A nematicidal granule containing 5-hydroxymethylfurfural and a method for preparing the same

Abstract

The present application belongs to the technical field of pesticide preparation, and particularly relates to a nematocidal granule containing 5-hydroxymethyl furfural and a preparation method thereof. The granule contains, by mass percentage, 1-20% of 5-hydroxymethyl furfural, 0.5-10% of a stabilizer, 0-10% of a binder I, 0-10% of a binder II, 0-4% of a lubricant, and the balance of a carrier; the stabilizer is one or more of sodium hydrosulfite, sodium metabisulfite, ascorbic acid, 2,6-di-tert-butyl-p-cresol, and acetylcholine. The pesticide granule prepared by the present application has good stability, is not prone to degradation of effective drug components, has good flowability, and has good mixing uniformity with soil, and has a positive significance for agricultural modernization.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of pesticide preparation, and particularly relates to a nematocide granule containing 5-hydroxymethylfurfural and a preparation method thereof. BACKGROUND

[0002] Root-knot nematodes are a kind of agricultural pests with serious harm, and the agricultural loss caused by the root-knot nematodes is about 100 billion US dollars per year in the world. At present, the common chemical means for preventing and treating the root-knot nematodes is mainly to use chemical pesticides with lethal effect. With the restriction or prohibition of the use of high-toxicity pesticides such as fenamiphos, carbofuran and terbufos, abamectin has become the main pesticide for preventing and treating nematodes. However, long-term single use of abamectin has caused great resistance of the nematodes. Therefore, there is an urgent need for a high-efficiency and low-toxicity nematode control pesticide to provide a new route for controlling nematode diseases.

[0003] 5-hydroxymethylfurfural is considered to be one of the most important biomass-based platform compounds, and is widely used in the preparation of multifunctional compounds such as fine chemicals, key pharmaceutical intermediates, functional polyesters, solvents and fuels. It is also an important bio-based material monomer, which can be synthesized from all types of C6 carbohydrates including monomer and polymer carbohydrates such as biomass raw materials of monosaccharide, glucose, sucrose, starch, inulin and cellulose. In previous studies, 5-hydroxymethylfurfural was found to have certain nematocidal activity under in vitro conditions. However, the original drug of 5-hydroxymethylfurfural has very poor stability at room temperature, and is usually stored in the form of solid crystal below 4 DEG C. This not only increases the storage cost of 5-hydroxymethylfurfural, but also greatly limits its application effect as a nematocide in practical application. SUMMARY

[0004] The technical problem to be solved by the present application is to provide a new nematocide granule containing 5-hydroxymethylfurfural and a preparation method thereof. By using a specific carrier to load the drug, the nematocide granule has good long-term storage performance and certain sustained-release performance, thereby being beneficial to the prevention and treatment of nematode diseases.

[0005] To solve the above technical problems, the technical scheme adopted by the present application is as follows:

[0006] A nematocide granule containing 5-hydroxymethylfurfural (5-HMF), wherein the 5-hydroxymethylfurfural accounts for 1-20% by mass percentage, the stabilizer accounts for 0.5-10% by mass percentage, the binder I accounts for 0-10% by mass percentage, the binder II accounts for 0-10% by mass percentage, the lubricant accounts for 0-4% by mass percentage, and the carrier accounts for the rest; the stabilizer is one or more of sodium hydrosulfite, sodium metabisulfite, ascorbic acid, 2,6-di-tert-butyl-p-cresol and acetylcholine.

[0007] Preferably, the nematocidal granules contain 5-12% 5-hydroxymethylfurfural, 0.5-6% stabilizer, 0.5-6% binder I, 0.5-6% binder II, 0.2-2.4% lubricant, and the rest is carrier.

[0008] Preferably, the stabilizer is one or more of sodium dithionite, sodium pyrosulfite, and acetylcholine.

[0009] The binder I is soluble starch; the binder II is β-cyclodextrin.

[0010] The lubricant is one or more of liquid paraffin, stearic acid, hydrogenated vegetable oil, and glycerol.

[0011] The carrier is bentonite.

[0012] A preparation method of the nematocidal granules containing 5-hydroxymethylfurfural, comprising the following steps:

[0013] (1) Dissolve 5-hydroxymethylfurfural in water according to the weight percentage, then add the stabilizer, binder I, and binder II, and stir until uniform, and then wait for use;

[0014] (2) Gradually add the carrier to the premix liquid according to the weight percentage, stir and knead until uniform to prepare wet material, and then wait for use;

[0015] (3) Put the wet material prepared in step (2) into an extrusion granulator, extrude into a long strip, and then take out after complete drying, crush, sieve, and obtain the finished product.

[0016] The application of the nematocidal granules containing 5-hydroxymethylfurfural, and the application of the granular preparation in killing nematodes.

[0017] The nematode is southern root-knot nematode.

[0018] Thanks to the above technical solutions, the present application has the following technical progress:

[0019] 1. The 5-hydroxymethylfurfural nematocidal granules prepared by the present application can be stored for a long time at room temperature, and the effective component 5-hydroxymethylfurfural will not degrade and deteriorate in this form.

[0020] 2. In the drying process of the 5-hydroxymethylfurfural nematocidal granules prepared by the present application, 5-hydroxymethylfurfural can stably exist at a high temperature of 110°C for 4 hours, which improves the efficiency of preparing the granules. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 The high-performance liquid chromatogram of 8.2% 5-hydroxymethylfurfural granules provided by the embodiment of the present application.

[0022] Figure 2 The high performance liquid chromatogram of 8.2% 5-hydroxymethylfurfural granules provided by the embodiment of the present application stored at room temperature for 3 months.

[0023] Figure 3 The high performance liquid chromatogram of 8.2% 5-hydroxymethylfurfural granules dried at 28℃ provided by the embodiment of the present application.

[0024] Figure 4 The high performance liquid chromatogram of 8.2% 5-hydroxymethylfurfural granules dried at 65℃ provided by the embodiment of the present application.

[0025] Figure 5 The high performance liquid chromatogram of 8.2% 5-hydroxymethylfurfural granules dried at 110℃ provided by the embodiment of the present application.

[0026] Figure 6 The average number of root nodules of different treatment groups in the pot experiment for 21 days provided by the embodiment of the present application. DETAILED DESCRIPTION

[0027] The present application will be further described in detail below with examples.

[0028] The chemical agents used in the following examples are all obtained by market purchase.

[0029] Example 1 5% 5-hydroxymethylfurfural granules

[0030] The components are weighed according to the following weight ratio: 5% 5-hydroxymethylfurfural, 5% stabilizer, 5% binder I, 5% binder II, and the rest is carrier; wherein the stabilizer is sodium hydrosulfite, the binder I is soluble starch, the binder II is β-cyclodextrin, and the carrier is bentonite.

[0031] The preparation method of the granules is as follows: 5-hydroxymethylfurfural is weighed according to the above percentage content, dissolved with an appropriate amount of water, and after complete dissolution, the stabilizer, binder I, and binder II are added, and the mixture is stirred uniformly to form a premix. Then the carrier is added to the premix, and the material is kneaded and stirred to form a uniform wet material. The wet material is put into an extrusion granulator, the machine frequency is set at 15-20 Hz, and a 1.25 mm aperture extrusion cylinder is used. The wet material is extruded into a long strip, which is completely dried at room temperature. Then the long strip is crushed into granules using a crusher, and the granules are sieved using a 12 mesh standard sieve. The powder is sieved out using a 60 mesh standard sieve to obtain the finished product.

[0032] Example 2 8.2% 5-hydroxymethylfurfural granules

[0033] The components are weighed according to the following weight ratio: 8.2% 5-hydroxymethylfurfural, 4% stabilizer, 4% binder I, 4% binder II, 1.6% lubricant, and the rest is carrier; wherein the stabilizer is sodium hyposulfite, the lubricant is liquid paraffin, the binder I is soluble starch, the binder II is β-cyclodextrin, and the carrier is bentonite.

[0034] The granule preparation method is as follows: 5-hydroxymethylfurfural is weighed according to the above percentage content, dissolved with an appropriate amount of water, and after complete dissolution, the stabilizer, binder I, and binder II are added, and stirred uniformly to form a premix. Then the carrier is added to the premix, the lubricant is added when the carrier is added to half of the mass, and then the material is uniformly stirred and kneaded into a wet material. The material is put into an extrusion granulator, the machine frequency is set to 15-20 Hz, a 1.0 mm aperture extrusion cylinder is used, the wet material is extruded into a long strip, and after complete drying at room temperature, the material is crushed into granules using a crusher, and then the granules are sieved using a 16 mesh standard sieve, and the powder is sieved out using a 60 mesh standard sieve to obtain the finished product.

[0035] The stability of the 8.2% 5-hydroxymethylfurfural granule preparation obtained in this example and 5-hydroxymethylfurfural is detected.

[0036] 1) Stability detection at room temperature:

[0037] The granule preparation obtained in the example and 5-hydroxymethylfurfural are stored at room temperature, and their contents are detected on the detection day, after two weeks of placement, and after three months of placement, respectively (see Figure 1 , Figure 2 and Table 1).

[0038] As can be seen from Figures 1-2 and Table 1, the area of the characteristic peak of the granule liquid chromatogram is almost unchanged. The content of the 8.2% 5-hydroxymethylfurfural granule preparation prepared in December 2022 is 8.17% (referring to the national standard GB22610-2008 carbosulfan) by calculating the content of the high performance liquid chromatogram. The content of the granule of the same batch detected in March 2023 is 8.15% by calculating the content of the high performance liquid chromatogram. As can be seen, the content is almost not reduced within 3 months of storage at room temperature. However, the 5-hydroxymethylfurfural technical material will change in quality within two weeks of storage at room temperature.

[0039] Table 1 Content of 5-hydroxymethylfurfural technical material and granule preparation prepared in Example 2 stored for 2 weeks and 3 months

[0040]

[0041] 2) High temperature stability detection

[0042] In this embodiment, when preparing granules using a granulator, the granules are extruded into long strips and dried at 28°C, 65°C, and 110°C respectively. After drying at different temperatures, the granules are pulverized and sieved to obtain the corresponding granules. The content of the obtained products is detected by high-performance liquid chromatography (HPLC) to determine the stability of the granules at different temperatures. The drying process at 28°C and 65°C lasted 16 days; drying at 110°C lasted 4 hours (see [link to previous instructions]). Figures 3-6 ).

[0043] Depend on Figures 3-6 It is evident that the granules prepared by this invention not only have good long-term storage performance at room temperature, but also maintain good stability even when exceeding the standards of heat storage experiments.

[0044] Example 3 9% 5-hydroxymethylfurfural granules-1

[0045] Weigh each component according to the following weight ratio: 9% 5-hydroxymethylfurfural, 4% binder I, 4% binder II, and the balance is carrier; wherein, the stabilizer is sodium metabisulfite, binder I is soluble starch, binder II is β-cyclodextrin, and the carrier is bentonite.

[0046] The granule preparation method is as follows: Weigh 5-hydroxymethylfurfural according to the above percentage content, dissolve it in an appropriate amount of water, and after it is completely dissolved, add binder I and binder II, stir thoroughly to make a premixed liquid, then add the carrier to the premixed liquid, stir and knead until the material is a uniform wet material, put it into an extrusion granulator, set the machine frequency to 15-20Hz, use an extrusion cylinder with a 1.25mm aperture to extrude the wet material into long strips, dry it completely at room temperature, then use a pulverizer to pulverize it into granules, sieve the granules with a 12-mesh standard sieve, and then sieve the powder with a 60-mesh standard sieve to obtain the finished product.

[0047] Example 4: 9% 5-hydroxymethylfurfural granules - 2

[0048] Weigh each component according to the following weight ratio: 9% 5-hydroxymethylfurfural, 2% stabilizer, 4.5% binder I, 4.5% binder II, and the balance is carrier; wherein, the stabilizer is ascorbic acid, binder I is soluble starch, binder II is β-cyclodextrin, and the carrier is bentonite.

[0049] The granule preparation method is as follows: 5-hydroxymethylfurfural is weighed according to the above percentage content, dissolved in water, after complete dissolution, the stabilizer, binder I and binder II are added, and the mixture is stirred uniformly to form a premix, then the carrier is added to the premix, and the wet material is kneaded until the material is uniform, then the wet material is put into an extrusion granulator, the machine frequency is set to 15-20 Hz, a 1.0 mm aperture extrusion barrel is used, the wet material is extruded into a long strip, and after complete drying at room temperature, the long strip is crushed into granules by using a crusher, the granules are sieved by using a 16 mesh standard sieve, and the powder is sieved out by using a 60 mesh standard sieve, to obtain the finished product.

[0050] Example 5 9% 5-hydroxymethylfurfural granules-3

[0051] The components are weighed according to the following weight ratio: 9% 5-hydroxymethylfurfural, 5% stabilizer, and the balance is the carrier; wherein the stabilizer is 2,6-di-tert-butyl-p-cresol, and the carrier is bentonite.

[0052] The granule preparation method is as follows: 5-hydroxymethylfurfural is weighed according to the above percentage content, dissolved in water, after complete dissolution, the stabilizer, binder I and binder II are added, and the mixture is stirred uniformly to form a premix, then the carrier is added to the premix, and the wet material is kneaded until the material is uniform, then the wet material is put into an extrusion granulator, the machine frequency is set to 15-20 Hz, a 1.0 mm aperture extrusion barrel is used, the wet material is extruded into a long strip, and after complete drying at room temperature, the long strip is crushed into granules by using a crusher, the granules are sieved by using a 16 mesh standard sieve, and the powder is sieved out by using a 60 mesh standard sieve, to obtain the finished product.

[0053] Example 6 11% 5-hydroxymethylfurfural granules

[0054] The components are weighed according to the following weight ratio: 11% 5-hydroxymethylfurfural, 1% stabilizer, and the balance is the carrier; wherein the stabilizer is acetylcholine.

[0055] The granule preparation method is as follows: 5-hydroxymethylfurfural is weighed according to the above percentage content, dissolved in water, after complete dissolution, the stabilizer, binder I and binder II are added, and the mixture is stirred uniformly to form a premix, then the carrier is added to the premix, and the wet material is kneaded until the material is uniform, then the wet material is put into an extrusion granulator, the machine frequency is set to 15-20 Hz, a 1.0 mm aperture extrusion barrel is used, the wet material is extruded into a long strip, and after complete drying at room temperature, the long strip is crushed into granules by using a crusher, the granules are sieved by using a 16 mesh standard sieve, and the powder is sieved out by using a 60 mesh standard sieve, to obtain the finished product.

[0056] Pot culture prevention effect test is carried out by using the granules prepared in the above examples

[0057] In order to better understand the present application, the 5-hydroxymethylfurfural nematicide granules prepared in Example 2 are taken as an example, indoor pot culture prevention effect experiments are carried out, and the mass ratio of each example to the potting soil is as follows:

[0058] Treatment group 1: 8.2% 5-hydroxymethylfurfural nematicide granules: soil = 1:20

[0059] Treatment group 2: 8.2% 5-hydroxymethylfurfural nematicide granules: soil = 1:30

[0060] Treatment group 3: 8.2% 5-hydroxymethylfurfural nematicide granules: soil = 1:40

[0061] Treatment group 4: 8.2% 5-hydroxymethylfurfural nematicide granules: soil = 1:50

[0062] Treatment group 5: 500 ppm 5-hydroxymethylfurfural technical material 90 ml / pot

[0063] Control group 1: blank bentonite granules: soil = 1:50

[0064] Control group 2: blank control

[0065] The indoor potting control effect test method is as follows: the composite potting soil is mixed with 5-hydroxymethylfurfural nematicide granules according to the above examples, and the cucumber seedlings at the one-leaf-one-heart stage with similar growth vigor are transplanted, and cultured in an artificial climate chamber for 21 days. The number of root nodules of the potted plants is counted and the control effect is calculated. Five groups of parallel experiments (see Figure 6 and Table 2).

[0066] The composite potting soil is soil mixed by earthworm manure: fine sand: loess = 1:1:1

[0067] The culture conditions of the artificial climate chamber are as follows: 16 h of daytime, temperature 28°C, humidity 75%; 8 h of night, temperature 20°C, humidity 75%.

[0068] The calculation method of the control effect is as follows:

[0069] Table 2 Average number of root nodules and relative control effect of different treatment groups for 21 days

[0070]

[0071] From Figure 6 and Table 2, it can be seen that 5-hydroxymethylfurfural nematicide granules have obvious control effect on nematodes in the root of cucumber plants in the potting control effect experiment.

[0072] The above embodiments only express several embodiments of the present application, the description is more specific and detailed, but it cannot be understood as the limitation of the patent scope of the present application, various components can be replaced by other equivalent materials not mentioned in the present application, and the purpose of the present application can still be achieved. It should be pointed out that for ordinary skilled in the art, without departing from the concept of the present application, several modifications and improvements can be made, which belong to the protection scope of the present application.

Claims

1. A nematicide granule containing 5-hydroxymethylfurfural (5-HMF), characterized in that: By mass percentage, it comprises 8.2% 5-hydroxymethylfurfural, 4% stabilizer, 4% binder I, 4% binder II, 1.6% lubricant, and the balance being carrier; among which, the stabilizer is sodium dithionite, the lubricant is liquid paraffin, binder I is soluble starch, binder II is β-cyclodextrin, and the carrier is bentonite.

2. A method for preparing the nematicide granules containing 5-hydroxymethylfurfural as described in claim 1, characterized in that: Weigh 5-hydroxymethylfurfural according to the stated percentage content, dissolve it in an appropriate amount of water, and after complete dissolution, add stabilizer, binder I, and binder II, and stir thoroughly to prepare a premix. Then add the carrier to the premix. When the carrier is added to half its mass, add the lubricant, and then stir and knead until the material is a uniform wet material. Put it into an extrusion granulator, set the machine frequency to 15~20Hz, and use an extrusion cylinder with a 1.0mm aperture to extrude the wet material into long strips. After completely drying at room temperature, use a pulverizer to pulverize it into granules, sieve the granules using a 16-mesh standard sieve, and then sieve the powder using a 60-mesh standard sieve to obtain the finished product.

3. The application of the nematicide granules containing 5-hydroxymethylfurfural as described in claim 1, characterized in that: The use of the granular formulation of claim 1 in killing nematodes.

4. The application of the nematicide granules containing 5-hydroxymethylfurfural according to claim 3, characterized in that: The nematode in question is the southern root-knot nematode.

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