing a serious threat to vegetables and flowers. The chemical control of gray mold is to use benzimidazole fungicides, but due to the long-term and frequent use of such drugs, Botrytis cinerea has developed drug resistance. Therefore, it is very important to develop a low-toxic, low-residue, environmentally friendly fungicide composition.

[0003] Quaternary ammonium salt cations have the characteristics of low toxicity and low stimulation, and are widely used in the fields of surfactants, bactericides, etc. Cinnamaldehyde is a class of aldehyde organic compounds, which is widely present in plants such as cinnamon and laurel, and has the effects of bactericidal, antibacterial, and antioxidant. It is non-toxic or low-toxic to the human body, and can play a strong inhibitory effect on the reproduction of microorganisms. Mint, also known as peppermint, has the effects of dispersing wind-heat and clearing the throat, and is widely used in the fields of food, tobacco, and cosmetics. The main component of clove buds is eugenol, which has the effects of bactericidal, anthelmintic, and analgesic, and is widely used in the fields of food, cosmetics, etc. Based on this, the present invention prepares a bactericidal composition, which uses cinnamaldehyde, peppermint, clove buds, etc. as raw materials, and the prepared bactericidal composition has the characteristics of green environmental protection and high bactericidal efficiency. Summary of the invention

[0004] The purpose of the present invention is to overcome the defects of the prior art and provide a high-efficiency bactericidal composition and a preparation method and application thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions: A high-efficiency bactericidal composition comprises cinnamaldehyde-based gemini quaternary ammonium salt and essential oil extract.

[0006] Furthermore, the preparation method of the high-efficiency bactericidal composition is: Cinnamaldehyde-based gemini quaternary ammonium salt and essential oil extract are added into deionized water, stirred and dispersed to obtain a high-efficiency bactericidal composition.

[0007] Furthermore, the concentration of the cinnamaldehyde-based gemini quaternary ammonium salt in the high-efficiency bactericidal composition is 20-50 μg / L; and the concentration of the essential oil extract is 10-50 mg / L.

[0008] Furthermore, the preparation method of the cinnamaldehyde-based gemini quaternary ammonium salt is: (1) Add diethylenetriamine and potassium hydroxide to an ethanol solvent, stir and disperse, then add cinnamaldehyde, control the temperature to 50-60°C, stir and react for 3-6 hours, and after the reaction is completed, cool to room temperature, filter, wash with ether, and dry to obtain intermediate 1; (2) Add the intermediate 1, 1,4-dibromobutane to an ethanol solvent, stir and disperse, heat to 100-115°C, react for 24-48 hours, and after the reaction is completed, cool to room temperature, wash with ether, and dry to obtain a cinnamaldehyde-based gemini quaternary ammonium salt.

[0009] Furthermore, in (1), the mass ratio of diethylenetriamine, potassium hydroxide and cinnamaldehyde is 1:(1-1.5):(2.5-3).

[0010] Furthermore, in (2), the mass ratio of the intermediate 1 and 1,4-dibromobutane is (4.5-6):1.

[0011] Furthermore, the preparation method of the essential oil extract is: S1, washing clove buds and mint leaves, drying, crushing, passing through a 40-mesh sieve, placing in a supercritical extraction device, and extracting by supercritical CO2 to obtain an essential oil extract 1 and a filter residue 1; S2. Add the filter residue 1 into an ethanol solvent, soak for 1-3 hours, place in a multi-frequency ultrasonic cleaning machine with a frequency of 40-50KHz at 40-55°C, and ultrasonicate for 30-60 minutes. After the cleaning, filter under negative pressure and evaporate to obtain essential oil extract 2 and filter residue 2.

[0012] S3, mixing the essential oil extract 1 and the essential oil extract 2 evenly to obtain an essential oil extract.

[0013] Furthermore, in S1, the carbon dioxide flow rate is set to 30 kg / h, the extraction pressure is set to 35 MPa, the extraction temperature is set to 45° C., and the extraction time is set to 2 h.

[0014] Furthermore, in S1, the mass ratio of clove buds to mint leaves is 1:(0.5-1).

[0015] Furthermore, in S2, the usage ratio of the filter residue 1 to ethanol is 1 g: (6-10) mL.

[0016] The high-efficiency bactericidal composition prepared by the preparation method of the present invention is used in agriculture.

[0017] 3. Beneficial technical effects The invention uses diethylenetriamine, cinnamaldehyde, 1,4-dibromobutane and the like as raw materials, undergoes aldehyde-amine condensation reaction and quaternization reaction to obtain cinnamaldehyde-based gemini quaternary ammonium salt, washes clove buds and mint leaves, and sequentially undergoes supercritical CO2 extraction and ultrasonic-assisted extraction to obtain essential oil extract. Finally, the cinnamaldehyde-based gemini quaternary ammonium salt and the essential oil extract are added to deionized water, stirred and dispersed, and a highly effective bactericidal composition is obtained.

[0018] The cinnamaldehyde used in the present invention is volatile itself, and the present invention chemically reacts it with diethylenetriamine to reduce its volatilization effect and prolong the antibacterial action time of the cinnamaldehyde. The present invention uses green, environmentally friendly, and low-toxic clove buds and mint as raw materials, and after two extractions, the utilization rate of the clove buds and mint can be improved to prevent waste, and the compounding of the clove buds and mint with cinnamaldehyde-based gemini quaternary ammonium salt has a better bactericidal effect on Botrytis cinerea than a single antibacterial component. The present invention reduces the use of chemical pesticides, reduces pesticide residues, reduces environmental pollution, and is of great significance for the high-quality and high-yield of crops. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is the reaction route for cinnamaldehyde-based gemini quaternary ammonium salts. DETAILED DESCRIPTION

[0020] The following is a further description of the highly effective bactericidal composition, preparation method and application of the present invention in conjunction with some specific embodiments. The specific embodiments are provided to further illustrate the present invention in detail, but do not limit the protection scope of the present invention. Example 1

[0021] (1) Add 15 g of diethylenetriamine and 15 g of potassium hydroxide to 200 mL of ethanol solvent, stir and disperse, then add 45 g of cinnamaldehyde, control the temperature to 55 ° C, stir and react for 6 hours. After the reaction is completed, cool to room temperature, filter, wash with ether, and dry to obtain intermediate 1.

[0022] (2) Add 50 g of intermediate 1 and 10 g of 1,4-dibromobutane to 200 mL of ethanol solvent, stir and disperse, heat to 110° C., react for 48 h. After the reaction is completed, cool to room temperature, wash with ether, and dry to obtain cinnamaldehyde-based gemini quaternary ammonium salt.

[0023] (3) 50 g of clove buds and 25 g of peppermint leaves were washed, dried, crushed, passed through a 40-mesh sieve, placed in a supercritical extraction device, and the carbon dioxide flow rate was set to 30 kg / h, the extraction pressure was 35 MPa, the extraction temperature was 45°C, and the extraction time was 2 h. After supercritical CO2 extraction, essential oil extract 1 and residue 1 were obtained.

[0024] (4) Add 20 g of the residue 1 into 120 mL of ethanol solvent, soak for 2 h, place in a multi-frequency ultrasonic cleaning machine at a frequency of 40 kHz at 55° C., and ultrasonicate for 50 min. After the cleaning, filter under negative pressure and perform rotary evaporation to obtain essential oil extract 2 and residue 2.

[0025] (5) The essential oil extract 1 and the essential oil extract 2 are evenly mixed to obtain an essential oil extract.

[0026] (6) Add cinnamaldehyde-based gemini quaternary ammonium salt and essential oil extract into deionized water, stir and disperse, control the concentration of cinnamaldehyde-based gemini quaternary ammonium salt to 20 μg / L, and the concentration of essential oil extract to 10 mg / L, to obtain a highly effective bactericidal composition. Example 2

[0027] (1) Add 15 g of diethylenetriamine and 20 g of potassium hydroxide to 200 mL of ethanol solvent, stir and disperse, then add 40 g of cinnamaldehyde, control the temperature to 60°C, stir and react for 4 h. After the reaction is completed, cool to room temperature, filter, wash with ether, and dry to obtain intermediate 1.

[0028] (2) Add 50 g of intermediate 1 and 10 g of 1,4-dibromobutane to 200 mL of ethanol solvent, stir and disperse, heat to 105° C., react for 48 h. After the reaction is completed, cool to room temperature, wash with ether, and dry to obtain cinnamaldehyde-based gemini quaternary ammonium salt.

[0029] (3) 50 g of clove buds and 30 g of peppermint leaves were washed, dried, crushed, passed through a 40-mesh sieve, placed in a supercritical extraction device, and the carbon dioxide flow rate was set to 30 kg / h, the extraction pressure was 35 MPa, the extraction temperature was 45°C, and the extraction time was 2 h. After supercritical CO2 extraction, essential oil extract 1 and residue 1 were obtained.

[0030] (4) Add 20 g of the residue 1 into 180 mL of ethanol solvent and soak for 3 h. Place the mixture in a multi-frequency ultrasonic cleaning machine at a frequency of 50 kHz at 40° C. and ultrasonicate for 30 min. After the ultrasonication, filter the mixture under negative pressure and perform rotary evaporation to obtain the essential oil extract 2 and the residue 2.

[0031] (5) The essential oil extract 1 and the essential oil extract 2 are evenly mixed to obtain an essential oil extract.

[0032] (6) Add cinnamaldehyde-based gemini quaternary ammonium salt and essential oil extract into deionized water, stir and disperse, control the concentration of cinnamaldehyde-based gemini quaternary ammonium salt to 30 μg / L, and the concentration of essential oil extract to 20 mg / L, to obtain a highly effective bactericidal composition. Example 3

[0033] (1) Add 15 g of diethylenetriamine and 22.5 g of potassium hydroxide to 200 mL of ethanol solvent, stir and disperse, then add 37.5 g of cinnamaldehyde, control the temperature to 50 ° C, stir and react for 3 h. After the reaction is completed, cool to room temperature, filter, wash with ether, and dry to obtain intermediate 1.

[0034] (2) Add 50 g of intermediate 1 and 10 g of 1,4-dibromobutane to 200 mL of ethanol solvent, stir and disperse, heat to 105° C., react for 24 h. After the reaction is completed, cool to room temperature, wash with ether, and dry to obtain cinnamaldehyde gemini quaternary ammonium salt.

[0035] (3) 50 g of clove buds and 35 g of peppermint leaves were washed, dried, crushed, passed through a 40-mesh sieve, placed in a supercritical extraction device, and the carbon dioxide flow rate was set to 30 kg / h, the extraction pressure was 35 MPa, the extraction temperature was 45°C, and the extraction time was 2 h. After supercritical CO2 extraction, essential oil extract 1 and residue 1 were obtained.

[0036] (4) Add 20 g of the residue 1 into 200 mL of ethanol solvent, soak for 1 h, place in a multi-frequency ultrasonic cleaning machine with a frequency of 40 kHz at 45° C., and ultrasonicate for 60 min. After the cleaning, filter under negative pressure and perform rotary evaporation to obtain essential oil extract 2 and residue 2.

[0037] (5) The essential oil extract 1 and the essential oil extract 2 are evenly mixed to obtain an essential oil extract.

[0038] (6) Add cinnamaldehyde-based gemini quaternary ammonium salt and essential oil extract into deionized water, stir and disperse, control the concentration of cinnamaldehyde-based gemini quaternary ammonium salt to 40 μg / L, and the concentration of essential oil extract to 30 mg / L, to obtain a highly effective bactericidal composition. Example 4

[0039] (1) Add 15 g of diethylenetriamine and 16 g of potassium hydroxide to 200 mL of ethanol solvent, stir and disperse, then add 40 g of cinnamaldehyde, control the temperature to 55 ° C, stir and react for 5 hours. After the reaction is completed, cool to room temperature, filter, wash with ether, and dry to obtain intermediate 1.

[0040] (2) 45 g of intermediate 1 and 10 g of 1,4-dibromobutane were added to 200 mL of ethanol solvent, stirred and dispersed, heated to 100 °C, and reacted for 36 h. After the reaction was completed, the mixture was cooled to room temperature, washed with ether, and dried to obtain cinnamaldehyde-based gemini quaternary ammonium salt.

[0041] (3) 50 g of clove buds and 40 g of peppermint leaves were washed, dried, crushed, passed through a 40-mesh sieve, placed in a supercritical extraction device, and the carbon dioxide flow rate was set to 30 kg / h, the extraction pressure was 35 MPa, the extraction temperature was 45°C, and the extraction time was 2 h. After supercritical CO2 extraction, essential oil extract 1 and residue 1 were obtained.

[0042] (4) Add 20 g of the residue 1 into 200 mL of ethanol solvent, soak for 1 h, place in a multi-frequency ultrasonic cleaning machine with a frequency of 40 kHz at 55° C., and ultrasonicate for 60 min. After the cleaning, filter under negative pressure and perform rotary evaporation to obtain essential oil extract 2 and residue 2.

[0043] (5) The essential oil extract 1 and the essential oil extract 2 are evenly mixed to obtain an essential oil extract.

[0044] (6) Add cinnamaldehyde-based gemini quaternary ammonium salt and essential oil extract into deionized water, stir and disperse, control the concentration of cinnamaldehyde-based gemini quaternary ammonium salt to 45 μg / L, and the concentration of essential oil extract to 40 mg / L, to obtain a highly effective bactericidal composition. Example 5

[0045] (1) Add 15 g of diethylenetriamine and 20 g of potassium hydroxide to 200 mL of ethanol solvent, stir and disperse, then add 12 g of cinnamaldehyde, control the temperature to 55 ° C, stir and react for 4 hours. After the reaction is completed, cool to room temperature, filter, wash with ether, and dry to obtain intermediate 1.

[0046] (2) Add 60 g of intermediate 1 and 10 g of 1,4-dibromobutane to 200 mL of ethanol solvent, stir and disperse, heat to 115° C., react for 48 h. After the reaction is completed, cool to room temperature, wash with ether, and dry to obtain cinnamaldehyde gemini quaternary ammonium salt.

[0047] (3) Wash 50 g of clove buds and 50 g of peppermint leaves, dry them, crush them, pass them through a 40-mesh sieve, and place them in a supercritical extraction equipment. Set the carbon dioxide flow rate to 30 kg / h, the extraction pressure to 35 MPa, the extraction temperature to 45°C, and the extraction time to 2 h. After supercritical CO2 extraction, obtain essential oil extract 1 and residue 1.

[0048] (4) Add 20 g of the residue 1 into 160 mL of ethanol solvent, soak for 2 h, place in a multi-frequency ultrasonic cleaning machine with a frequency of 50 kHz at 45°C, and ultrasonicate for 30 min. After the cleaning, filter under negative pressure and perform rotary evaporation to obtain essential oil extract 2 and residue 2.

[0049] (5) The essential oil extract 1 and the essential oil extract 2 are evenly mixed to obtain an essential oil extract.

[0050] (6) Add cinnamaldehyde-based gemini quaternary ammonium salt and essential oil extract into deionized water, stir and disperse, control the concentration of cinnamaldehyde-based gemini quaternary ammonium salt to 50 μg / L, and the concentration of essential oil extract to 50 mg / L, to obtain a highly effective bactericidal composition.

[0051] Comparative Example 1 The high-efficiency bactericidal composition and its preparation method provided in this comparative example are substantially the same as those in Example 1, with the main difference being that in step (6), no cinnamaldehyde-based gemini quaternary ammonium salt is contained.

[0052] Comparative Example 2 The high-efficiency bactericidal composition and its preparation method provided in this comparative example are substantially the same as those in Example 1, with the main difference being that in step (6), no essential oil extract is contained.

[0053] The slant-stored Botrytis cinerea was inoculated onto a potato dextrose agar plate and cultured at 25°C for 7 days. The plate was then rinsed with sterile water and the count was adjusted to 1×10 using a hemocytometer. 6 The spore suspension of 100 μL / mL was prepared for standby use, the fungicide composition was dripped onto a potato dextrose agar plate, 10 μL of the spore suspension was transferred to the center of the plate using a pipette, the blank control group was treated with sterile water, the spore germination was observed for 12 hours, and the spore germination inhibition rate was calculated. Spore germination rate (%) = number of spore germination / total number of spore germination × 100%, spore germination inhibition rate (%) = (spore germination rate of the control group - spore germination rate of the treatment group) / spore germination rate of the control group × 100%.

[0054] Table 1: Spore germination inhibition rate (%) Example 1 62.3 Example 2 70.9 Example 3 86.4 Example 4 98.3 Example 5 99.9 Comparative Example 1 41.0 Comparative Example 2 28.6 As can be seen from the table, the inhibition rate of Examples 1-5 is greater than that of Comparative Examples 1-2, indicating that the combination of cinnamaldehyde-based quaternary ammonium salt and plant essential oil has a good inhibitory effect on Botrytis cinerea.

[0055] Select clean tomato fruits free of pests and diseases, disinfect them with 0.2% sodium hypochlorite solution, rinse them with sterile water, dry them, and make a circular wound with a depth of 3 mm and a diameter of 2 mm on the tomato. Inject 5 μL, 1×10 6 The spore suspension of 100 / mL was cultured at 25°C for 12 hours, then immersed in a high-efficiency fungicide composition for 5 minutes, taken out, and cultured at 25°C for 3 days, and the diameter of the lesion was measured.

[0056] Table 2: Diameter of lesion / mm Example 1 28.4 Example 2 21.6 Example 3 18.0 Example 4 14.8 Example 5 12.2 Comparative Example 1 38.4 Comparative Example 2 42.6 It can be seen from the table that the tomatoes treated with the high-efficiency fungicide composition of Examples 1-5 have a good fungicide and inhibitory effect on gray mold lesions. Therefore, the high-efficiency fungicide composition prepared by the present invention has a good fungicide and inhibitory effect.

[0057] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention specification, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A highly effective bactericidal composition, characterized in that: The high-efficiency bactericidal composition comprises cinnamaldehyde-based gemini quaternary ammonium salt and essential oil extract; The preparation method of the high-efficiency bactericidal composition is: Cinnamaldehyde-based gemini quaternary ammonium salt and essential oil extract are added into deionized water, stirred and dispersed to obtain a high-efficiency bactericidal composition.

2. The high-efficiency bactericidal composition according to claim 1, characterized in that: The concentration of the cinnamaldehyde-based gemini quaternary ammonium salt in the high-efficiency bactericidal composition is 20-50 μg / L; the concentration of the essential oil extract is 10-50 mg / L.

3. The high-efficiency bactericidal composition according to claim 1, characterized in that: The preparation method of the cinnamaldehyde-based gemini quaternary ammonium salt is: (1) Add diethylenetriamine and potassium hydroxide to an ethanol solvent, stir and disperse, then add cinnamaldehyde, control the temperature to 50-60°C, stir and react for 3-6 hours, and after the reaction is completed, cool to room temperature, filter, wash with ether, and dry to obtain intermediate 1; (2) Add the intermediate 1, 1,4-dibromobutane to an ethanol solvent, stir and disperse, heat to 100-115°C, react for 24-48 hours, and after the reaction is completed, cool to room temperature, wash with ether, and dry to obtain a cinnamaldehyde-based gemini quaternary ammonium salt.

4. The high-efficiency bactericidal composition according to claim 3, characterized in that: In the above (1), the mass ratio of diethylenetriamine, potassium hydroxide and cinnamaldehyde is 1:(1-1.5):(2.5-3).

5. The high-efficiency bactericidal composition according to claim 3, characterized in that: In the above (2), the mass ratio of the intermediate 1 and 1,4-dibromobutane is (4.5-6):

1.

6. The high-efficiency bactericidal composition according to claim 1, characterized in that: The preparation method of the essential oil extract is: S1, washing clove buds and mint leaves, drying, crushing, passing through a 40-mesh sieve, placing in a supercritical extraction device, and extracting by supercritical CO2 to obtain an essential oil extract 1 and a filter residue 1; S2, adding the filter residue 1 to an ethanol solvent, soaking for 1-3 hours, placing it in a multi-frequency ultrasonic cleaning machine with a frequency of 40-50KHz at 40-55°C, ultrasonicating for 30-60 minutes, after which, filtering under negative pressure, rotary evaporation, and obtaining essential oil extract 2 and filter residue 2; S3, mixing the essential oil extract 1 and the essential oil extract 2 evenly to obtain an essential oil extract.

7. The high-efficiency bactericidal composition according to claim 6, characterized in that: In S1, the carbon dioxide flow rate is set to 30 kg / h, the extraction pressure is set to 35 MPa, the extraction temperature is set to 45° C., and the extraction time is set to 2 h.

8. The high-efficiency bactericidal composition according to claim 6, characterized in that: In S1, the mass ratio of clove buds to mint leaves is 1:(0.5-1).

9. The high-efficiency bactericidal composition according to claim 6, characterized in that: In the S2, the usage ratio of the filter residue 1 to ethanol is 1 g: (6-10) mL.

10. Use of the high-efficiency fungicidal composition prepared by the preparation method according to claim 1 in preventing and controlling gray mold.

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