Agricultural organosilicon synergist and preparation method thereof

Abstract

The present invention relates to the field of organic chemical products, and discloses an agricultural organosilicon synergist and a preparation method thereof. The preparation method includes: using cardanol as a raw material, synthesizing an unsaturated cardanol polyoxyethylene ether through an ethylene oxide addition reaction, selecting an aluminum-nickel alloy catalyst, continuing catalytic hydrogenation at normal temperature and pressure, and obtaining a corresponding saturated product, using acrylic acid as a modifier and grafting it onto the cardanol polyoxyethylene ether through an esterification reaction to obtain acrylic acid cardanol polyoxyethylene ether; using homemade mesoporous silicon as a carrier, γ-aminopropyl triethoxysilane as a modifier, and chloroplatinic acid as a platinum source, a heterogeneous catalyst is prepared; using acrylic acid cardanol polyoxyethylene ether and hexamethyl trisiloxane as the main raw materials, a hydrosilylation reaction is carried out under the catalysis of a heterogeneous catalyst to obtain an agricultural organosilicon synergist.

Description

Technical Field

[0001] The invention relates to the field of organic chemical products, and in particular to an agricultural organosilicon synergist and a preparation method thereof. Background Art

[0002] As we all know, most of the pesticides used in the world, including herbicides, insecticides, fungicides, plant growth regulators, etc., are toxic to varying degrees, and pesticide residues in agricultural products have become a global public hazard. With the increasing resistance of agricultural pests and fungi, the use of various pesticides is required to be larger and larger, which seriously threatens human health. In order to improve the efficacy and reduce the amount of pesticides used, humans have been exploring the use of various pesticide synergists, and the most used are organic surfactants, penetrants, wetting agents, etc., and because the surface tension of these organic surfactants is mostly above 25mN / m, their synergistic effect is not very obvious. It was not until the 1970s that people noticed organosilicon surfactants. In the 1980s, the research on organosilicon surfactants as pesticide synergists was very active. In the 1990s, it began to be used abroad, and it was found that organosilicon pesticide synergists are highly efficient, non-toxic, and have outstanding surface properties.

[0003] Studies have shown that the use of organosilicon pesticide synergists can increase the coverage of the pesticide solution on plant leaves and pest bodies, accelerate the plant's absorption rate of the pesticide solution, and improve resistance to rain erosion. It not only effectively prevents the loss of the pesticide solution and improves the efficacy of the pesticide, but also saves spray water and reduces environmental pollution.

[0004] Cardanol is a compound extracted from discarded cashew shells. As a renewable resource, it can replace phenolic substances prepared from petroleum. Cardanol contains a benzene ring, which can provide the system with a certain permeability and high temperature resistance; the meta-position of the phenolic hydroxyl group on the benzene ring contains a long carbon chain with a double bond, which gives the system excellent toughness and hydrophobicity; the phenolic hydroxyl group has a strong hydrophilicity, which can provide the body with wetting and surface activity on the contact surface. Cardanol polyoxyethylene ether synthesized from cardanol is a non-toxic, low-odor, non-flammable light yellow liquid. It will not generate alkylphenol polyoxyethylene ether compounds after biodegradation. Therefore, over time, when the macromolecules of the cardanol polyoxyethylene ether molecular compound are decomposed into smaller molecules, no substances that pollute the environment will be produced. At present, this type of green and environmentally friendly surfactant with superior performance has a very great research significance.

[0005] Prior art, such as Chinese patent application CN101720779A, discloses an organosilicon pesticide synergist and its preparation method, wherein a single polyether-terminated organosilicon synergist is prepared by addition reaction of a synthetic special polyether with hexamethyldisilazane, and due to the introduction of a polyether structure, the foaming property of the synergist is suppressed and the surface activity is good. However, the molecular weight of the special polyether is small and only a single polyether structure is introduced, which has little effect on the surface activity of hydrogenated silicone oil.

[0006] Prior art, such as Chinese patent application CN101011062A, discloses an organosilicon pesticide synergist and a preparation method thereof. The Si-H addition catalyst used is platinum-1.3-divinyltetramethyldisiloxane-acetylacetone. This precious metal catalyst is expensive and difficult to separate from the product. In addition, a large amount of heat is released during the Si-H addition reaction, resulting in side reactions and material impact. Summary of the invention

[0007] The purpose of the present invention is to overcome the deficiencies of the prior art and provide an agricultural organosilicon synergist and a preparation method thereof. The synergist has extremely low surface tension and foaming properties and has excellent wettability and spreadability.

[0008] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0009] An agricultural organosilicon synergist and a preparation method thereof, comprising the following steps:

[0010] Step (1), mixing cardanol with a 50 wt% NaOH aqueous solution, heating, dehydrating, adding ethylene oxide and reacting, and after the reaction is completed, adjusting the pH, filtering, and drying to obtain unsaturated cardanol polyoxyethylene ether;

[0011] Unsaturated cardanol polyoxyethylene ether, an aluminum-nickel alloy catalyst, and anhydrous ethanol are mixed for reaction. After the reaction is completed, the aluminum-nickel alloy catalyst is removed by filtering, and the filtrate is taken and the organic solvent anhydrous ethanol is removed by rotary evaporation to obtain hydrogenated cardanol polyoxyethylene ether;

[0012] Mix hydrogenated cardanol polyoxyethylene ether, hydroquinone and p-toluenesulfonic acid, add acrylic acid and react, after the reaction is completed, obtain a crude reaction product, mix the crude reaction product with dichloromethane, adjust the pH, stand for stratification, take the lower layer of liquid, wash, separate the liquids, and remove dichloromethane by rotary evaporation to obtain modified cardanol polyoxyethylene ether;

[0013] Step (2), mixing hexadecyltrimethylammonium bromide (CTAB), distilled water, and 25 wt% ammonia water, adding tetraethyl orthosilicate (TEOS) and stirring to react, cooling after the reaction, crystallizing, and obtaining a reaction product after the crystallization, washing, drying, grinding, dispersing, and calcining to obtain mesoporous silicon;

[0014] Mix mesoporous silica and toluene, add γ-aminopropyltriethoxysilane (APTES) dropwise, raise the temperature to react after the addition is complete, cool and filter to obtain a reaction product after the reaction is complete, wash and dry to obtain amino mesoporous silica;

[0015] The amino-modified mesoporous silica and acetone are mixed and stirred, and a 0.05 mol / L chloroplatinic acid-ethanol solution is added to react. After the reaction is completed, the mixture is cooled, filtered, and the filter cake is taken and dried to obtain a heterogeneous catalyst.

[0016] Step (3), mixing the modified cardanol polyoxyethylene ether, the heterogeneous catalyst and the hexamethyltrisiloxane and reacting them, cooling the mixture after the reaction is completed, and removing the unreacted raw materials by rotary evaporation to obtain an agricultural organosilicon synergist.

[0017] Preferably, in the step (1), when preparing the unsaturated cardanol polyoxyethylene ether: the dehydration condition is dehydration under vacuum for 1-2h; the mass ratio of cardanol, 50wt% NaOH aqueous solution, and ethylene oxide is 302: (0.2-1.2): 264; the reaction conditions are: at a temperature of 120-140°C, 2×10 5 -3×10 5 The reaction was carried out under pressure for 8-12 hours; the pH adjustment method was: adding acetic acid to adjust the pH to 6.

[0018] Preferably, in the step (1), when preparing hydrogenated cardanol polyoxyethylene ether: the mass ratio of unsaturated cardanol polyoxyethylene ether, aluminum-nickel alloy catalyst, and anhydrous ethanol is 10: (0.5-2.5): (25-45); the reaction conditions are: reacting for 10-14 hours in an inert gas atmosphere, at a pressure of 2-6 MPa, and at room temperature.

[0019] Preferably, in the step (1), when preparing the modified cardanol polyoxyethylene ether: the mass ratio of hydrogenated cardanol polyoxyethylene ether, hydroquinone, p-toluenesulfonic acid and acrylic acid is 2000:(4-16):(40-80):(80-100); the reaction conditions are: reacting at a temperature of 90-130°C for 6-8h; the pH adjustment method is: adding 0.05 mol / L NaOH aqueous solution to adjust the pH to neutral.

[0020] Preferably, in the step (2), when preparing mesoporous silicon: the mass ratio of hexadecyltrimethylammonium bromide, distilled water, 25wt% ammonia water, and tetraethyl orthosilicate is (1-3):(260-300):(160-200):(10-14); the reaction conditions are: stirring the reaction at 60-70°C for 6-8h; the crystallization time is: 20-24h; and the calcination conditions are: calcining at 560-600°C for 6-8h.

[0021] Preferably, in the step (2), when preparing amino-modified mesoporous silicon, the mass ratio of mesoporous silicon, toluene and γ-aminopropyltriethoxysilane is (80-100):(5000-5200):(60-80); the reaction conditions are: in a nitrogen atmosphere, at a temperature of 110-130°C for 20-24h.

[0022] Preferably, in the step (2), when preparing the heterogeneous catalyst: the mass ratio of amino mesoporous silica, acetone, and chloroplatinic acid-ethanol solution is (80-100):(2000-2400):(8-12); the reaction conditions are: in a nitrogen atmosphere, at a temperature of 70-90°C for 10-12h.

[0023] Preferably, in the step (3), the mass ratio of the modified cardanol polyoxyethylene ether, the heterogeneous catalyst and the hexamethyltrisiloxane is (700-800):(40-50):(180-220); the reaction conditions are: reacting in a nitrogen atmosphere at a temperature of 80-100°C for 8-12 hours.

[0024] Preferably, an agricultural organosilicon synergist is prepared by the method for preparing an agricultural organosilicon synergist as described above.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] Agricultural organosilicon synergists are mainly prepared by the hydrosilylation reaction of polyether containing C=C and silicone oil containing Si-H, and the commonly used alkylphenol is a compound of medium toxicity. The present invention uses cardanol and ethylene oxide to react to obtain cardanol polyoxyethylene ether. Cardanol is a new type of green and environmentally friendly material, which is cheap and easy to obtain. Since ethylene oxide introduces polyether segments to strengthen the chelating ability and dispersing ability, the chelating and dispersing performance of cardanol polyoxyethylene ether is enhanced, it is easy to dissolve and will not produce precipitation, it can be evenly dispersed in the solution, and can be used as a dispersant; conventional polysiloxane surfactants will produce abundant foam during use, and have strong foam stability, which brings troubles to the actual application process. In the present invention, by introducing cardanol polyoxyethylene ether, the foaming property of the surfactant can be improved and the amount of defoamer used can be reduced; over time, when the macromolecules of the cardanol polyoxyethylene ether molecular compound are decomposed into smaller molecules, no substances that pollute the environment will be produced.

[0027] In the present invention, acrylic acid is used as a modifier, and under the action of an inhibitor and a catalyst, it is grafted onto the cardanol polyoxyethylene ether through an esterification reaction, and a vinyl functional group is introduced, so that it can undergo a hydrosilylation reaction with a Si-H-containing silicone oil; in the present invention, hexamethyltrisiloxane is used to synthesize a dipolyether-terminated organic silicon synergist, so that the wettability, permeability and spreadability are better, thereby improving the performance after compounding with pesticides.

[0028] The catalysts commonly used in the preparation of agricultural organosilicon synergists are homogeneous catalysts such as Speier and Karstedt, which are difficult to separate from the product after the reaction and cannot be recycled, resulting in a waste of precious metals and affecting the performance and appearance of the product. The present invention immobilizes the active component platinum on homemade mesoporous silicon to prepare a heterogeneous catalyst, which has good mechanical strength and high stability in the reaction medium, is easy to separate from the reaction system, can be repeatedly used, can reduce production costs, reduce the loss of precious metals and pollution to the environment.

[0029] The agricultural organosilicon synergist prepared by the present invention has an extremely low liquid surface tension of about 19 to 23 mN / m, can be used as an extender, a penetrant and an emulsifying dispersant, has good stability in a wide range of pH values, is non-toxic, has good physiological safety performance, is suitable for various herbicides, insecticides, fungicides, plant growth regulators, biological pesticides and foliar fertilizers, and can save spray water and pesticide dosage; the preparation method of the present invention has lower residue, less environmental pollution, and has the advantages of less side reactions and high yield. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is a process flow chart for preparing agricultural organosilicon synergist in the present invention;

[0031] Figure 2 It is a histogram of surface tension in the comprehensive performance test of the agricultural organosilicon synergist prepared in Examples 1-5 and Comparative Examples 1-2 of the present invention;

[0032] Figure 3 It is a contact angle bar graph of the comprehensive performance test of the agricultural organosilicon synergist prepared in Examples 1-5 and Comparative Examples 1-2 of the present invention;

[0033] Figure 4 It is a bar graph of the foaming power in the comprehensive performance test of the agricultural organosilicon synergist prepared in Examples 1-5 and Comparative Examples 1-2 of the present invention;

[0034] Figure 5 It is a bar graph of the spreading ability of the agricultural organosilicon synergist prepared in Examples 1-5 and Comparative Examples 1-2 of the present invention in the comprehensive performance test. DETAILED DESCRIPTION

[0035] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than 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.

[0036] Example 1

[0037] This embodiment discloses an agricultural organosilicon synergist and a preparation method thereof, comprising the following steps:

[0038] Step (1), mixing cardanol with a 50 wt% NaOH aqueous solution, stirring and heating to 120°C in a high temperature reaction kettle, dehydrating for 1 h under vacuum conditions, adding ethylene oxide in a nitrogen atmosphere, and heating at 140°C, 3×10 5 The reaction was carried out under a pressure of Pa for 8 hours. After the reaction was completed, acetic acid was added to adjust the pH to 6, and the by-products produced by neutralization were filtered out. The filtrate was taken and dried at a temperature of 100° C. for 6 hours to obtain unsaturated cardanol polyoxyethylene ether;

[0039] Wherein, the mass ratio of cardanol, 50wt% NaOH aqueous solution, and ethylene oxide is 302:1.2:264;

[0040] Unsaturated cardanol polyoxyethylene ether, aluminum-nickel alloy catalyst and anhydrous ethanol are mixed in a high-pressure sealed container at a mass ratio of 10:2.5:45, and reacted for 10 hours at room temperature in an inert gas atmosphere and a pressure of 6 MPa. After the reaction is completed, the aluminum-nickel alloy catalyst is filtered out, and the filtrate is taken and the organic solvent anhydrous ethanol is removed by rotary evaporation at a temperature of 60° C. to obtain hydrogenated cardanol polyoxyethylene ether;

[0041] The hydrogenated cardanol polyoxyethylene ether, hydroquinone and p-toluenesulfonic acid were mixed, nitrogen was introduced, mechanical stirring was carried out and the temperature was raised to 70°C, acrylic acid was added, and the reaction was carried out at a temperature of 130°C for 6 hours to obtain a crude reaction product, the crude reaction product was mixed with dichloromethane at a mass ratio of 20:120, 0.05 mol / L NaOH aqueous solution was added to adjust the pH to neutral, and the upper layer liquid (i.e., hydroquinone, p-toluenesulfonic acid, and excess unreacted acrylic acid) was removed, the lower layer liquid was taken, and a saturated sodium chloride solution with a volume of 10 times that of the lower layer liquid was added for washing three to four times, the liquid was separated, and the organic phase was taken, and dichloromethane was removed by rotary evaporation at a temperature of 30°C to obtain modified cardanol polyoxyethylene ether;

[0042] Wherein, the mass ratio of hydrogenated cardanol polyoxyethylene ether, hydroquinone, p-toluenesulfonic acid and acrylic acid is 2000:16:80:100;

[0043] Step (2), mixing hexadecyltrimethylammonium bromide (CTAB), distilled water, and 25 wt% ammonia water, stirring at a constant temperature of 70°C for 1 hour, adding tetraethyl orthosilicate (TEOS), stirring and reacting at 70°C for 6 hours, cooling after the reaction, and crystallizing at room temperature for 20 hours. After the crystallization, a reaction product is obtained, and deionized water and anhydrous ethanol with a volume of 10 times that of the reaction product are added for washing three times, respectively, and dried at 100°C for 12 hours, ground and dispersed, and calcined at 600°C for 6 hours to obtain mesoporous silicon;

[0044] The mass ratio of hexadecyltrimethylammonium bromide, distilled water, 25wt% ammonia water and tetraethyl orthosilicate is 3:300:200:14;

[0045] Mix mesoporous silicon and toluene, add γ-aminopropyltriethoxysilane (APTES) dropwise for 1 hour, stir for 0.5 hour in a nitrogen atmosphere, heat up, react at 130°C for 20 hours, cool and filter to obtain a reaction product, add 10 times the volume of the reaction product of toluene and anhydrous ethanol respectively to wash four times, and dry at 100°C for 12 hours to obtain amino mesoporous silicon;

[0046] Wherein, the mass ratio of mesoporous silica, toluene, and γ-aminopropyltriethoxysilane is 100:5200:80;

[0047] The amino mesoporous silica and acetone were mixed, stirred for 0.5 h in a nitrogen atmosphere, and a 0.05 mol / L chloroplatinic acid-ethanol solution was added, and the mixture was reacted at 90°C for 10 h. After the reaction was completed, the mixture was cooled, filtered, and the filter cake was taken and vacuum dried at 60°C for 4 h to obtain a heterogeneous catalyst.

[0048] Wherein, the mass ratio of amino mesoporous silica, acetone, and chloroplatinic acid-ethanol solution is 100:2400:12;

[0049] Step (3), mixing the modified cardanol polyoxyethylene ether, the heterogeneous catalyst, and hexamethyltrisiloxane in a mass ratio of 800:50:220, reacting for 8 hours in a nitrogen atmosphere at 100°C, cooling after the reaction, and removing the unreacted raw materials by rotary evaporation at 30°C to obtain an agricultural organosilicon synergist.

[0050] Example 2

[0051] This embodiment discloses an agricultural organosilicon synergist and a preparation method thereof, comprising the following steps:

[0052] Step (1), mixing cardanol with a 50 wt% NaOH aqueous solution, stirring and heating to 100°C in a high temperature reaction kettle, dehydrating for 2 h under vacuum conditions, adding ethylene oxide in a nitrogen atmosphere, and heating at 120°C, 2×10 5 The reaction was carried out under a pressure of Pa for 12 hours. After the reaction was completed, acetic acid was added to adjust the pH to 6, and the by-products produced by neutralization were filtered out. The filtrate was taken and dried at 80° C. for 8 hours to obtain unsaturated cardanol polyoxyethylene ether;

[0053] Wherein, the mass ratio of cardanol, 50wt% NaOH aqueous solution, and ethylene oxide is 302:0.2:264;

[0054] Unsaturated cardanol polyoxyethylene ether, aluminum-nickel alloy catalyst and anhydrous ethanol are mixed in a high-pressure sealed container at a mass ratio of 10:0.5:25, and reacted for 14 hours at room temperature in an inert gas atmosphere and a pressure of 2MPa. After the reaction is completed, the aluminum-nickel alloy catalyst is filtered out, and the filtrate is taken and the organic solvent anhydrous ethanol is removed by rotary evaporation at a temperature of 50°C to obtain hydrogenated cardanol polyoxyethylene ether;

[0055] The hydrogenated cardanol polyoxyethylene ether, hydroquinone and p-toluenesulfonic acid were mixed, nitrogen was introduced, mechanical stirring was carried out and the temperature was raised to 60°C, acrylic acid was added, and the reaction was carried out at 90°C for 8h to obtain a crude reaction product, the crude reaction product was mixed with dichloromethane at a mass ratio of 20:100, 0.05 mol / L NaOH aqueous solution was added to adjust the pH to neutral, and the upper layer liquid (i.e., hydroquinone, p-toluenesulfonic acid, and excess unreacted acrylic acid) was removed, the lower layer liquid was taken, and a saturated sodium chloride solution with a volume of 8 times that of the lower layer liquid was added for washing three to four times, the liquid was separated, and the organic phase was taken, and dichloromethane was removed by rotary evaporation at 20°C to obtain modified cardanol polyoxyethylene ether;

[0056] Among them, the mass ratio of hydrogenated cardanol polyoxyethylene ether, hydroquinone, p-toluenesulfonic acid, and acrylic acid is 2000:4:40:80;

[0057] Step (2), mixing hexadecyltrimethylammonium bromide (CTAB), distilled water, and 25 wt% ammonia water, stirring at a constant temperature of 60° C. for 2 h, adding tetraethyl orthosilicate (TEOS), stirring and reacting at 60° C. for 8 h, cooling after the reaction, and crystallizing at room temperature for 24 h. After the crystallization, a reaction product is obtained, and deionized water and anhydrous ethanol are added three times in volume of the reaction product to wash the product, respectively, and the product is dried at 80° C. for 16 h, ground and dispersed, and calcined at 560° C. for 8 h to obtain mesoporous silicon;

[0058] The mass ratio of hexadecyltrimethylammonium bromide, distilled water, 25wt% ammonia water and tetraethyl orthosilicate is 1:260:160:10;

[0059] Mix mesoporous silicon and toluene, add γ-aminopropyltriethoxysilane (APTES) dropwise for 2 hours, stir for 1 hour in a nitrogen atmosphere, heat up, react at 110°C for 24 hours, cool and filter to obtain a reaction product, add 8 times the volume of the reaction product of toluene and anhydrous ethanol respectively to wash four times, dry at 80°C for 16 hours to obtain amino mesoporous silicon;

[0060] Wherein, the mass ratio of mesoporous silica, toluene, and γ-aminopropyltriethoxysilane is 80:5000:60;

[0061] The amino-modified mesoporous silica and acetone were mixed, stirred for 1 hour in a nitrogen atmosphere, and a 0.05 mol / L chloroplatinic acid-ethanol solution was added, and the mixture was reacted at 70°C for 12 hours. After the reaction was completed, the mixture was cooled, filtered, and the filter cake was taken and vacuum dried at 50°C for 6 hours to obtain a heterogeneous catalyst.

[0062] The mass ratio of amino-modified mesoporous silica, acetone, and chloroplatinic acid-ethanol solution is 80:2000:8;

[0063] Step (3), mixing the modified cardanol polyoxyethylene ether, the heterogeneous catalyst, and hexamethyltrisiloxane in a mass ratio of 700:40:180, reacting for 12 hours in a nitrogen atmosphere at 80°C, cooling after the reaction, and removing the unreacted raw materials by rotary evaporation at 20°C to obtain an agricultural organosilicon synergist.

[0064] Example 3

[0065] This embodiment discloses an agricultural organosilicon synergist and a preparation method thereof, comprising the following steps:

[0066] Step (1), mixing cardanol with a 50wt% NaOH aqueous solution, stirring and heating to 115°C in a high-temperature reaction kettle, dehydrating for 1h under vacuum conditions, adding ethylene oxide in a nitrogen atmosphere, reacting at 135°C and 3×105Pa pressure for 9h, and after the reaction, adding acetic acid to adjust the pH to 6, filtering to remove by-products generated by neutralization, taking the filtrate, and drying at 95°C for 6.5h to obtain unsaturated cardanol polyoxyethylene ether;

[0067] Wherein, the mass ratio of cardanol, 50wt% NaOH aqueous solution, and ethylene oxide is 302:1:264;

[0068] Unsaturated cardanol polyoxyethylene ether, aluminum-nickel alloy catalyst and anhydrous ethanol are mixed in a high-pressure sealed container at a mass ratio of 10:2:40, and reacted for 11 hours at room temperature in an inert gas atmosphere and a pressure of 5 MPa. After the reaction is completed, the aluminum-nickel alloy catalyst is filtered out, and the filtrate is taken and the organic solvent anhydrous ethanol is removed by rotary evaporation at a temperature of 58° C. to obtain hydrogenated cardanol polyoxyethylene ether;

[0069] The hydrogenated cardanol polyoxyethylene ether, hydroquinone and p-toluenesulfonic acid were mixed, nitrogen was introduced, mechanical stirring was carried out and the temperature was raised to 68°C, acrylic acid was added, and the reaction was carried out at a temperature of 120°C for 6.5 hours to obtain a crude reaction product, the crude reaction product was mixed with dichloromethane at a mass ratio of 20:115, 0.05 mol / L NaOH aqueous solution was added to adjust the pH to neutral, and the upper layer liquid (i.e., hydroquinone, p-toluenesulfonic acid, excess unreacted acrylic acid) was removed, the lower layer liquid was taken, and a saturated sodium chloride solution with a volume of 10 times that of the lower layer liquid was added for washing three to four times, the liquid was separated, and the organic phase was taken, and dichloromethane was removed by rotary evaporation at a temperature of 30°C to obtain modified cardanol polyoxyethylene ether;

[0070] Among them, the mass ratio of hydrogenated cardanol polyoxyethylene ether, hydroquinone, p-toluenesulfonic acid, and acrylic acid is 2000:13:70:95;

[0071] Step (2), mixing hexadecyltrimethylammonium bromide (CTAB), distilled water, and 25 wt% ammonia water, stirring at a constant temperature of 68° C. for 1 h, adding tetraethyl orthosilicate (TEOS), stirring and reacting at 68° C. for 6.5 h, cooling after the reaction, and crystallizing at room temperature for 21 h. After the crystallization, a reaction product is obtained, and deionized water and anhydrous ethanol with a volume of 10 times that of the reaction product are added for washing three times, respectively, and dried at 95° C. for 13 h, ground and dispersed, and calcined at 590° C. for 6.5 h to obtain mesoporous silicon;

[0072] The mass ratio of hexadecyltrimethylammonium bromide, distilled water, 25wt% ammonia water and tetraethyl orthosilicate is 2.5:290:190:13;

[0073] Mix mesoporous silicon and toluene, add γ-aminopropyltriethoxysilane (APTES) dropwise for 1 hour, stir for 0.5 hour in nitrogen atmosphere, heat up, react at 125°C for 21 hours, cool and filter to obtain a reaction product, add 10 times the volume of the reaction product of toluene and anhydrous ethanol respectively to wash four times, dry at 95°C for 13 hours to obtain amino mesoporous silicon;

[0074] Among them, the mass ratio of mesoporous silica, toluene, and γ-aminopropyltriethoxysilane is 95:5150:75;

[0075] The amino mesoporous silica and acetone were mixed, stirred for 0.5 h in a nitrogen atmosphere, and a 0.05 mol / L chloroplatinic acid-ethanol solution was added, and the mixture was reacted at 85°C for 10.5 h. After the reaction was completed, the mixture was cooled, filtered, and the filter cake was taken and vacuum dried at 58°C for 4.5 h to obtain a heterogeneous catalyst.

[0076] The mass ratio of amino mesoporous silica, acetone, and chloroplatinic acid-ethanol solution is 95:2300:11;

[0077] Step (3), mixing the modified cardanol polyoxyethylene ether, the heterogeneous catalyst, and hexamethyltrisiloxane in a mass ratio of 775:48:210, reacting for 9 hours in a nitrogen atmosphere at 95°C, cooling after the reaction, and removing the unreacted raw materials by rotary evaporation at 30°C to obtain an agricultural organosilicon synergist.

[0078] Example 4

[0079] This embodiment discloses an agricultural organosilicon synergist and a preparation method thereof, comprising the following steps:

[0080] Step (1), mixing cardanol with a 50 wt% NaOH aqueous solution, stirring and heating to 110°C in a high temperature reaction kettle, dehydrating for 1.5 h under vacuum conditions, adding ethylene oxide in a nitrogen atmosphere, and heating at 130°C, 2.5×10 5 The reaction was carried out under a pressure of Pa for 10 hours. After the reaction was completed, acetic acid was added to adjust the pH to 6, and the by-products produced by neutralization were filtered out. The filtrate was taken and dried at 90° C. for 7 hours to obtain unsaturated cardanol polyoxyethylene ether;

[0081] Wherein, the mass ratio of cardanol, 50wt% NaOH aqueous solution, and ethylene oxide is 302:0.7:264;

[0082] Unsaturated cardanol polyoxyethylene ether, aluminum-nickel alloy catalyst and anhydrous ethanol are mixed in a high-pressure sealed container at a mass ratio of 10:1.5:35, and reacted for 12 hours at room temperature in an inert gas atmosphere and a pressure of 4 MPa. After the reaction is completed, the aluminum-nickel alloy catalyst is filtered out, and the filtrate is taken and the organic solvent anhydrous ethanol is removed by rotary evaporation at a temperature of 55° C. to obtain hydrogenated cardanol polyoxyethylene ether;

[0083] The hydrogenated cardanol polyoxyethylene ether, hydroquinone and p-toluenesulfonic acid were mixed, nitrogen was introduced, mechanical stirring was carried out and the temperature was raised to 65°C, acrylic acid was added, and the reaction was carried out at a temperature of 110°C for 7 hours to obtain a crude reaction product, the crude reaction product was mixed with dichloromethane at a mass ratio of 20:110, 0.05 mol / L NaOH aqueous solution was added to adjust the pH to neutral, and the upper layer liquid (i.e., hydroquinone, p-toluenesulfonic acid, and excess unreacted acrylic acid) was removed, the lower layer liquid was taken, and a saturated sodium chloride solution with a volume of 9 times that of the lower layer liquid was added for washing three to four times, the liquid was separated, and the organic phase was taken, and dichloromethane was removed by rotary evaporation at a temperature of 25°C to obtain modified cardanol polyoxyethylene ether;

[0084] Wherein, the mass ratio of hydrogenated cardanol polyoxyethylene ether, hydroquinone, p-toluenesulfonic acid and acrylic acid is 2000:10:60:90;

[0085] Step (2), mixing hexadecyltrimethylammonium bromide (CTAB), distilled water, and 25 wt% ammonia water, stirring at a constant temperature of 65° C. for 1.5 h, adding tetraethyl orthosilicate (TEOS), stirring and reacting at 65° C. for 7 h, cooling after the reaction, and crystallizing at room temperature for 22 h. After the crystallization, a reaction product is obtained, and deionized water and anhydrous ethanol are added three times in volume of the reaction product for washing, respectively, and dried at 90° C. for 14 h, ground and dispersed, and calcined at 580° C. for 7 h to obtain mesoporous silicon;

[0086] The mass ratio of hexadecyltrimethylammonium bromide, distilled water, 25wt% ammonia water and tetraethyl orthosilicate is 2:280:180:12;

[0087] Mix mesoporous silicon and toluene, add γ-aminopropyltriethoxysilane (APTES) dropwise for 1.5 hours, stir for 0.7 hours in a nitrogen atmosphere, heat up, react at 120°C for 22 hours, cool and filter to obtain a reaction product, add 9 times the volume of the reaction product of toluene and anhydrous ethanol respectively to wash four times, and dry at 90°C for 14 hours to obtain amino mesoporous silicon;

[0088] The mass ratio of mesoporous silica, toluene and γ-aminopropyltriethoxysilane is 90:5100:70;

[0089] The amino mesoporous silica and acetone were mixed, stirred in a nitrogen atmosphere for 0.7 h, 0.05 mol / L chloroplatinic acid-ethanol solution was added, and the mixture was reacted at 80°C for 11 h. After the reaction was completed, the mixture was cooled, filtered, and the filter cake was taken and vacuum dried at 55°C for 5 h to obtain a heterogeneous catalyst.

[0090] Wherein, the mass ratio of amino mesoporous silica, acetone, and chloroplatinic acid-ethanol solution is 90:2200:10;

[0091] Step (3), mixing the modified cardanol polyoxyethylene ether, the heterogeneous catalyst, and hexamethyltrisiloxane in a mass ratio of 750:45:200, reacting for 10 hours in a nitrogen atmosphere at 90°C, cooling after the reaction, and removing the unreacted raw materials by rotary evaporation at 25°C to obtain an agricultural organosilicon synergist.

[0092] Example 5

[0093] This embodiment discloses an agricultural organosilicon synergist and a preparation method thereof, comprising the following steps:

[0094] Step (1), mixing cardanol with a 50 wt% NaOH aqueous solution, stirring and heating to 105°C in a high temperature reaction kettle, dehydrating for 2 h under vacuum conditions, adding ethylene oxide in a nitrogen atmosphere, and heating at 125°C, 2.5×10 5 The reaction was carried out under a pressure of Pa for 11 hours. After the reaction was completed, acetic acid was added to adjust the pH to 6, and the by-products produced by neutralization were filtered out. The filtrate was taken and dried at 85° C. for 7.5 hours to obtain unsaturated cardanol polyoxyethylene ether;

[0095] Wherein, the mass ratio of cardanol, 50wt% NaOH aqueous solution, and ethylene oxide is 302:0.4:264;

[0096] Unsaturated cardanol polyoxyethylene ether, aluminum-nickel alloy catalyst and anhydrous ethanol are mixed in a high-pressure sealed container at a mass ratio of 10:1:30, and reacted for 13 hours at room temperature in an inert gas atmosphere and a pressure of 3 MPa. After the reaction is completed, the aluminum-nickel alloy catalyst is filtered out, and the filtrate is taken and the organic solvent anhydrous ethanol is removed by rotary evaporation at a temperature of 52° C. to obtain hydrogenated cardanol polyoxyethylene ether;

[0097] The hydrogenated cardanol polyoxyethylene ether, hydroquinone and p-toluenesulfonic acid were mixed, nitrogen was introduced, mechanical stirring was carried out and the temperature was raised to 62°C, acrylic acid was added, and the reaction was carried out at a temperature of 100°C for 7.5 hours to obtain a crude reaction product, the crude reaction product was mixed with dichloromethane at a mass ratio of 20:105, 0.05 mol / L NaOH aqueous solution was added to adjust the pH to neutral, and the upper layer liquid (i.e., hydroquinone, p-toluenesulfonic acid, and excess unreacted acrylic acid) was removed, the lower layer liquid was taken, and a saturated sodium chloride solution with a volume of 8 times that of the lower layer liquid was added for washing three to four times, the liquid was separated, and the organic phase was taken, and dichloromethane was removed by rotary evaporation at a temperature of 20°C to obtain modified cardanol polyoxyethylene ether;

[0098] Among them, the mass ratio of hydrogenated cardanol polyoxyethylene ether, hydroquinone, p-toluenesulfonic acid, and acrylic acid is 2000:7:50:85;

[0099] Step (2), mixing hexadecyltrimethylammonium bromide (CTAB), distilled water, and 25 wt% ammonia water, stirring at a constant temperature of 62° C. for 2 h, adding tetraethyl orthosilicate (TEOS), stirring and reacting at 62° C. for 7.5 h, cooling after the reaction, and crystallizing at room temperature for 23 h. After the crystallization, obtaining a reaction product, adding deionized water and anhydrous ethanol 8 times the volume of the reaction product for washing three times, drying at 85° C. for 15 h, grinding and dispersing, and calcining at 570° C. for 7.5 h to obtain mesoporous silicon;

[0100] The mass ratio of hexadecyltrimethylammonium bromide, distilled water, 25wt% ammonia water and tetraethyl orthosilicate is 1.5:270:170:11;

[0101] Mix mesoporous silicon and toluene, add γ-aminopropyltriethoxysilane (APTES) dropwise for 2 hours, stir for 1 hour in a nitrogen atmosphere, heat up, react at 115°C for 23 hours, cool and filter to obtain a reaction product, add 8 times the volume of the reaction product of toluene and anhydrous ethanol respectively to wash four times, dry at 85°C for 15 hours to obtain amino mesoporous silicon;

[0102] Among them, the mass ratio of mesoporous silica, toluene, and γ-aminopropyltriethoxysilane is 85:5050:65;

[0103] The amino mesoporous silica and acetone were mixed, stirred for 1 hour in a nitrogen atmosphere, and a 0.05 mol / L chloroplatinic acid-ethanol solution was added, and the mixture was reacted at 75°C for 11.5 hours. After the reaction was completed, the mixture was cooled, filtered, and the filter cake was taken and vacuum dried at 52°C for 5.5 hours to obtain a heterogeneous catalyst.

[0104] The mass ratio of amino-modified mesoporous silica, acetone, and chloroplatinic acid-ethanol solution is 85:2100:9;

[0105] Step (3), mixing the modified cardanol polyoxyethylene ether, the heterogeneous catalyst, and hexamethyltrisiloxane in a mass ratio of 725:42:190, reacting for 11 hours in a nitrogen atmosphere at 85°C, cooling after the reaction, and removing the unreacted raw materials by rotary evaporation at 20°C to obtain an agricultural organosilicon synergist.

[0106] Comparative Example 1

[0107] This comparative example discloses an agricultural organosilicon synergist and a preparation method thereof, comprising the following steps:

[0108] Step (1), mixing cardanol with a 50 wt% NaOH aqueous solution, stirring and heating to 100°C in a high temperature reaction kettle, dehydrating for 2 h under vacuum conditions, adding ethylene oxide in a nitrogen atmosphere, and heating at 120°C, 2×10 5 The reaction was carried out under a pressure of Pa for 12 hours. After the reaction was completed, acetic acid was added to adjust the pH to 6, and the by-products produced by neutralization were filtered out. The filtrate was taken and dried at 80° C. for 8 hours to obtain unsaturated cardanol polyoxyethylene ether;

[0109] Wherein, the mass ratio of cardanol, 50wt% NaOH aqueous solution, and ethylene oxide is 302:0.2:264;

[0110] Unsaturated cardanol polyoxyethylene ether, aluminum-nickel alloy catalyst and anhydrous ethanol are mixed in a high-pressure sealed container at a mass ratio of 10:0.5:25, and reacted for 14 hours at room temperature in an inert gas atmosphere and a pressure of 2MPa. After the reaction is completed, the aluminum-nickel alloy catalyst is filtered out, and the filtrate is taken and the organic solvent anhydrous ethanol is removed by rotary evaporation at a temperature of 50°C to obtain hydrogenated cardanol polyoxyethylene ether;

[0111] The hydrogenated cardanol polyoxyethylene ether, hydroquinone and p-toluenesulfonic acid were mixed, nitrogen was introduced, mechanical stirring was carried out and the temperature was raised to 60°C, acrylic acid was added, and the reaction was carried out at 90°C for 8h to obtain a crude reaction product, the crude reaction product was mixed with dichloromethane at a mass ratio of 20:100, 0.05 mol / L NaOH aqueous solution was added to adjust the pH to neutral, and the upper layer liquid (i.e., hydroquinone, p-toluenesulfonic acid, and excess unreacted acrylic acid) was removed, the lower layer liquid was taken, and a saturated sodium chloride solution with a volume of 8 times that of the lower layer liquid was added for washing three to four times, the liquid was separated, and the organic phase was taken, and dichloromethane was removed by rotary evaporation at 20°C to obtain modified cardanol polyoxyethylene ether;

[0112] Among them, the mass ratio of hydrogenated cardanol polyoxyethylene ether, hydroquinone, p-toluenesulfonic acid, and acrylic acid is 2000:4:40:80;

[0113] Step (2), the modified cardanol polyoxyethylene ether, the homogeneous catalyst 0.05 mol / L chloroplatinic acid-ethanol solution, hexamethyltrisiloxane in a mass ratio of 700:40:180 mixed, in a nitrogen atmosphere, at a temperature of 80 ° C for 12 hours, after the reaction is completed, cooled, at 20 ° C temperature rotary evaporation to remove the unreacted raw materials, to obtain an agricultural organosilicon synergist.

[0114] Comparative Example 2

[0115] This comparative example discloses an agricultural organosilicon synergist and a preparation method thereof, comprising the following steps:

[0116] Step (1), mixing cardanol with a 50 wt% NaOH aqueous solution, stirring and heating to 100°C in a high temperature reaction kettle, dehydrating for 2 h under vacuum conditions, adding ethylene oxide in a nitrogen atmosphere, and heating at 120°C, 2×10 5 The reaction was carried out under a pressure of Pa for 12 hours. After the reaction was completed, acetic acid was added to adjust the pH to 6, and the by-products produced by neutralization were filtered out. The filtrate was taken and dried at 80° C. for 8 hours to obtain unsaturated cardanol polyoxyethylene ether;

[0117] Wherein, the mass ratio of cardanol, 50wt% NaOH aqueous solution, and ethylene oxide is 302:0.2:264;

[0118] Unsaturated cardanol polyoxyethylene ether, aluminum-nickel alloy catalyst and anhydrous ethanol are mixed in a high-pressure sealed container at a mass ratio of 10:0.5:25, and reacted for 14 hours at room temperature in an inert gas atmosphere and a pressure of 2MPa. After the reaction is completed, the aluminum-nickel alloy catalyst is filtered out, and the filtrate is taken and the organic solvent anhydrous ethanol is removed by rotary evaporation at a temperature of 50°C to obtain hydrogenated cardanol polyoxyethylene ether;

[0119] The hydrogenated cardanol polyoxyethylene ether, hydroquinone and p-toluenesulfonic acid were mixed, nitrogen was introduced, mechanical stirring was carried out and the temperature was raised to 60°C, acrylic acid was added, and the reaction was carried out at 90°C for 8h to obtain a crude reaction product, the crude reaction product was mixed with dichloromethane at a mass ratio of 20:100, 0.05 mol / L NaOH aqueous solution was added to adjust the pH to neutral, and the upper layer liquid (i.e., hydroquinone, p-toluenesulfonic acid, and excess unreacted acrylic acid) was removed, the lower layer liquid was taken, and a saturated sodium chloride solution with a volume of 8 times that of the lower layer liquid was added for washing three to four times, the liquid was separated, and the organic phase was taken, and dichloromethane was removed by rotary evaporation at 20°C to obtain modified cardanol polyoxyethylene ether;

[0120] Among them, the mass ratio of hydrogenated cardanol polyoxyethylene ether, hydroquinone, p-toluenesulfonic acid, and acrylic acid is 2000:4:40:80;

[0121] Step (2), mixing hexadecyltrimethylammonium bromide (CTAB), distilled water, and 25 wt% ammonia water, stirring at a constant temperature of 60° C. for 2 h, adding tetraethyl orthosilicate (TEOS), stirring and reacting at 60° C. for 8 h, cooling after the reaction, and crystallizing at room temperature for 24 h. After the crystallization, a reaction product is obtained, and deionized water and anhydrous ethanol are added three times in volume of the reaction product to wash the product, respectively, and the product is dried at 80° C. for 16 h, ground and dispersed, and calcined at 560° C. for 8 h to obtain mesoporous silicon;

[0122] The mass ratio of hexadecyltrimethylammonium bromide, distilled water, 25wt% ammonia water and tetraethyl orthosilicate is 1:260:160:10;

[0123] Mix mesoporous silicon and toluene, add γ-aminopropyltriethoxysilane (APTES) dropwise for 2 hours, stir for 1 hour in a nitrogen atmosphere, heat up, react at 110°C for 24 hours, cool and filter to obtain a reaction product, add 8 times the volume of the reaction product of toluene and anhydrous ethanol respectively to wash four times, dry at 80°C for 16 hours to obtain amino mesoporous silicon;

[0124] Wherein, the mass ratio of mesoporous silica, toluene, and γ-aminopropyltriethoxysilane is 80:5000:60;

[0125] The amino-modified mesoporous silica and acetone were mixed, stirred for 1 hour in a nitrogen atmosphere, and a 0.05 mol / L chloroplatinic acid-ethanol solution was added, and the mixture was reacted at 70°C for 12 hours. After the reaction was completed, the mixture was cooled, filtered, and the filter cake was taken and vacuum dried at 50°C for 6 hours to obtain a heterogeneous catalyst.

[0126] The mass ratio of amino-modified mesoporous silica, acetone, and chloroplatinic acid-ethanol solution is 80:2000:8;

[0127] Step (3), mixing the modified cardanol polyoxyethylene ether, the heterogeneous catalyst, and heptamethyltrisiloxane in a mass ratio of 350:40:180, reacting for 12 hours in a nitrogen atmosphere at 80°C, cooling after the reaction, and removing the unreacted raw materials by rotary evaporation at 20°C to obtain an agricultural organosilicon synergist.

[0128] In the above embodiments and comparative examples: cardanol comes from Guangzhou Yusheng Chemical Co., Ltd., CAS No.: 501-26-8; sodium hydroxide comes from Sinopharm Chemical Reagent Co., Ltd., CAS No.: 14014-06-3; ethylene oxide comes from Tianjin Wanfu Chemical Raw Materials Co., Ltd., CAS No.: 75-21-8; glacial acetic acid comes from Sinopharm Chemical Reagent Co., Ltd., CAS No.: 64-19-7; aluminum-nickel alloy catalyst comes from Shandong Jiahong Chemical Co., Ltd., CAS No.: 12635-29-9; anhydrous ethanol comes from Tianjin Hualian Chemical Co., Ltd., CAS No.: 64-17-5; hydroquinone comes from Tianjin Komiou Chemical Reagent Co., Ltd., CAS No.: 123-31-9; p-toluenesulfonic acid comes from Tianjin Baishi Chemical Co., Ltd., CAS No.: 104-15-4; acrylic acid comes from Tianjin Beilian Fine Chemicals Development Co., Ltd., CAS No.: 79-10-7; dichloromethane comes from Tianjin Fuchen Chemical Reagent Factory, CAS No.: 75-09 -2; sodium chloride was from Tianjin Tianxin Fine Chemical Development Center, CAS No.: 7647-14-5; hexadecyltrimethylammonium bromide was from Aladdin Reagent Co., Ltd., CAS No.: 57-09-0; ammonia was from Tianjin Baishi Chemical Co., Ltd., CAS No.: 1336-21-6; ethyl orthosilicate was from Aladdin Reagent Co., Ltd., CAS No.: 78-10-4; toluene was from Guangzhou Chemical Reagent Factory, CAS No.: 108-88-3; γ-aminopropyltriethoxysilane was from Aladdin Reagent Co., Ltd., CAS No.: 919-30-2; acetone was from Nanjing Kaiyan Environmental Protection Technology Co., Ltd., CAS No.: 67-64-1; chloroplatinic acid hexahydrate was from Shanghai Sanaisi Reagent Co., Ltd., CAS No.: 18497-13-7; hexamethyltrisiloxane was from Hubei Nona Technology Co., Ltd., CAS No.: 541-05-9; heptamethyltrisiloxane was from Yangzhou Chenhua New Materials Co., Ltd., CAS No.: 1873-88-7.

[0129] Test example

[0130] The comprehensive performance test of the agricultural organosilicon synergist prepared in Examples 1-5 and Comparative Examples 1-2 was carried out. The specific test results are shown in Table 1:

[0131] Table 1

[0132]

[0133] The detection of each index in Table 1 was carried out according to the following methods: the surface tension was measured by using the JK99B tensiometer of Beijing Zhongyi Kexin Technology Co., Ltd.; the contact angle test operation included: after the sample was dissolved in distilled water and diluted to a certain concentration, a small amount of the diluted sample was taken with a 10 μL microinjector, and vertically dropped onto the cucumber leaf laid on a glass slide, and the contact angle at 5 s was measured by using the Theta contact angle surface tension meter at 25°C. The smaller the contact angle, the better the wetting performance; the foaming performance of the product was measured by the oscillation method, and the specific test operation included: taking 50 mL of a sample with a concentration of 0.1 wt% in a 100 mL measuring cylinder, plugging the measuring cylinder mouth with a stopper, and shaking the measuring cylinder up and down 30 times, and recording the total height of the liquid and the foam immediately after 30 s, respectively, and repeating the experiment three times, taking the average value, and calculating the total height according to the formula P F =H / H0Calculate P F (H is the total height of liquid and foam, mm; H0 is the initial liquid height, mm), the smaller the foaming force, the lower the foaming performance; the test operation of spreading ability includes: using a 50μL micro-injector to drop 20μL of 0.1wt% sample and pure water on the paraffin sheet, recording the time with a stopwatch, and measuring the diffusion area of ​​the droplet on the paraffin after 5 minutes. Repeat the experiment three times and take the average value. Calculate SA according to the formula SA=S / S0 (S is the spreading diameter of the silicone enhancer, cm 2 ; S0 is the spreading diameter of pure water, cm 2 ), the result reflects the spreading ability of the product.

[0134] It can be seen from the test results in Table 1 that the agricultural organosilicon synergist prepared by the present invention has extremely low surface tension and foaming properties, and has excellent wettability and spreadability.

[0135] In Comparative Example 1, when the hydrosilylation reaction of polyether and silicone oil is carried out, the catalyst used is a commonly used homogeneous catalyst. Although its catalytic activity is also high, it is difficult to separate from the product after the reaction, which affects the purity of the product. In addition, a large amount of heat is released during the hydrosilylation reaction, resulting in side reactions and material impact. As a result, the general performance of the agricultural organosilicon synergist synthesized in Comparative Example 1 is lower than that of the embodiments.

[0136] The hydrogen-containing silicone oil used in Comparative Example 2 is heptamethyltrisiloxane, which contains only one Si-H bond in its structural formula. Compared with hexamethyltrisiloxane, only a single polyether structure is introduced. The introduction of the polyether structure can improve the surface properties and defoaming and anti-foaming properties of the surfactant. At the same time, when the molecular weight of the polyether is large, the surface activity of the product increases with the increase of the hydrogen content of the silicone oil. Therefore, the surface tension and foaming performance of Comparative Example 2 are higher than those of the embodiment, while the wetting performance and spreading performance are lower than those of the embodiment.

[0137] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing an agricultural organosilicon synergist, characterized in that: The following steps are involved: Step (1), mixing cardanol with a NaOH aqueous solution, heating, dehydrating, adding ethylene oxide and reacting, and after the reaction is completed, purifying to obtain unsaturated cardanol polyoxyethylene ether; Unsaturated cardanol polyoxyethylene ether, an aluminum-nickel alloy catalyst, and anhydrous ethanol are mixed for reaction, and after the reaction is completed, the mixture is purified to obtain hydrogenated cardanol polyoxyethylene ether; Mix hydrogenated cardanol polyoxyethylene ether, hydroquinone and p-toluenesulfonic acid, add acrylic acid and react, and purify after the reaction to obtain modified cardanol polyoxyethylene ether; Step (2), mixing the modified cardanol polyoxyethylene ether, the heterogeneous catalyst and hexamethyltrisiloxane and reacting them, cooling and rotary evaporating after the reaction to obtain an agricultural organosilicon synergist.

2. The method for preparing an agricultural organosilicon synergist according to claim 1, characterized in that: In the step (1), when preparing unsaturated cardanol polyoxyethylene ether: the NaOH aqueous solution is a 50wt% NaOH aqueous solution; the dehydration condition is dehydration under vacuum for 1-2h; the mass ratio of cardanol, 50wt% NaOH aqueous solution, and ethylene oxide is 302: (0.2-1.2): 264; the reaction conditions are: at a temperature of 120-140°C, 2×10 5 -3×10 5 React under pressure for 8-12 hours.

3. The method for preparing an agricultural organosilicon synergist according to claim 1, characterized in that: In the step (1), when preparing hydrogenated cardanol polyoxyethylene ether: the mass ratio of unsaturated cardanol polyoxyethylene ether, aluminum-nickel alloy catalyst, and anhydrous ethanol is 10:(0.5-2.5):(25-45); the reaction conditions are: reacting for 10-14 hours in an inert gas atmosphere, at a pressure of 2-6 MPa, and at room temperature.

4. The method for preparing an agricultural organosilicon synergist according to claim 1, characterized in that: In the step (1), when preparing the modified cardanol polyoxyethylene ether: the mass ratio of hydrogenated cardanol polyoxyethylene ether, hydroquinone, p-toluenesulfonic acid, and acrylic acid is 2000:(4-16):(40-80):(80-100); the reaction conditions are: reacting at a temperature of 90-130°C for 6-8h.

5. The method for preparing an agricultural organosilicon synergist according to claim 1, characterized in that: In the step (1), when preparing the modified cardanol polyoxyethylene ether, the purification step is: mixing the crude reaction product with dichloromethane in a mass ratio of 20:(100-120), adding 0.05 mol / L NaOH aqueous solution to adjust the pH to neutral, standing to separate the layers, removing the upper layer of liquid, taking the lower layer of liquid, washing, and removing the dichloromethane by rotary evaporation.

6. The method for preparing an agricultural organosilicon synergist according to claim 1, characterized in that: In the step (2), the heterogeneous catalyst is prepared by the following steps: mixing hexadecyltrimethylammonium bromide, water and ammonia water, adding tetraethyl orthosilicate and stirring for reaction, cooling after the reaction, crystallizing, and obtaining a reaction product after the crystallization, drying, crushing and calcining to obtain mesoporous silicon; Mixing mesoporous silica, toluene and γ-aminopropyltriethoxysilane, heating and reacting, and purifying after the reaction to obtain amino-modified mesoporous silica; The amino-modified mesoporous silica and acetone are mixed and stirred, and a chloroplatinic acid-ethanol solution is added to react. After the reaction is completed, the catalyst is purified to obtain a heterogeneous catalyst.

7. The method for preparing a heterogeneous catalyst according to claim 6, characterized in that: When preparing mesoporous silicon: the mass ratio of hexadecyltrimethylammonium bromide, distilled water, 25wt% ammonia water, and tetraethyl orthosilicate is (1-3):(260-300):(160-200):(10-14); the reaction conditions are: stirring the reaction at 60-70°C for 6-8h; the crystallization time is 20-24h; the calcination conditions are: calcining at 560-600°C for 6-8h; when preparing amino mesoporous silicon: the mass ratio of mesoporous silicon, toluene, and γ-aminopropyltriethoxysilane is (80-100):(5000-5200):(60-80); the reaction conditions are: in a nitrogen atmosphere, react at 110-130°C for 20-24h.

8. The method for preparing a heterogeneous catalyst according to claim 6, characterized in that: When preparing a heterogeneous catalyst: the mass ratio of amino mesoporous silica, acetone, and chloroplatinic acid-ethanol solution is (80-100):(2000-2400):(8-12); the reaction conditions are: in a nitrogen atmosphere, react at a temperature of 70-90°C for 10-12h.

9. The method for preparing an agricultural organosilicon synergist according to claim 1, characterized in that: In the step (2), the mass ratio of the modified cardanol polyoxyethylene ether, the heterogeneous catalyst and the hexamethyltrisiloxane is (700-800):(40-50):(180-220); the reaction conditions are: reacting in a nitrogen atmosphere at a temperature of 80-100° C. for 8-12 hours.

10. An agricultural organosilicon synergist prepared by the method for preparing an agricultural organosilicon synergist as claimed in any one of claims 1 to 9.

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