Application of organic silicon as leaf surface spreading agent and preparation

Abstract

The invention provides an application of organic silicon as a leaf surface spreading agent. A preparation method of the organic silicon comprises the following steps: A, mixing allyl alcohol polyether with side chain hydrogen-containing silicone oil and allyl glycidyl ether; and B, heating, adding a catalyst, and carrying out an addition reaction to obtain the organic silicon. The invention also provides a preparation obtained by the application, the preparation comprises a mixture of the organic silicon and a water-soluble liquid medicine, and the water-soluble liquid medicine comprises one or more of a pesticide and a foliar fertilizer. According to the preparation method, the side chain hydrogen-containing silicone oil is modified by controlling the hydrogen content of the side chain hydrogen-containing silicone oil, and organic silicon is added as a leaf surface spreading agent, so that spreading of preparations such as pesticides and leaf fertilizers on plant leaf surfaces can be promoted, meanwhile, liquid medicine is promoted to permeate into plants from the plant surfaces, the effect of the liquid medicine is comprehensively improved, and the effect of the liquid medicine is improved. The obvious effect on improving the agricultural benefits is achieved.

Description

Technical Field

[0001] The invention relates to the technical field of agricultural adjuvants, and in particular to the application and preparation of organosilicon as a foliar spreading agent. Background Art

[0002] Pesticides and foliar fertilizers are commonly used preparations of modern pesticides. However, the surface of plants generally repels liquids, especially water-soluble liquids. After applying pesticides to plants, when the surface tension of the liquid is lower than the surface tension of the leaves, it will be adsorbed and wetted on the surface of the target crop. On the contrary, the liquid shrinks and gathers on the surface of the target crop, and the droplets roll down, causing the liquid to be lost.

[0003] However, adding organosilicon spreading agents to these pesticides and foliar fertilizers can effectively reduce the surface tension of the liquid medicine, reduce the contact angle between the droplets and the surface of the crop leaves, and make the liquid medicine have a strong spreading ability on the plant leaves, thereby significantly enhancing the wetting performance on the plant surface. When applied to pesticides, this spreading performance of organosilicon spreading agents can make the liquid medicine cover and adhere to a larger area on the plant surface, allowing the pesticide to directly contact and kill pests; when applied to foliar fertilizers, it can also improve the spreading effect of the fertilizer liquid on the leaves, thereby improving the absorption efficiency of the leaves for foliar fertilizers.

[0004] Although there are many methods for modifying silicone, how to further improve the application effect of modified silicone as a foliar spreading agent is still an important issue that needs to be solved. Summary of the invention

[0005] The purpose of the present invention is to solve the problem of poor liquid spreadability and liquid penetration when modified organic silicon is used as a foliar spreading agent.

[0006] To solve the above problems, the present invention adopts the following technical solutions: The present invention provides an application of an organosilicon as a foliar spreading agent, wherein the structure of the organosilicon is shown in structural formula I. ; Among them, 55≤x≤59, 6≤y+z≤11; EO is ethoxy, PO is propoxy; 20≤m≤30, 7≤n≤15.

[0007] As a preferred embodiment of the present invention, the preparation of the organosilicon comprises the following steps: A. Mix allyl alcohol polyether with side chain hydrogen-containing silicone oil and allyl glycidyl ether; B. After heating, a catalyst is added to carry out an addition reaction to obtain the organosilicon.

[0008] Furthermore, in the preparation of the organosilicon, the hydrogen content of the side chain hydrogen-containing silicone oil is 0.13% to 0.16%, the viscosity is 130 to 150 cP, and the relative molecular mass is 4600 to 5200.

[0009] Furthermore, in the preparation of the organosilicon, the structure of the allyl alcohol polyether is as shown in structural formula II, ; Among them, EO is ethoxy, PO is propoxy, 20≤m≤30, 7≤n≤15.

[0010] Furthermore, in the preparation of the organosilicon, the relative molecular mass of the allyl alcohol polyether is 1800.

[0011] Furthermore, in the preparation of the organosilicon, the mass ratio of the side chain hydrogen-containing silicone oil, the allyl alcohol polyether and the allyl glycidyl ether is 94-106:300:4.

[0012] Furthermore, in the preparation of the organosilicon, in step B, the catalyst includes chloroplatinic acid; the mass of the catalyst includes 10 to 30 ppm of the total mass of the side chain hydrogen-containing silicone oil, the allyl alcohol polyether and the allyl glycidyl ether; In step B, the temperature of adding the catalyst and the addition reaction is 85-105° C., and the time of the addition reaction is 3-4 hours; in step B, the addition reaction is stirred.

[0013] Furthermore, in the preparation of the organosilicon, before the mixing in step A, the allyl alcohol polyether is heated to 100° C. for half an hour to remove moisture; in step B, N is introduced into the reaction container during the addition reaction. 2 .

[0014] The present invention also provides a preparation obtained by the above application, wherein the preparation comprises a mixture of the organosilicon and a water-soluble medicinal solution.

[0015] Furthermore, the water-soluble liquid medicine includes one or more of pesticides and foliar fertilizers.

[0016] As a preferred solution for the present invention, allyl alcohol polyether adopts F-6.

[0017] As a preferred embodiment of the present invention, the structure of the allyl glycidyl ether is shown in Structure III. .

[0018] Compared with the prior art, the implementation of the present invention has the following beneficial effects: 1. The preparation method of the present invention modifies the side chain hydrogen-containing silicone oil by controlling the hydrogen content of the side chain hydrogen-containing silicone oil, so that the organosilicon prepared by the present invention has a certain range of polyether levels. Adding the organosilicon of the present invention as a foliar spreading agent can promote the spreading of pesticides, foliar fertilizers and other preparations on the leaves of plants, and at the same time promote the penetration of water-soluble liquid medicine from the plant surface into the interior of the plant, thereby achieving a comprehensive improvement in the effect of the liquid medicine, which plays a significant role in improving agricultural benefits.

[0019] 2. In the spraying of pesticides, foliar fertilizers and other liquid medicines, adding the organosilicon of the present invention as a foliar spreading agent can reduce the amount of liquid medicine used. In addition to improving the effective utilization rate of the liquid medicine, it can also avoid large-volume spraying of crops, which has important environmental significance.

[0020] 3. The organosilicon of the present invention is non-ionic as a foliar spreading agent and is non-toxic and harmless to the human body. Therefore, it is compatible with most spray preparations, and the products after addition are also green and safe. At the same time, it is suitable for large-scale industrial production and has high practical value. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 Comparison of the states of spreading agent aqueous solution on the lotus leaf surface. DETAILED DESCRIPTION

[0022] In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention will be further described in detail below in conjunction with specific implementation methods and drawings.

[0023] Table 1 Information of some raw materials

[0024] .

[0025] Example 1 Preparation of polyether-modified silicone using a 1000kg scale industrial production method: The side chain hydrogen-containing silicone oil has a viscosity of 130cP, a hydrogen content of 0.13%, and a relative molecular mass of about 4600.

[0026] 750 kg of allyl alcohol polyether was put into the reactor, stirred and heated to 100 °C for half an hour (to remove moisture), then 235 kg of the above-mentioned side chain hydrogen silicone oil and 10 kg of allyl glycidyl ether were added, and 10 g of chloroplatinic acid catalyst (dissolved in 800 mL of anhydrous ethanol) was added at 85-95 °C for addition reaction until the reaction liquid became transparent and then reacted for another half an hour to obtain polyether-modified silicone. The total time of the addition reaction was 4 hours, and N was introduced during the reaction. 2 .

[0027] The obtained organosilicon structure is shown in Formula I,

[0028] Where x=55, y+z=6.

[0029] Example 2 Preparation of polyether-modified silicone using a 1000kg scale industrial production method: The viscosity of the side chain hydrogen-containing silicone oil is 150cP, the hydrogen content is 0.16%, and the relative molecular mass is about 5200.

[0030] 750 kg of allyl alcohol polyether was put into the reactor, stirred and heated to 100 °C for half an hour (to remove moisture), then 265 kg of the above-mentioned side chain hydrogen silicone oil and 10 kg of allyl glycidyl ether were added, and 10 g of chloroplatinic acid catalyst (dissolved in 800 mL of anhydrous ethanol) was added at 95-105 °C for addition reaction until the reaction liquid became transparent and then reacted for another half an hour to obtain polyether-modified silicone. The total time of the addition reaction was 3.5 h, and N was introduced during the reaction. 2 .

[0031] The obtained organosilicon structure is shown in Formula I, wherein x=59, y+z=11.

[0032] Example 3 Preparation of polyether-modified silicone using a 1000kg scale industrial production method: The side chain hydrogen-containing silicone oil has a viscosity of 135cP, a hydrogen content of 0.14%, and a relative molecular mass of 4920.

[0033] 750 kg of allyl alcohol polyether was put into the reactor, stirred and heated to 100 °C for half an hour (to remove moisture), then 250 kg of the above side chain hydrogen silicone oil and 10 kg of allyl glycidyl ether were added, and 10 g of chloroplatinic acid catalyst (dissolved in 800 mL of anhydrous ethanol) was added at 90-100 °C for addition reaction until the reaction liquid became transparent and then reacted for another half an hour to obtain polyether-modified silicone. The total time of the addition reaction was 3.5 h, and N was introduced during the reaction. 2 .

[0034] The obtained organosilicon structure is shown in Formula I, wherein x=57, y+z=9.

[0035] Comparative Example 1 The side chain hydrogen-containing silicone oil has a viscosity of 195cP, a hydrogen content of 0.18%, and a relative molecular mass of about 8000.

[0036] 750 kg of allyl alcohol polyether was put into the reactor, stirred and heated to 100 ° C for half an hour (to remove moisture), then 408 kg of the above-mentioned side chain hydrogen silicone oil and 10 kg of allyl glycidyl ether were added, and 10 g of chloroplatinic acid catalyst (dissolved in 800 mL of anhydrous ethanol) was added at 90-100 ° C for addition reaction until the reaction liquid became transparent and then reacted for another half an hour to obtain polyether-modified silicone. The total time of the addition reaction was 3.5 hours, and N was introduced during the reaction. 2 The obtained organosilicon structure is shown in Formula I.

[0037] Comparative Example 2 The difference between this comparative example and comparative example 1 is that the viscosity of the side chain hydrogen-containing silicone oil is 130 cP, the hydrogen content is 0.07%, and the relative molecular mass is about 8000. The structure of the obtained organosilicon is shown in Formula I.

[0038] Effect Example 1 Double-terminal hydrogenated silicone oil (hydrogen content 0.14%, relative molecular mass about 6000) was selected as other organosilicon foliar spreading agents. The organosilicon prepared in Examples 1, 2, 3 and Comparative Examples 1 and 2 and the above other organosilicon foliar spreading agents were diluted with water at a mass ratio of 1:10 to obtain each group of spreading agent aqueous solutions.

[0039] Fresh leaves of the plant green radish were used to test the performance of the spreading agent aqueous solution. The specific test method is as follows: 1) Hydrophilic time: Use a micropipette to transfer 50 μL of the aqueous solution of the spreading agent to be tested onto a horizontally placed leaf, and record the time it takes for the leaf to be wetted (from the time the drop is placed on the leaf to the time when the mirror reflection disappears completely), which is the hydrophilic time; repeat three times and take the average value.

[0040] 2) Expansion diameter: Use a micropipette to transfer 50 μL of the spreading agent aqueous solution to a horizontally placed leaf. Then measure the maximum and minimum diameters of the droplet. The average of the two is the expansion diameter. Repeat three times and take the average value.

[0041] 3) Liquid Carrying Rate: Liquid carrying rate is the percentage of the weight of liquid on the blade to the weight of the blade itself; let A be the weight of the blade before immersion and B be the weight of the blade after immersion, then liquid carrying rate = (BA) / A * 100%. The specific determination method is: first determine the weight of the blade before immersion; then immerse the blade in the spreading agent aqueous solution; after immersion for 30 minutes, remove the residual liquid on the surface of the blade, and determine the weight of the blade at this time as the weight of the blade after immersion; calculate the liquid carrying rate of the spreading agent aqueous solution to be tested according to the above liquid carrying rate formula.

[0042] The measurement results of each group are shown in Table 2.

[0043] Table 2 Performance test results of spreading agent aqueous solution

[0044] As can be seen from Table 2, when the organosilicon in Examples 1 to 3 is used as a foliar spreading agent, the hydrophilic time (46-53 min) of the spreading agent aqueous solution is significantly reduced compared with the blank control (310 min), the expansion diameter (7.4-8.1 mm) is significantly increased compared with the blank control (5.0 mm), and the liquid carrying rate (14.62%-15.79%) is significantly increased compared with the blank control (10.29%). This shows that adding the organosilicon of the present invention to the aqueous solution has better foliar spreading effect and penetration effect than directly using the aqueous solution.

[0045] As can be seen from Table 2, when the organosilicon of Examples 1 to 3 is used as a foliar spreading agent, the hydrophilic time (46-53 min) of the spreading agent aqueous solution is significantly reduced compared with the organosilicon of Comparative Example 1 (130 min), the organosilicon of Comparative Example 2 (285 min), and other organosilicon foliar spreading agents (160 min), and the expansion diameter is significantly increased. This shows that the organosilicon of Examples 1 to 3 has a significantly better effect on reducing the surface tension of the aqueous solution than the organosilicon of Comparative Example 1, the organosilicon of Comparative Example 2, or other organosilicon foliar spreading agents. Adding the organosilicon of the present invention to the aqueous solution has a better foliar spreading effect than adding other organosilicon.

[0046] As can be seen from Table 2, when the organosilicones of Examples 1 to 3 are used as foliar spreading agents, their liquid carrying rates (14.62%-15.79%) are improved compared to the organosilicon of Comparative Example 1 (13.05%), and are more significantly improved compared to the organosilicon of Comparative Example 2 (10.61%) and other organosilicon foliar spreading agents (12.96%). This shows that the organosilicon of Examples 1 to 3 also has a better effect on the permeability of aqueous solution than the organosilicon of Comparative Example 1, the organosilicon of Comparative Example 2 or other organosilicon foliar spreading agents. Adding the organosilicon of the present invention to the aqueous solution has a better foliar penetration effect than adding other organosilicones.

[0047] Effect Example 2 Take the organosilicon prepared in Examples 1, 2, 3 and Comparative Examples 1 and 2 and the other organosilicon foliar spreading agents, dilute them with water at a mass ratio of 1:10, and obtain spreading agent aqueous solutions. Then, spray each group of spreading agent aqueous solutions evenly on the leaf surface of fresh lotus leaves, and observe the state of the aqueous solution on the leaf surface after spraying. The state comparison of each group is shown in Figure 1 .

[0048] Depend on Figure 1It can be seen that the leaf surface directly sprayed with tap water is covered with relatively uniform small droplets, indicating that the leaf surface itself has obvious water repellency; the silicone of comparative example 1, silicone of comparative example 2, and other silicone leaf surface spreading agents are added to the water, and droplets are attached to the leaf surface after spraying; and the silicone of embodiment 1, silicone of embodiment 2, and silicone of embodiment 3 are added to the water, and the aqueous solution on the leaf surface after spraying is in the state of a water film. This shows that the silicone of embodiments 1 to 3 of the present invention can reduce the surface tension of the aqueous solution, making the originally water-repellent leaf surface show hydrophilicity, and the improvement of the leaf surface spreading performance of the aqueous solution by the silicone of embodiments 1 to 3 is better than that of the silicone of comparative example 1, comparative example 2, or other silicone leaf surface spreading agents.

[0049] From the above Effect Examples 1 and 2, it can be seen that when the organosilicon modified with side chain hydrogenated silicone oil prepared by the present invention (the hydrogen content of the side chain hydrogenated silicone oil is 0.13% to 0.16%) is added to the aqueous solution, its leaf surface spreading effect and penetration effect are better than those of the double-terminal hydrogenated silicone oil, and also better than those of other organosilicon modified with side chain hydrogenated silicone oil (the hydrogen content of the side chain hydrogenated silicone oil is lower than 0.13% or higher than 0.16%). The preparation method of the present invention performs polyether modification and epoxy modification on the side chain hydrogenated silicone oil, and by controlling the hydrogen content of the side chain hydrogenated silicone oil, the organosilicon of the present invention not only improves the spreading effect of the liquid medicine, but also promotes the liquid medicine to penetrate from the plant surface into the plant interior, thereby achieving a balance between the spreading ability and penetration ability of the pesticide or foliar fertilizer liquid medicine on the leaves.

[0050] The above disclosure is only the preferred embodiment of the present invention, which certainly cannot be used to limit the scope of the present invention. Therefore, equivalent changes made according to the claims of the present invention are still within the scope of the present invention.

Claims

1. An application of organosilicon as a leaf spreading agent, characterized in that: The structure of the organosilicon is shown in structural formula I, ； Among them, 55≤x≤59, 6≤y+z≤11; EO is ethoxy, PO is propoxy; 20≤m≤30, 7≤n≤15.

2. The use of the organosilicon as a foliar spreading agent according to claim 1, characterized in that: The preparation of the organosilicon comprises the following steps: A. Mix allyl alcohol polyether with side chain hydrogen-containing silicone oil and allyl glycidyl ether; B. After heating, a catalyst is added to carry out an addition reaction to obtain the organosilicon.

3. The use of the organosilicon as a foliar spreading agent according to claim 2, characterized in that: The side chain hydrogen-containing silicone oil has a hydrogen content of 0.13% to 0.16%, a viscosity of 130 to 150 cP, and a relative molecular mass of 4600 to 5200.

4. The use of the organosilicon as a foliar spreading agent according to claim 2, characterized in that: In the preparation of the organosilicon, the structure of the allyl alcohol polyether is shown in structural formula II. ； Among them, EO is ethoxy, PO is propoxy, 20≤m≤30, 7≤n≤15.

5. The use of the organosilicon as a foliar spreading agent according to claim 2, characterized in that: In the preparation of the organosilicon, the relative molecular mass of the allyl alcohol polyether is 1800.

6. The use of the organosilicon as a foliar spreading agent according to claim 2, characterized in that: In the preparation of the organosilicon, the mass ratio of the side chain hydrogen-containing silicone oil, the allyl alcohol polyether and the allyl glycidyl ether is 94-106:300:

4.

7. The use of the organosilicon as a foliar spreading agent according to claim 2, characterized in that: In the preparation of the organosilicon, the catalyst includes chloroplatinic acid; the mass of the catalyst includes 10 to 30 ppm of the total mass of the side chain hydrogen-containing silicone oil, the allyl alcohol polyether and the allyl glycidyl ether; In step B, the temperature of adding the catalyst and the addition reaction is 85-105° C., and the time of the addition reaction is 3-4 hours; in step B, the addition reaction is stirred.

8. The use of the organosilicon as a foliar spreading agent according to claim 2, characterized in that: In the preparation of the organosilicon, before the mixing in step A, the allyl alcohol polyether is heated to 100° C. for half an hour to remove moisture; in step B, N2 is introduced into the reaction container during the addition reaction.

9. A preparation obtained by the use as claimed in claim 1, characterized in that The preparation comprises a mixture of the organosilicon and a water-soluble drug solution.

10. The preparation obtained by the use according to claim 9, characterized in that The water-soluble liquid medicine includes one or more of pesticides and foliar fertilizers.

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