Preparation method of disease-resistant foliar fertilizer with nano chelating agent applied to apple trees

Abstract

The invention relates to a preparation method of a disease-resistant foliar fertilizer with a nano chelating agent applied to apple trees, and belongs to the technical field of fruit tree disease resistance. The preparation method comprises the following steps: stirring and mixing chicken, concentrated sulfuric acid and water, heating for acidolysis reaction to obtain an acidolysis solution, and standing for layering to obtain an amino acid solution at the lower layer; adding ammonia water into the amino acid liquid, and adjusting the pH value to be neutral; adding activated carbon into the neutralized amino acid liquid, stirring at normal temperature, and filtering; adding zinc sulfate, manganese sulfate and a chelating agent into the filtered amino acid solution, and stirring at room temperature to obtain a clear chelated amino acid salt solution; continuously adding a surfactant, a preservative and monopotassium phosphate, standing, and filtering to obtain the amino acid selenium leaf fertilizer. The amino acid selenium leaf fertilizer prepared by the invention has the effects of reducing the leaf disease condition of apple trees, improving the control effect and effectively improving the disease resistance of the apple trees.

Description

Technical Field

[0001] The invention relates to the technical field of disease resistance of fruit trees, in particular to a method for preparing disease-resistant foliar fertilizer for apple trees using a nano chelating agent. Background Art

[0002] Apple leaf spot is an important disease in apple production, which is particularly prone to epidemic spread in hot and rainy seasons and causes huge economic losses.

[0003] Chinese patent CN110200002B: provides a composition for improving the disease resistance of fruit trees, belonging to the technical field of pesticides. The composition comprises the following components in parts by weight: 25-35 parts of pyraclostrobin, 0.03-0.08 parts of brassinolide, 15-25 parts of dipotassium hydrogen phosphate and 10-20 parts of superphosphate.

[0004] Chinese patent CN119019374A: discloses a carbazole compound, a synthesis method and an application thereof for controlling plant pathogenic bacteria. The carbazole compound is a compound represented by the following general formula (I). The synthesis method uses 9H-carbazole, ethyl bromoacetate, hydrazine hydrate, phenyl isothiocyanate and substituted benzyl halide as raw materials, and prepares the target compound through a five-step reaction.

[0005] Chinese patent CN105981728B: Provides a pesticide composition containing a triazole fungicide, which contains an active component A and a triazole fungicide. The triazole fungicide is selected from fenbuconazole, epoxiconazole, tebuconazole, hexaconazole, propiconazole, prothioconazole, difenoconazole, diniconazole, etc.

[0006] At present, the prevention and control of apple leaf spot disease is mainly based on chemical control. Although there are many effective agents, their modes of action are relatively simple, mainly concentrated in triazole drugs, which are prone to drug resistance. Summary of the invention

[0007] In order to solve the above problems, the present invention provides a method for preparing a disease-resistant foliar fertilizer for apple trees using a nano-chelating agent, and the operating steps are as follows:

[0008] S1: According to weight, 70-100 parts of chicken, 7-10 parts of concentrated sulfuric acid, and 7-10 parts of water are stirred and mixed, and then heated to perform acid hydrolysis reaction to obtain an acid hydrolyzate. After standing and stratifying, the lower layer is an amino acid liquid;

[0009] S2: Add ammonia water to the amino acid solution to adjust the pH value to neutral;

[0010] S3: Add 5-10 parts of activated carbon to the neutralized amino acid solution, stir at room temperature for 20-40 minutes, and filter;

[0011] S4: Add 1-5 parts of zinc sulfate, 1-3 parts of manganese sulfate, and 0.8-1.6 parts of a chelating agent to the filtered amino acid solution, and stir at room temperature for 10-20 minutes to obtain a clear chelated amino acid salt solution;

[0012] S5: Continue to add 0.1-1 parts of surfactant, 0.01-0.05 parts of preservative, and 1-3 parts of potassium dihydrogen phosphate, let stand for 1-2 days, filter, and obtain amino acid selenium foliar fertilizer.

[0013] The acid hydrolysis reaction temperature is 100-110° C. and the time is 150-180 min.

[0014] The mass concentration of the ammonia water is 25-28%.

[0015] The surfactant is one of Tween-20, Tween-40, Tween-60 and Tween-80.

[0016] The preservative is one of sorbic acid, potassium sorbate, benzoic acid and sodium benzoate.

[0017] The amino acid selenium foliar fertilizer is diluted 300-700 times with clean water and then applied.

[0018] The preparation method of the nano chelating agent is as follows:

[0019] K1: Weigh 3-6 parts of (ferrocenyl) hexanethiol CAS No.: 134029-92-8, 100-120 parts of DMF, 1-4 parts of trans-1,3-butadiene-1,4-dicarboxylic acid CAS: 3588-17-8, 0.3-0.6 parts of L-allylglycine CAS: 195316-72-4, 10-17 parts of nano titanium dioxide, and 0.003-0.03 parts of photoinitiator, and stir and mix them uniformly to obtain a mixture;

[0020] K2: The above mixture is stirred and reacted at 60-70°C for 100-150 minutes under nitrogen protection; a click chemistry reaction is carried out under ultraviolet light with a maximum absorption wavelength of 365nm. After the reaction is completed, DMF is removed by distillation to obtain the desired nano-chelating agent.

[0021] The photoinitiator is one of benzophenone, 4-chlorobenzophenone and 4-methylbenzophenone.

[0022] Reaction mechanism

[0023] Thiol-olefin click chemistry is an efficient and highly selective synthesis method, and its reaction mechanism mainly includes free radical reaction and Michael addition reaction.

[0024] In the Michael addition reaction mechanism, the thiol group acts as a nucleophile to attack the electron-deficient carbon-carbon double bond in the olefin to form a carbon-sulfur bond and generate a negative carbon ion intermediate. This intermediate is then protonated or reacts with other electrophiles to complete the addition process. This reaction mechanism is often used in organic synthesis to construct complex molecular structures.

[0025] Ferrocenyl hexanethiol is subjected to thiol-olefin click chemistry reaction with trans-1,3-butadiene-1,4-dicarboxylic acid and L-allylglycine, respectively, to obtain a mixed compound of ferrocenyl-butadiene-1,4-dicarboxylic acid / glycine.

[0026] Technical Effects

[0027] The invention discloses a method for preparing a disease-resistant foliar fertilizer for apple trees using a nano-chelating agent. Compared with the prior art, the invention has the following significant effects:

[0028] 1. Selenium is an important mineral element related to plant disease resistance. Under low concentration conditions, it can usually promote plant growth, slow down plant aging, reduce plant lipid peroxidation, and relieve plant oxidative stress. It can also alleviate the harm caused by certain adverse conditions to plants. It works synergistically with fungicides. Fungi isolated from rotten bananas and tomatoes can tolerate higher doses of fungicides. When selenium is added, a smaller dose of fungicide can inhibit the fungi.

[0029] 2. Applying amino acid selenium foliar fertilizer for many consecutive years during the growing season of apple trees can significantly improve the resistance of apple tree branches to the spread of rot diseases, and have a certain control effect on the occurrence of rot diseases in apple trees in the field. DETAILED DESCRIPTION

[0030] In order to further explain the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following is a detailed description in combination with embodiments and comparative examples:

[0031] The diluted amino acid selenium foliar fertilizer was sprayed once at 10, 20, and 30 days after the apple blossoms, and every 10 days after the fruit set, until 10-15 days before the fruit matures. Referring to the survey results of apple leaf spot disease (GB / T17980.124-2004), the leaf disease index was calculated, and the control effect was calculated. The results are shown in Table 1.

[0032] Example 1 A method for preparing a disease-resistant foliar fertilizer for apple trees using a nano-chelating agent, the operating steps of the method are as follows:

[0033] S1: 70g chicken, 7g concentrated sulfuric acid and 7g water were stirred and mixed, and then heated for acid hydrolysis to obtain an acid hydrolyzate. After standing and stratifying, the lower layer was an amino acid solution;

[0034] S2: Add ammonia water to the amino acid solution to adjust the pH value to neutral;

[0035] S3: Add 5 g of activated carbon to the neutralized amino acid solution, stir at room temperature for 20 min, and filter;

[0036] S4: Add 1 g zinc sulfate, 1 g manganese sulfate, and 0.8 g chelating agent to the filtered amino acid solution, and stir at room temperature for 10 minutes to obtain a clear chelated amino acid salt solution;

[0037] S5: Continue to add 0.1g surfactant, 0.01g preservative, and 1g potassium dihydrogen phosphate, let stand for 1 day, filter, and obtain amino acid selenium foliar fertilizer.

[0038] The acid hydrolysis reaction temperature is 100° C. and the time is 150 min.

[0039] The mass concentration of the ammonia water is 25%.

[0040] The surfactant is Tween-20.

[0041] The preservative is sorbic acid.

[0042] The amino acid selenium foliar fertilizer is diluted 300 times with clean water and then applied.

[0043] The preparation method of the nano chelating agent is as follows:

[0044] K1: weigh 3 g (ferrocenyl) hexanethiol CAS No.: 134029-92-8, 100 g DMF, 1 g trans-1,3-butadiene-1,4-dicarboxylic acid CAS: 3588-17-8, 0.3 g L-allylglycine CAS: 195316-72-4, 10 g nano titanium dioxide, and 0.003 g photoinitiator, stir and mix well to obtain a mixture;

[0045] K2: The above mixture was stirred and reacted at 60°C for 100 minutes under nitrogen protection; a click chemistry reaction was carried out under ultraviolet light with a maximum absorption wavelength of 365nm. After the reaction was completed, DMF was removed by distillation to obtain the desired nano-chelating agent.

[0046] The photoinitiator is benzophenone.

[0047] Example 2 A method for preparing a disease-resistant foliar fertilizer for apple trees using a nano-chelating agent, the operating steps of the method are as follows:

[0048] S1: 75g chicken, 8g concentrated sulfuric acid and 8g water were stirred and mixed, and then heated for acid hydrolysis to obtain an acid hydrolyzate. After standing and stratification, the lower layer was an amino acid solution;

[0049] S2: Add ammonia water to the amino acid solution to adjust the pH value to neutral;

[0050] S3: Add 6 g of activated carbon to the neutralized amino acid solution, stir at room temperature for 25 min, and filter;

[0051] S4: Add 2 g zinc sulfate, 2 g manganese sulfate, and 1 g chelating agent to the filtered amino acid solution, and stir at room temperature for 15 minutes to obtain a clear chelated amino acid salt solution;

[0052] S5: Continue to add 0.5g surfactant, 0.02g preservative, and 2g potassium dihydrogen phosphate, let stand for 1 day, filter, and obtain amino acid selenium foliar fertilizer.

[0053] The acid hydrolysis reaction temperature is 105° C. and the time is 160 min.

[0054] The mass concentration of the ammonia water is 26%.

[0055] The surfactant is Tween-40.

[0056] The preservative is potassium sorbate.

[0057] The amino acid selenium foliar fertilizer is diluted 400 times with clean water and then applied.

[0058] The preparation method of the nano chelating agent is as follows:

[0059] K1: Weigh 4 g (ferrocenyl) hexanethiol CAS No.: 134029-92-8, 105 g DMF, 2 g trans-1,3-butadiene-1,4-dicarboxylic acid CAS: 3588-17-8, 0.4 g L-allylglycine CAS: 195316-72-4, 12 g nano titanium dioxide, and 0.01 g photoinitiator, stir and mix well to obtain a mixture;

[0060] K2: The above mixture was stirred and reacted at 65°C for 110 minutes under nitrogen protection; a click chemistry reaction was carried out under ultraviolet light with a maximum absorption wavelength of 365nm. After the reaction was completed, DMF was removed by distillation to obtain the desired nano-chelating agent.

[0061] The photoinitiator is 4-chlorobenzophenone.

[0062] Example 3 A method for preparing a disease-resistant foliar fertilizer for apple trees using a nano-chelating agent, the operating steps of the method are as follows:

[0063] S1: 95g chicken, 9g concentrated sulfuric acid and 9g water were stirred and mixed, and then heated for acid hydrolysis to obtain an acid hydrolyzate. After standing and stratification, the lower layer was an amino acid solution;

[0064] S2: Add ammonia water to the amino acid solution to adjust the pH value to neutral;

[0065] S3: Add 9 g of activated carbon to the neutralized amino acid solution, stir at room temperature for 35 min, and filter;

[0066] S4: Add 4 g zinc sulfate, 2 g manganese sulfate, and 1.4 g chelating agent to the filtered amino acid solution, and stir at room temperature for 15 minutes to obtain a clear chelated amino acid salt solution;

[0067] S5: Continue to add 0.5g surfactant, 0.04g preservative, and 2g potassium dihydrogen phosphate, let stand for 2 days, filter, and obtain amino acid selenium foliar fertilizer.

[0068] The acid hydrolysis reaction temperature is 105° C. and the time is 170 min.

[0069] The mass concentration of the ammonia water is 27%.

[0070] The surfactant is Tween-60.

[0071] The preservative is benzoic acid.

[0072] The amino acid selenium foliar fertilizer is diluted 600 times with clean water and then applied.

[0073] The preparation method of the nano chelating agent is as follows:

[0074] K1: weigh 5 g (ferrocenyl) hexanethiol CAS No.: 134029-92-8, 115 g DMF, 3 g trans-1,3-butadiene-1,4-dicarboxylic acid CAS: 3588-17-8, 0.5 g L-allylglycine CAS: 195316-72-4, 15 g nano titanium dioxide, and 0.02 g photoinitiator, stir and mix well to obtain a mixture;

[0075] K2: The above mixture was stirred and reacted at 65°C for 140 minutes under nitrogen protection; a click chemistry reaction was carried out under ultraviolet light with a maximum absorption wavelength of 365nm. After the reaction was completed, DMF was removed by distillation to obtain the desired nano-chelating agent.

[0076] The photoinitiator is 4-chlorobenzophenone.

[0077] Example 4 A method for preparing a disease-resistant foliar fertilizer for apple trees using a nano-chelating agent, the operating steps of the method are as follows:

[0078] S1: 100g chicken, 10g concentrated sulfuric acid and 10g water were stirred and mixed, and then heated for acid hydrolysis to obtain an acid hydrolyzate. After standing and stratification, the lower layer was an amino acid solution;

[0079] S2: Add ammonia water to the amino acid solution to adjust the pH value to neutral;

[0080] S3: Add 10 g of activated carbon to the neutralized amino acid solution, stir at room temperature for 40 min, and filter;

[0081] S4: Add 5 g zinc sulfate, 3 g manganese sulfate, and 1.6 g chelating agent to the filtered amino acid solution, and stir at room temperature for 20 minutes to obtain a clear chelated amino acid salt solution;

[0082] S5: Continue to add 1g surfactant, 0.05g preservative, and 3g potassium dihydrogen phosphate, let stand for 2 days, filter, and obtain amino acid selenium foliar fertilizer.

[0083] The acid hydrolysis reaction temperature is 110° C. and the time is 180 min.

[0084] The mass concentration of the ammonia water is 28%.

[0085] The surfactant is Tween-80.

[0086] The preservative is sodium benzoate.

[0087] The amino acid selenium foliar fertilizer is diluted 700 times with clean water and then applied.

[0088] The preparation method of the nano chelating agent is as follows:

[0089] K1: weigh 6 g (ferrocenyl) hexanethiol CAS No.: 134029-92-8, 120 g DMF, 4 g trans-1,3-butadiene-1,4-dicarboxylic acid CAS: 3588-17-8, 0.6 g L-allylglycine CAS: 195316-72-4, 17 g nano titanium dioxide, and 0.03 g photoinitiator, stir and mix well to obtain a mixture;

[0090] K2: The above mixture was stirred and reacted at 70°C for 150 minutes under nitrogen protection; a click chemistry reaction was carried out under ultraviolet light with a maximum absorption wavelength of 365nm. After the reaction was completed, DMF was removed by distillation to obtain the desired nano-chelating agent.

[0091] The photoinitiator is 4-methylbenzophenone.

[0092] Comparative Example 1 does not add a chelating agent, and the rest is the same as Example 1.

[0093] In Comparative Example 2, trans-1,3-butadiene-1,4-dicarboxylic acid was not added, and the other steps were the same as those in Example 1.

[0094] Comparative Example 3 did not add L-allyl glycine, and the rest was the same as Example 1.

[0095] Table 1

[0096]

[0097]

[0098] Through the data analysis of the above embodiments and comparative examples, the amino acid selenium foliar fertilizer prepared by the present invention has the effects of reducing the leaf disease of apple trees, improving the prevention and control effect, and can effectively improve the disease resistance of apple trees.

[0099] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A method for preparing a disease-resistant foliar fertilizer for apple trees using a nano-chelating agent, characterized in that: The operation steps are: S1: According to weight, 70-100 parts of chicken, 7-10 parts of concentrated sulfuric acid, and 7-10 parts of water are stirred and mixed, and then heated to perform acid hydrolysis reaction to obtain an acid hydrolyzate. After standing and stratifying, the lower layer is an amino acid liquid; S2: Add ammonia water to the amino acid solution to adjust the pH value to neutral; S3: Add 5-10 parts of activated carbon to the neutralized amino acid solution, stir at room temperature for 20-40 minutes, and filter; S4: Add 1-5 parts of zinc sulfate, 1-3 parts of manganese sulfate, and 0.8-1.6 parts of a chelating agent to the filtered amino acid solution, and stir at room temperature for 10-20 minutes to obtain a clear chelated amino acid salt solution; S5: Continue to add 0.1-1 parts of surfactant, 0.01-0.05 parts of preservative, and 1-3 parts of potassium dihydrogen phosphate, let stand for 1-2 days, filter, and obtain amino acid selenium foliar fertilizer; The chelating agent is prepared by reacting (ferrocenyl) hexanethiol, trans-1,3-butadiene-1,4-dicarboxylic acid and L-allylglycine.

2. A method for preparing a disease-resistant foliar fertilizer for apple trees using a nano-chelating agent according to claim 1, characterized in that: The acid hydrolysis reaction temperature is 100-110° C. and the time is 150-180 min.

3. A method for preparing a disease-resistant foliar fertilizer for apple trees using a nano-chelating agent according to claim 1, characterized in that: The mass concentration of the ammonia water is 25-28%.

4. The method for preparing a disease-resistant foliar fertilizer for apple trees using a nano-chelating agent according to claim 1, characterized in that: The surfactant is one of Tween-20, Tween-40, Tween-60 and Tween-80.

5. The method for preparing a disease-resistant foliar fertilizer for apple trees using a nano-chelating agent according to claim 1, characterized in that: The preservative is one of sorbic acid, potassium sorbate, benzoic acid and sodium benzoate.

6. The method for preparing a disease-resistant foliar fertilizer for apple trees using a nano-chelating agent according to claim 1, characterized in that: The amino acid selenium foliar fertilizer is diluted 300-700 times with clean water and then applied.

7. The method for preparing a disease-resistant foliar fertilizer for apple trees using a nano-chelating agent according to claim 1, characterized in that: The preparation method of the nano chelating agent is as follows: K1: weigh 3-6 parts of (ferrocenyl) hexanethiol, 100-120 parts of DMF, 1-4 parts of trans-1,3-butadiene-1,4-dicarboxylic acid, 0.3-0.6 parts of L-allylglycine, 10-17 parts of nano titanium dioxide, and 0.003-0.03 parts of a photoinitiator, and stir and mix them uniformly to obtain a mixture; K2: The above mixture is stirred and reacted at 60-70°C for 100-150 minutes under nitrogen protection; a click chemistry reaction is carried out under ultraviolet light with a maximum absorption wavelength of 365nm. After the reaction is completed, DMF is removed by distillation to obtain the desired nano-chelating agent.

8. The method for preparing a disease-resistant foliar fertilizer for apple trees using a nano-chelating agent according to claim 7, characterized in that: The photoinitiator is one of benzophenone, 4-chlorobenzophenone and 4-methylbenzophenone.

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