Application of silicone in as a foliar spreading agent and its preparation

Abstract

The present invention provides an application of silicone as a leaf surface spreading agent. The preparation of the silicone comprises the following steps: A. Mix allyl alcohol polyether, hydrogen-containing silicone oil with side chains, and allyl glycidyl ether; B. After raising the temperature, add a catalyst and carry out an addition reaction to obtain the silicone. The present invention also provides a preparation obtained by the above application. The preparation comprises the mixture of the silicone and a water-soluble liquid medicine, and the water-soluble liquid medicine comprises one or more of pesticides and leaf fertilizers. The preparation method of the present invention modifies the hydrogen-containing silicone oil with side chains by controlling the hydrogen content, and adding the silicone of the present invention as a leaf surface spreading agent can promote the spreading of preparations such as pesticides and leaf fertilizers on the leaf surface of plants, and at the same time, promote the penetration of the liquid medicine from the plant surface into the plant interior, realizing the comprehensive improvement of the liquid medicine effect, and playing a significant role in improving agricultural benefits.

Description

Technical Field

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

[0002] Pesticides and foliar fertilizers are common preparations in modern agriculture. However, the plant surface generally has a repulsive effect on liquids, especially water-soluble liquid medicines. After applying the medicine to the plant, when the surface tension of the liquid medicine is lower than the surface tension of the leaf surface, it adsorbs and wets on the surface of the target crop. On the contrary, the liquid medicine shrinks and aggregates on the surface of the target crop, and the liquid droplets roll off, resulting in the loss of the liquid medicine.

[0003] However, adding an organosilicon spreading agent to the use of these pesticides and foliar fertilizers can effectively reduce the surface tension of the liquid medicine, reduce the contact angle between the liquid drop and the surface of the crop leaf, and enable the liquid medicine to have a strong spreading ability on the plant leaf, thereby significantly enhancing the wetting performance on the plant surface. When the spreading performance of the organosilicon spreading agent is applied to pesticides, the liquid medicine can cover and adhere to a larger area of the plant surface, and the pesticide can directly contact and kill pests; when applied to foliar fertilizers, it can also improve the spreading effect of the fertilizer solution on the leaf, and then improve the absorption efficiency of the leaf for the foliar fertilizer.

[0004] Although there are many methods for modifying organosilicon, how to further improve the application effect of the modified organosilicon as a leaf spreading agent is still an important problem to be solved at present. Summary of the Invention

[0005] The purpose of the present invention is to solve the problems of poor spreading property and poor permeability of the liquid medicine when the modified organosilicon is used as a leaf spreading agent.

[0006] To solve the above problems, the present invention adopts the following technical solutions:

[0007] The present invention provides an application of organosilicon as a leaf spreading agent, and the structure of the organosilicon is shown in Structural Formula I,

[0008] ;

[0009] wherein, 55 ≤ x ≤ 59, 6 ≤ y + z ≤ 11;

[0010] EO is ethoxy group, PO is propoxy group; 20 ≤ m ≤ 30, 7 ≤ n ≤ 15.

[0011] As a preferred embodiment of the application of the present invention, the preparation of the organosilicon includes the following steps:

[0012] A. Mix allyl alcohol polyether, hydrogen-containing silicone oil with side chains, and allyl glycidyl ether;

[0013] B. After heating, add a catalyst and carry out an addition reaction to obtain the silicone.

[0014] Further, in the preparation of the silicone, the hydrogen content of the hydrogen-containing silicone oil in the side chain is 0.13% - 0.16%, the viscosity is 130 - 150 cP, and the relative molecular mass is 4600 - 5200.

[0015] Further, in the preparation of the silicone, the structure of the allyl alcohol polyether is as shown in Structural Formula II,

[0016] ;

[0017] wherein, EO is ethoxy, PO is propoxy, 20 ≤ m ≤ 30, and 7 ≤ n ≤ 15.

[0018] Further, in the preparation of the silicone, the relative molecular mass of the allyl alcohol polyether is 1800.

[0019] Further, in the preparation of the silicone, the mass ratio of the hydrogen-containing silicone oil in the side chain, the allyl alcohol polyether, and the allyl glycidyl ether is 94 - 106:300:4.

[0020] Further, in the preparation of the silicone, in step B, the catalyst includes chloroplatinic acid; the mass of the catalyst is 10 - 30 ppm of the total mass of the hydrogen-containing silicone oil in the side chain, the allyl alcohol polyether, and the allyl glycidyl ether;

[0021] In step B, the temperature for adding the catalyst and carrying out the addition reaction is 85 - 105 °C, and the time for the addition reaction is 3 - 4 hours; in step B, the addition reaction process is stirred.

[0022] Further, in the preparation of the silicone, 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 vessel during the addition reaction.

[0023] The present invention also provides a preparation obtained by the above application, and the preparation includes the mixture of the silicone and a water-soluble liquid medicine.

[0024] Further, the water-soluble liquid medicine includes one or more of pesticides and foliar fertilizers.

[0025] As a preferred embodiment of the application of the present invention, F-6 is used as the allyl alcohol polyether.

[0026] As a preferred embodiment of the application of the present invention, the structure of the allyl glycidyl ether is as shown in Structural Formula III,

[0027] 。

[0028] Compared with the prior art, implementing the present invention has the following beneficial effects:

[0029] 1. The preparation method of the present invention modifies the hydrogen-containing silicone oil with hydrogen content in the side chain to obtain silicone with a certain range of polyether level. Adding the silicone of the present invention as a leaf surface spreading agent can promote the spreading of preparations such as pesticides and foliar fertilizers on the leaf surface of plants, and at the same time, it can also prompt the water-soluble liquid medicine to penetrate from the plant surface into the interior of the plant, realizing the comprehensive improvement of the liquid medicine effect, which plays a significant role in improving agricultural benefits.

[0030] 2. In the spraying of liquid medicines such as pesticides and foliar fertilizers, adding the silicone of the present invention as a leaf surface spreading agent can reduce the dosage of the liquid medicine. In addition to improving the effective utilization rate of the liquid medicine, it can also avoid large-capacity spraying on crops, which has important environmental significance.

[0031] 3. The silicone of the present invention as a leaf surface spreading agent is non-ionic and non-toxic and harmless to the human body. Therefore, it can be compatible with the vast majority of spray preparations, and the added product is 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

[0032] Figure 1 It is a comparison of the states of the spreading agent aqueous solution on the leaf surface of a lotus leaf. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0033] To make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the specific embodiments and the drawings.

[0034] Table 1 Information of Some Raw Materials

[0035]

[0036] 。

[0037] Example 1

[0038] Use the 1000 kg large-scale industrial production method to prepare polyether-modified silicone:

[0039] The viscosity of the hydrogen-containing silicone oil in the side chain is 130 cP, the hydrogen content is 0.13%, and the relative molecular mass is about 4600.

[0040] Put 750 kg of allyl alcohol polyether into the reaction kettle. After stirring and heating to 100 °C for half an hour (to remove moisture), add 235 kg of the above-mentioned hydrogen-containing silicone oil with side chains and 10 kg of allyl glycidyl ether. Add 10 g of chloroplatinic acid catalyst (dissolved in 800 mL of absolute ethanol) at 85 - 95 °C for addition reaction. React for another half an hour after the reaction solution becomes transparent to obtain the polyether-modified silicone. The total time of the addition reaction is 4 h, and N2 is introduced during the reaction.

[0041] The obtained silicone has the structure shown in Formula I,

[0042]

[0043] where x = 55 and y + z = 6.

[0044] Example 2

[0045] Prepare polyether-modified silicone by a 1000 kg large-scale industrial production method:

[0046] The viscosity of the hydrogen-containing silicone oil with side chains is 150 cP, the hydrogen content is 0.16%, and the relative molecular mass is about 5200.

[0047] Put 750 kg of allyl alcohol polyether into the reaction kettle. After stirring and heating to 100 °C for half an hour (to remove moisture), add 265 kg of the above-mentioned hydrogen-containing silicone oil with side chains and 10 kg of allyl glycidyl ether. Add 10 g of chloroplatinic acid catalyst (dissolved in 800 mL of absolute ethanol) at 95 - 105 °C for addition reaction. React for another half an hour after the reaction solution becomes transparent to obtain the polyether-modified silicone. The total time of the addition reaction is 3.5 h, and N2 is introduced during the reaction.

[0048] The obtained silicone has the structure shown in Formula I, where x = 59 and y + z = 11.

[0049] Example 3

[0050] Prepare polyether-modified silicone by a 1000 kg large-scale industrial production method:

[0051] The viscosity of the hydrogen-containing silicone oil with side chains is 135 cP, the hydrogen content is 0.14%, and the relative molecular mass is 4920.

[0052] Put 750 kg of allyl alcohol polyether into the reaction kettle. After stirring and heating to 100 °C for half an hour (to remove moisture), add 250 kg of the above-mentioned hydrogen-containing silicone oil with side chains and 10 kg of allyl glycidyl ether. Add 10 g of chloroplatinic acid catalyst (dissolved in 800 mL of absolute ethanol) at 90 - 100 °C for addition reaction. React for another half an hour after the reaction solution becomes transparent to obtain the polyether-modified silicone. The total time of the addition reaction is 3.5 h, and N2 is introduced during the reaction.

[0053] The obtained silicone structure is shown in Formula I, where x = 57 and y + z = 9.

[0054] Comparative Example 1

[0055] The hydrogen-containing silicone oil with side chains has a viscosity of 195 cP, a hydrogen content of 0.18%, and a relative molecular mass of about 8000.

[0056] Put 750 kg of allyl alcohol polyether into a reaction kettle, stir and heat up to 100 °C for half an hour (to remove moisture), then add 408 kg of the above-mentioned hydrogen-containing silicone oil with side chains and 10 kg of allyl glycidyl ether, and add 10 g of chloroplatinic acid catalyst (dissolved in 800 mL of absolute ethanol) at 90 - 100 °C for addition reaction. React for another half an hour until the reaction solution becomes transparent to obtain the polyether-modified silicone. The total time of the addition reaction is 3.5 h, and N2 is introduced during the reaction. The obtained silicone structure is shown in Formula I.

[0057] Comparative Example 2

[0058] The difference between this comparative example and Comparative Example 1 is that: the hydrogen-containing silicone oil with side chains has a viscosity of 130 cP, a hydrogen content of 0.07%, and a relative molecular mass of about 8000. The obtained silicone structure is shown in Formula I.

[0059] Effect Example 1

[0060] Select the hydrogen-containing silicone oil with both ends (hydrogen content 0.14%, relative molecular mass about 6000) as other silicone leaf spreading agents. Dilute the silicones prepared in Examples 1, 2, 3 and Comparative Examples 1, 2 and the above-mentioned other silicone leaf spreading agents with water at a mass ratio of 1:10 to obtain the spreading agent aqueous solutions of each group.

[0061] Use the fresh leaves of Epipremnum aureum to measure the performance of the spreading agent aqueous solutions. The measurement method is as follows:

[0062] 1) Hydrophilic time: Use a micropipette to transfer 50 μL of the spreading agent aqueous solution to a horizontally placed leaf, and record the time when the leaf is wetted (from the moment it is dropped on the leaf until the specular reflection completely disappears), which is the hydrophilic time; repeat three times and take the average value.

[0063] 2) Spreading diameter: Use a micropipette to transfer 50 μL of the spreading agent aqueous solution to a horizontally placed leaf, and immediately measure the maximum diameter and the minimum diameter of the liquid drop. Take the average of the two as the spreading diameter; repeat three times and then take the average value.

[0064] 3) Liquid-carrying rate: The liquid-carrying rate is the percentage of the weight of the liquid carried on the leaf blade to the weight of the leaf blade itself. Let A be the weight of the leaf blade before soaking and B be the weight of the leaf blade after soaking. Then the liquid-carrying rate = (B - A) / A * 100%. The specific measurement method is as follows: First, measure the weight of the leaf blade before soaking. Then, soak the leaf blade in the aqueous solution of the spreading agent. After soaking for 30 minutes, remove the residual liquid on the surface of the leaf blade and measure the weight of the leaf blade at this time as the weight of the leaf blade after soaking. Calculate the liquid-carrying rate of the aqueous solution of the spreading agent to be measured according to the above liquid-carrying rate formula.

[0065] The measurement results of each group are shown in Table 2.

[0066] Table 2 Performance measurement results of the aqueous solution of the spreading agent

[0067]

[0068] As can be seen from Table 2, when the organosilicons of Examples 1 to 3 are used as the leaf surface spreading agents respectively, the hydrophilic time (46 - 53 min) of their aqueous solutions of the spreading agents is significantly lower than that of the blank control (310 min), the spreading diameter (7.4 - 8.1 mm) is significantly larger than that of the blank control (5.0 mm), and the liquid-carrying rate (14.62% - 15.79%) is significantly higher than that of the blank control (10.29%). This shows that adding the organosilicon of the present invention to the aqueous solution has better leaf surface spreading effect and penetration effect than directly using the aqueous solution.

[0069] As can be seen from Table 2, when the organosilicons of Examples 1 to 3 are used as the leaf surface spreading agents respectively, the hydrophilic time (46 - 53 min) of their aqueous solutions of the spreading agents is significantly lower than that of the organosilicon of Comparative Example 1 (130 min), the organosilicon of Comparative Example 2 (285 min), and other organosilicon leaf surface spreading agents (160 min), and at the same time the spreading diameter is significantly increased. This shows that the organosilicons of Examples 1 to 3 have significantly better effects 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 leaf surface spreading agents. Adding the organosilicon of the present invention to the aqueous solution has better leaf surface spreading effect than adding other organosilicons.

[0070] As can be seen from Table 2, when the organosilicons of Examples 1 to 3 are used as the leaf surface spreading agents respectively, their liquid-carrying rate (14.62% - 15.79%) is higher than that of the organosilicon of Comparative Example 1 (13.05%), and is significantly higher than that of the organosilicon of Comparative Example 2 (10.61%) and other organosilicon leaf surface spreading agents (12.96%). This shows that the organosilicons of Examples 1 to 3 also have better effects on improving the permeability of the aqueous solution than the organosilicon of Comparative Example 1, the organosilicon of Comparative Example 2, or other organosilicon leaf surface spreading agents. Adding the organosilicon of the present invention to the aqueous solution has better leaf surface penetration effect than adding other organosilicons.

[0071] Effect Example 2

[0072] Take the silicone rubbers prepared in Examples 1, 2, 3 and Comparative Examples 1, 2 and the above other silicone leaf surface spreading agents, and dilute them with water at a mass ratio of 1:10 respectively to obtain an aqueous solution of the spreading agent. Then, evenly spray each group of the aqueous solution of the spreading agent 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 。

[0073] As can be Figure 1 seen, the leaf surface sprayed directly with tap water is covered with relatively uniform small droplets, indicating that the leaf surface itself has obvious water repellency; when the silicone rubbers of Comparative Example 1, the silicone rubbers of Comparative Example 2, and other silicone leaf surface spreading agents are added to water respectively, droplets adhere to the leaf surface after spraying; while when the silicone rubbers of Example 1, the silicone rubbers of Example 2, and the silicone rubbers of Example 3 are added to water respectively, the aqueous solution on the leaf surface presents a water film state after spraying. This shows that the silicone rubbers of Examples 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 silicone rubbers of Examples 1 to 3 have a better improvement on the leaf surface spreading performance of the aqueous solution than the silicone rubbers of Comparative Example 1, Comparative Example 2 or other silicone leaf surface spreading agents.

[0074] In summary, as can be seen from Effect Example 1 and Effect Example 2, when the silicone rubber modified with hydrogen-containing silicone oil in the side chain (the hydrogen content of the hydrogen-containing silicone oil in the side chain is 0.13% to 0.16%) prepared by the present invention is added to an aqueous solution, its leaf surface spreading effect and penetration effect are better than those of the double-end hydrogen-containing silicone oil and also better than those of other silicone rubbers modified with hydrogen-containing silicone oil in the side chain (the hydrogen content of the hydrogen-containing silicone oil in the side chain is lower than 0.13% or higher than 0.16%). The preparation method of the present invention conducts polyether modification and epoxy modification on the hydrogen-containing silicone oil in the side chain, and by controlling the hydrogen level of the hydrogen-containing silicone oil in the side chain, the silicone rubber 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, so as to balance the spreading ability and penetration ability of the pesticide or foliar fertilizer liquid medicine on the leaf surface.

[0075] The above-disclosed are only the preferred embodiments of the present invention, and of course, the scope of the rights of the present invention cannot be limited thereby. Therefore, equivalent changes made according to the claims of the present invention still fall within the scope covered by the present invention.

Claims

1. Application of silicone in as a leaf surface spreading agent, characterized in that, The structure of the silicone is shown in Structural Formula I, ； where 55 ≤ x ≤ 59 and 6 ≤ y + z ≤ 11; EO is ethoxy and PO is propoxy; 20 ≤ m ≤ 30 and 7 ≤ n ≤ 15; The preparation of the silicone comprises the following steps: A. Mix allyl alcohol polyether, hydrogen-containing silicone oil with side chains, and allyl glycidyl ether; B. After raising the temperature, add a catalyst and carry out an addition reaction to obtain the silicone; The hydrogen content of the hydrogen-containing silicone oil with side chains is 0.13% - 0.16%, the viscosity is 130 - 150 cP, and the relative molecular mass is 4600 - 5200.

2. The application of the silicone according to claim 1 as a leaf surface spreading agent, characterized in that, In the preparation of the silicone, the structure of the allyl alcohol polyether is shown in Structural Formula II, ； where EO is ethoxy, PO is propoxy, 20 ≤ m ≤ 30, and 7 ≤ n ≤ 15.

3. The application of the silicone according to claim 1 as a leaf surface spreading agent, characterized in that, In the preparation of the silicone, the relative molecular mass of the allyl alcohol polyether is 1800.

4. The application of the silicone as claimed in claim 1 in being used as a leaf surface spreading agent, characterized in that, In the preparation of the silicone, the mass ratio of the hydrogen-containing silicone oil with side chains, the allyl alcohol polyether, and the allyl glycidyl ether is 94 - 106:300:

4.

5. The application of silicone as a leaf spreading agent according to claim 1, wherein In the preparation of the silicone, the catalyst includes chloroplatinic acid; the mass of the catalyst is 10 - 30 ppm of the total mass of the hydrogen-containing silicone oil with side chains, the allyl alcohol polyether, and the allyl glycidyl ether; In step B, the temperature for adding the catalyst and carrying out the addition reaction is 85 - 105°C, and the time for the addition reaction is 3 - 4 hours; in step B, stirring is carried out during the addition reaction.

6. The application of silicone as a foliar spreading agent according to claim 1, characterized in that, In the preparation of the silicone, 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 vessel during the addition reaction.

7. A preparation obtained by the application as described in claim 1, characterized in that, The preparation includes the mixture of the silicone and a water-soluble liquid medicine.

8. The preparation obtained by the application according to claim 7, characterized in that, The water-soluble liquid medicine includes one or more of pesticides and foliar fertilizers.

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