Organosilicon pesticide wetting agent and preparation process thereof

Abstract

The invention discloses an organosilicon pesticide wetting agent and a preparation process thereof, and relates to the technical field of wetting agents, the organosilicon pesticide wetting agent comprises the following raw material components: 50-150 parts of hydrogen-containing silicone oil, 50-150 parts of allyl polyether, 0.1-3 parts of a catalyst, and 30-80 parts of a nonionic surfactant, the invention relates to a polystyrolsulfon acid composition which comprises the following components in parts by weight: 50-150 parts of polystyrolsulfon acid, 1-10 parts of a thickening agent, 100-250 parts of glycerol, 25-55 parts of a first additive substance, 20-50 parts of a second additive substance and 5-15 parts of trace elements. The allyl polyether and the hydrogen-containing silicone oil are subjected to an addition reaction to generate polyether modified organic silicon with small molecular weight, the wettability of the wetting agent is improved, the modified organic silicon wetting agent is combined with the nonionic surfactant, the wettability is further improved, and the wetting effect is improved. And by grafting the branched chain on the hydrophobic group of the organosilicon compound wetting agent, the wetting effect of the wetting agent can be effectively improved, and the effective components of the pesticide can wet the surfaces of crops.

Description

Technical Field

[0001] The invention relates to the technical field of wetting agents, in particular to an organosilicon pesticide wetting agent and a preparation process thereof. Background Art

[0002] Wetting agents mainly increase the adhesion of spray liquid on the surface of crops by changing the surface tension and wettability of liquids, helping pesticides to wet the surface of crop leaves as quickly as possible and reducing the possibility of pesticides sliding and flowing on the leaves. However, the wetting effect of existing wetting agents is poor, and they cannot effectively reduce the surface tension of liquids, thereby reducing the adhesion effect of pesticides on crops. In addition, the anti-foaming effect of existing wetting agents is poor, which has an adverse effect on the spraying of pesticides.

[0003] The defects of existing pesticide wetting agents are: The existing wetting agents have poor wetting effects and cannot effectively reduce the surface tension of the liquid, thereby reducing the adhesion effect of the pesticide on the crops. In addition, the existing wetting agents have poor anti-foaming effects, which have an adverse effect on the spraying of pesticides. Summary of the invention

[0004] The purpose of the present invention is to provide an organosilicon pesticide wetting agent and a preparation process thereof to solve the problems raised in the above background technology.

[0005] To achieve the above object, the present invention provides the following technical solution: an organosilicon pesticide wetting agent, the raw materials of which include the following components: 50-150 parts of hydrogenated silicone oil, 50-150 parts of propylene polyether, 0.1-3 parts of catalyst, 30-80 parts of nonionic surfactant, 50-150 parts of polystyrene sulfonic acid, 1-10 parts of thickener, 100-250 parts of glycerol, 25-55 parts of first additive, 20-50 parts of second additive, and 5-15 parts of trace elements; The hydrogen-containing silicone oil is heptamethyltrisiloxane or hexamethyldisiloxane.

[0006] A method for preparing an organosilicon pesticide wetting agent comprises the following steps: Step 1: Put 50-125 parts of hydrogenated silicone oil, 50-150 parts of propylene polyether and 0.1-1 parts of catalyst into a reaction kettle, and carry out addition reaction for 5-8 hours at a temperature of 100-150°C to obtain a polyether-modified organosilicon precursor; Step 2: Take 100-150 parts of glycerol, add the polyether-modified organosilicon precursor in step 1 to the glycerol for pretreatment, then add 30-55 parts of the first additive, stir and react at 50-70° C. for 10-15 minutes, then add a catalyst, react at 60-80° C. for 1.5-2 hours to obtain a modified organosilicon precursor; Step 3: Add 25-55 parts of the second additive to the modified organosilicon precursor in step 2, react at 50-80° C. for 10-15 minutes, then add a catalyst, react for 1.5-2.5 hours, and obtain a polyether-modified organosilicon precursor; Step 4: Mix the polyether-modified silicone matrix obtained in step 3 with 40-80 parts of a nonionic surfactant, react for 1-1.5 hours at a temperature of 60-100° C., and generate an organosilicon compound wetting agent; Step 5: Mix the organosilicon compound wetting agent in step 4 with 50-140 parts of polystyrene sulfonic acid, and react for 0.5-2 hours at a temperature of 50-100° C. to generate a branched organosilicon compound wetting agent; Step six: Add 1-8 parts of thickener and 5-15 parts of trace elements to the branched organosilicon compound wetting agent in step five, mix and react for 0.5-1 hour to obtain the organosilicon pesticide wetting agent.

[0007] Preferably, the catalyst comprises one of dilute hydrochloric acid, trichlorofluoroolefin, hydrogen chloride and triethylenetriamine.

[0008] Preferably, the first additive comprises at least one of polyvinyl alcohol and polyethylene glycol.

[0009] Preferably, the second additive includes at least one of trimethylchlorosilane, alkyl alcohol, trifluorochloromethylsilane, fluorovinyl ether, and phenyltrichlorosilane.

[0010] Preferably, the nonionic surfactant in step 4 includes one of sodium ethyl acetate sulfonate, polyethylene glycol-6 carboxylate, polyoxyethylene ether carboxylate, sodium lauryl alcohol sulfonate, and polyoxyethylene polypropylene block copolymer.

[0011] Preferably, the thickener in step six comprises carboxymethyl cellulose or polyvinyl alcohol.

[0012] Preferably, the trace elements in step six include one or more of iron, nitrogen, zinc and potassium chelates.

[0013] Preferably, in step 1, the mass ratio of hydrogenated silicone oil to propylene polyether is (0.5-2):1.

[0014] Preferably, in step 4, the mass ratio of the polyether-modified silicone matrix to the non-ionic surfactant is (1-4):1.

[0015] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention uses propenyl polyether and hydrogen-containing silicone oil to carry out addition reaction to generate small molecular weight polyether-modified silicone, which is beneficial to improving the wettability of the wetting agent. By adding the first additive, a hydrophilic matrix is ​​introduced to improve the dispersion effect of the wetting agent in the pesticide, improve the water solubility of the pesticide, and prevent the precipitation of the pesticide. In addition, by grafting side chains on the hydrophobic base of the organosilicon compound wetting agent, the wetting effect of the wetting agent can be effectively improved, which is beneficial to make the active ingredients of the pesticide wet the crop surface.

[0016] 2. The present invention uses a second additive to react with a modified organosilicon precursor, thereby facilitating the introduction of hydrophobic groups into the pesticide wetting agent, thereby improving the permeability of the wetting agent to the surface of non-polar substances, and by entering the hydrophobic fluoroalkyl group, it can reduce the surface tension of the wetting agent, enhance the adhesion of the wetting agent, and thus improve the adhesion of the pesticide on the crop surface and prolong the adhesion time.

[0017] 3. The present invention facilitates the improvement of the binding force between the modified silicone and the nonionic surfactant, thereby improving the stability and durability of the wetting agent, by causing the free hydroxyl groups in the polyether-modified silicone to undergo an esterification reaction with the carboxyl groups in the nonionic surfactant, or by combining the free siloxy bonds in the polyether-modified silicone with the hydroxyl groups in the nonionic surfactant.

[0018] 4. The present invention modifies the hydrogen-containing silicone oil into polyether and adds polystyrene sulfonic acid, so that the organosilicon compound wetting agent has a side chain perpendicular to the alkyl group, thereby increasing the steric hindrance of the molecular chain of the organosilicon wetting agent and improving the anti-foaming performance of the pesticide wetting agent, thereby avoiding the phenomenon that after using the wetting agent, the prepared pesticide sprayer produces more foam and affects the pesticide spraying effect.

[0019] 5. The present invention adds trace elements to make the wetting agent have the performance of enhancing crop growth and disease resistance, and by adding a thickener, the precipitation of trace elements is avoided and the mixing uniformity of trace elements in the wetting agent and the pesticide preparation liquid is improved. DETAILED DESCRIPTION

[0020] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0021] Embodiment 1, Step 1: 50 parts of heptamethyltrisiloxane, 100 parts of propylene polyether and 0.2 parts of trichlorofluoroene were put into a reaction kettle, and the reaction was carried out at a temperature of 110° C. for 6 hours to obtain a polyether-modified organosilicon precursor; Step 2: Take 120 parts of glycerol, add the polyether-modified organosilicon precursor in step 1 to the glycerol for pretreatment, then add 35 parts of polyvinyl alcohol, stir and react at 60°C for 13 minutes, then add 0.5 parts of dilute hydrochloric acid, react at 75°C for 1.5 hours to obtain a modified organosilicon precursor; Step 3: Add 15 parts of trimethylchlorosilane and 15 parts of phenyltrichlorosilane to the modified organosilicon precursor in step 2, react at 60° C. for 12 minutes, then add 0.5 parts of hydrogen chloride and react for 2 hours to obtain a polyether-modified organosilicon precursor; Step 4: Mix the polyether-modified silicone matrix obtained in step 3 with 50 parts of sodium ethyl acetate sulfonate, and react at a temperature of 40° C. for 1 hour to allow the carboxyl groups in the polyether-modified silicone matrix to undergo an esterification reaction with the carboxyl groups in the sodium ethyl acetate sulfonate to generate an organosilicon compound wetting agent; Step 5: Mix the organosilicon compound wetting agent in step 4 with 80 parts of polystyrene sulfonic acid, and react at 60° C. for 0.8 h to generate a branched organosilicon compound wetting agent; Step 6: Add 3 parts of carboxymethyl cellulose and 6 parts of trace elements to the branched organosilicon compound wetting agent in step 3, mix and react for 0.8 hours to obtain an organosilicon pesticide wetting agent.

[0022] Embodiment 2: Step 1: 80 parts of heptamethyltrisiloxane, 100 parts of propylene polyether and 0.2 parts of trichlorofluoroene were put into a reaction kettle, and the reaction was carried out at a temperature of 125° C. for 7.5 hours to obtain a polyether-modified organosilicon precursor; Step 2: Take 120 parts of glycerol, add the polyether-modified organosilicon precursor in step 1 to the glycerol for pretreatment, then add 35 parts of polyvinyl alcohol, stir and react at 60°C for 13 minutes, then add 0.7 parts of dilute hydrochloric acid, react at 75°C for 1.5 hours to obtain a modified organosilicon precursor; Step 3: Add 15 parts of trimethylchlorosilane and 15 parts of phenyltrichlorosilane to the modified organosilicon precursor in step 2, react at 60° C. for 12 minutes, then add 0.7 parts of hydrogen chloride and react for 2 hours to obtain a polyether-modified organosilicon precursor; Step 4: Mix the polyether-modified silicone matrix obtained in step 3 with 60 parts of sodium ethyl acetate sulfonate, and react at a temperature of 50° C. for 1 hour to allow the carboxyl groups in the polyether-modified silicone matrix to undergo an esterification reaction with the carboxyl groups in the sodium ethyl acetate sulfonate to generate an organosilicon compound wetting agent; Step 5: Mix the organosilicon compound wetting agent in step 4 with 100 parts of polystyrene sulfonic acid, and react for 1 hour at a temperature of 80° C. to generate a branched organosilicon compound wetting agent; Step 4: Add 5 parts of carboxymethyl cellulose and 8 parts of trace elements to the branched organosilicon compound wetting agent in step 3, mix and react for 1 hour to obtain an organosilicon pesticide wetting agent.

[0023] Embodiment 3, Step 1: 90 parts of hexamethyldioxysilane, 90 parts of propylene polyether and 0.5 parts of trichlorofluoroene are put into a reaction kettle, and the addition reaction is carried out for 7.5 hours at a temperature of 140° C. to obtain a polyether-modified organosilicon precursor; Step 2: Take 130 parts of glycerol, add the polyether-modified organosilicon precursor in step 1 to the glycerol for pretreatment, then add 35 parts of polyethylene glycol, stir and react at 65°C for 12 minutes, then add 0.5 parts of dilute hydrochloric acid, react at 75°C for 1.5 hours to obtain a modified organosilicon precursor; Step 3: Add 10 parts of alkyl alcohol, 10 parts of fluorovinyl ether and 10 parts of phenyltrichlorosilane to the modified organosilicon precursor in step 2, react at 60° C. for 12 minutes, then add 0.5 parts of triethylenetriamine and react for 2 hours to obtain a polyether-modified organosilicon precursor; Step 4: Mix the polyether-modified silicone matrix obtained in step 3 with 55 parts of sodium lauric acid sulfonate, and react at a temperature of 55° C. for 1 hour to allow the carboxyl groups in the polyether-modified silicone matrix to undergo an esterification reaction with the carboxyl groups in the sodium lauric acid sulfonate to generate an organosilicon compound wetting agent; Step 5: Mix the organosilicon compound wetting agent in step 4 with 70 parts of polystyrene sulfonic acid, and react at a temperature of 85° C. for 1.5 hours to generate a branched organosilicon compound wetting agent; Step 4: Add 7 parts of carboxymethyl cellulose and 6 parts of trace elements to the branched organosilicon compound wetting agent in step 3, mix and react for 1 hour to obtain an organosilicon pesticide wetting agent.

[0024] Embodiment 4: Step 1: 150 parts of heptamethyltrisiloxane, 90 parts of propylene polyether and 0.6 parts of trichlorofluoroene are put into a reaction kettle, and the reaction is carried out at a temperature of 120° C. for 6 hours to obtain a polyether-modified organosilicon precursor; Step 2: Take 120 parts of glycerol, add the polyether-modified organosilicon precursor in step 1 to the glycerol for pretreatment, then add 35 parts of polyvinyl alcohol, stir and react at 60°C for 13 minutes, then add 0.6 parts of dilute hydrochloric acid, react at 75°C for 1.5 hours to obtain a modified organosilicon precursor; Step 3: Add 15 parts of trimethylchlorosilane and 15 parts of phenyltrichlorosilane to the modified organosilicon precursor in step 2, react at 60° C. for 12 minutes, then add 0.7 parts of triethylenetriamine, react for 2 hours, and obtain a polyether-modified organosilicon precursor; Step 4: Mix the polyether-modified silicone matrix obtained in step 3 with 50 parts of polyoxyethylene-polypropylene-ethylene block copolymer, and react at a temperature of 55° C. for 1.2 hours. The heptamethyltrisiloxane that has not reacted with the propylene polyether in step 1 has free siloxy bonds, so that the free siloxy bonds in the polyether-modified silicone matrix react with the hydroxyl groups in the polyoxyethylene-polypropylene-ethylene block copolymer to form ester bonds, thereby forming an organosilicon compound wetting agent. Step 5: Mix the organosilicon compound wetting agent in step 4 with 80 parts of polystyrene sulfonic acid, and react at 75° C. for 1.3 hours to generate a branched organosilicon compound wetting agent; Step 4: Add 3 parts of polyvinyl alcohol and 6 parts of trace elements to the branched organosilicon compound wetting agent in step 3, mix and react for 1 hour to obtain an organosilicon pesticide wetting agent.

[0025] Embodiment 5, Step 1: 150 parts of hexamethyldioxysilane, 80 parts of propylene polyether and 0.6 parts of trichlorofluoroene were put into a reaction kettle, and the reaction was carried out at a temperature of 130° C. for 7.5 hours to obtain a polyether-modified organosilicon precursor; Step 2: Take 120 parts of glycerol, add the polyether-modified organosilicon precursor in step 1 to the glycerol for pretreatment, then add 40 parts of polyvinyl alcohol, stir and react at 60°C for 13 minutes, then add 0.6 parts of dilute hydrochloric acid, react at 75°C for 1.5 hours to obtain a modified organosilicon precursor; Step 3: Add 20 parts of trimethylchlorosilane, 10 parts of trifluorochloromethylsilane and 10 parts of phenyltrichlorosilane to the modified organosilicon precursor in step 2, react at 65° C. for 15 minutes, then add 0.7 parts of triethylenetriamine and react for 2 hours to obtain a polyether-modified organosilicon precursor; Step 4: Mix the polyether-modified silicone matrix obtained in step 3 with 40 parts of polyoxyethylene-polypropylene block copolymer, and react at a temperature of 55° C. for 1.2 hours to allow the free siloxane bonds in the polyether-modified silicone matrix to react with the hydroxyl groups in the polyoxyethylene-polypropylene block copolymer to form ester bonds, thereby obtaining an organosilicon compound wetting agent; Step 5: Mix the organosilicon compound wetting agent in step 4 with 90 parts of polystyrene sulfonic acid, and react for 1.5 hours at 80° C. to generate a branched organosilicon compound wetting agent; Step 6: Add 5 parts of polyvinyl alcohol and 8 parts of trace elements to the branched organosilicon compound wetting agent in step 3, mix and react for 0.5 to 1 hour to obtain an organosilicon pesticide wetting agent.

[0026] Comparative Example 1: 80 parts of heptamethyltrisiloxane were taken as the silicone type wetting agent.

[0027] Comparative Example 2: 60 parts of a nonionic surfactant are taken as a wetting agent, and further, the nonionic surfactant is polyoxyethylene ether carboxylate.

[0028] The ingredients and components of the pesticide wetting agent in the embodiments and comparative examples are as follows:

[0029] The pesticide wetting agents in Example 1, Example 2, Example 3, Example 4, Example 5, Comparative Example 1 and Comparative Example 2 were tested for performance, and the testing method specifically includes the following steps: Determination of surface tension and droplet expansion area: the surface tension of the liquid was determined by the platinum plate method, and the droplet expansion area was determined by the integral method. 20 ml of the pesticide wetting agent in Example 1, Example 2, Example 3, Example 4, Example 5, Comparative Example 1 and Comparative Example 2 were mixed with the same volume of pesticide, a layer of liquid was prepared, and the target was acted on. For the anti-foaming test, 20 ml of the pesticide wetting agent in Example 1, Example 2, Example 3, Example 4, Example 5, Comparative Example 1 and Comparative Example 2 were mixed with 200 ml of water respectively, placed in a sealed container, and shaken with the same force and the same number of times to observe the foam in the container. The performance test results are shown in the following table:

[0030] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

Claims

1. An organosilicon pesticide wetting agent, characterized in that: The raw materials include the following components: 50-150 parts of hydrogenated silicone oil, 50-150 parts of propylene polyether, 0.1-3 parts of catalyst, 30-80 parts of nonionic surfactant, 50-150 parts of polystyrene sulfonic acid, 1-10 parts of thickener, 100-250 parts of glycerol, 25-55 parts of first additive, 20-50 parts of second additive, and 5-15 parts of trace elements; The hydrogen-containing silicone oil is heptamethyltrisiloxane or hexamethyldisiloxane.

2. A method for preparing an organosilicon pesticide wetting agent, used for preparing an organosilicon pesticide wetting agent as claimed in claim 1, characterized in that: The following steps are involved: Step 1: Put 50-125 parts of hydrogenated silicone oil, 50-150 parts of propylene polyether and 0.1-1 parts of catalyst into a reaction kettle, and carry out addition reaction for 5-8 hours at a temperature of 100-150°C to obtain a polyether-modified organosilicon precursor; Step 2: Take 100-150 parts of glycerol, add the polyether-modified organosilicon precursor in step 1 to the glycerol for pretreatment, then add 30-55 parts of the first additive, stir and react at 50-70° C. for 10-15 minutes, then add a catalyst, react at 60-80° C. for 1.5-2 hours to obtain a modified organosilicon precursor; Step 3: Add 25-55 parts of the second additive to the modified organosilicon precursor in step 2, react at 50-80° C. for 10-15 minutes, then add a catalyst, react for 1.5-2.5 hours, and obtain a polyether-modified organosilicon precursor; Step 4: Mix the polyether-modified silicone matrix obtained in step 3 with 40-80 parts of a nonionic surfactant, react for 1-1.5 hours at a temperature of 60-100° C., and generate an organosilicon compound wetting agent; Step 5: Mix the organosilicon compound wetting agent in step 4 with 50-140 parts of polystyrene sulfonic acid, and react for 0.5-2 hours at a temperature of 50-100° C. to generate a branched organosilicon compound wetting agent; Step six: Add 1-8 parts of thickener and 5-15 parts of trace elements to the branched organosilicon compound wetting agent in step five, mix and react for 0.5-1 hour to obtain the organosilicon pesticide wetting agent.

3. The method for preparing an organosilicon pesticide wetting agent according to claim 2, characterized in that: The catalyst comprises one of dilute hydrochloric acid, trichlorofluoroolefin, hydrogen chloride and triethylenetriamine.

4. The method for preparing an organosilicon pesticide wetting agent according to claim 2, characterized in that: The first additive includes at least one of polyvinyl alcohol and polyethylene glycol.

5. The method for preparing an organosilicon pesticide wetting agent according to claim 2, characterized in that: The second additive includes at least one of trimethylchlorosilane, alkyl alcohol, trifluorochloromethylsilane, fluorovinyl ether, and phenyltrichlorosilane.

6. The method for preparing an organosilicon pesticide wetting agent according to claim 2, characterized in that: The nonionic surfactant in step 4 includes one of sodium ethyl acetate sulfonate, polyethylene glycol-6 carboxylate, polyoxyethylene ether carboxylate, sodium lauryl alcohol sulfonate, and polyoxyethylene polypropylene block copolymer.

7. The method for preparing an organosilicon pesticide wetting agent according to claim 2, characterized in that: In step six, the thickener includes carboxymethyl cellulose or polyvinyl alcohol.

8. The method for preparing an organosilicon pesticide wetting agent according to claim 2, characterized in that: The trace elements in step six include one or more of iron, nitrogen, zinc and potassium chelates.

9. The method for preparing an organosilicon pesticide wetting agent according to claim 2, characterized in that: In the step 1, the mass ratio of hydrogenated silicone oil to propylene polyether is (0.5-2):

1.

10. The method for preparing an organosilicon pesticide wetting agent according to claim 2, characterized in that: In the step 4, the mass ratio of the polyether-modified silicone matrix to the non-ionic surfactant is (1-4):1.

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