Pyrithiobac-methyl ionic liquid as well as preparation method and application thereof

Abstract

The invention discloses pyrithiobac-methyl ionic liquid and a preparation method and application thereof, the structural general formula of the pyrithiobac-methyl ionic liquid is shown as (I), in the formula, A is a tertiary amine cation, and B is a tertiary amine cation. The compound is selected from any one of 3-hexadecyl-1-methyl-1H-imidazole-3-onium, 4-hexadecyl-4-methylmorpholine-4-onium, 4-hydroxy-1-methyl-1-hexadecyl piperidine-1-ammonium and N, N-diethyl-N-(2-ethoxyl) hexadecyl quaternary ammonium, and the compound is selected from any one of 3-hexadecyl-1-methyl-1H-imidazole-3-onium, 4-hexadecyl-4-methylmorpholine-4-onium, 4-hydroxy-1-methyl-1-hexadecyl piperidine-1-ammonium and N, N-diethyl-N-(2- According to the invention, pyrithiobac-methyl acid is used as an anion, and forms the functionalized pyrithiobac-methyl ionic liquid together with a structural modified amine cation structural framework, and the functionalized pyrithiobac-methyl ionic liquid can be prepared through an ion exchange reaction and an acid-base neutralization reaction, and shows relatively high thermal stability, excellent physical and chemical properties and biological activity. The pyrithiobac-methyl ionic liquid is used as an active component to prepare a microcapsule suspending agent, so that low-dose continuous drug release can be realized, and the service cycle of a herbicide is prolonged; the application range of the ionic liquid in the field of plant protection is expanded, the herbicidal activity of a traditional pyrithiobac-methyl pesticide is improved, the use efficiency of the pesticide is improved, and the use amount of the pesticide is reduced, so that the environmental pollution is reduced. # imgabs0 #

Description

Technical Field

[0001] The invention relates to a pyrithione-butyl ionic liquid and a preparation method and application thereof, belonging to the technical field of plant protection. Background Art

[0002] Cotton is one of the most important crops in the world and the main source of income for more than 100 million cotton farmers in my country. Both the main and by-products of cotton have high utilization value. Fabrics involved in agriculture and textile industry, from cottonseed oil to cotton yarn, cotton cloth, clothing, etc. A major difficulty in cotton planting is that weeds in the field will form competitive growth with cotton, thereby inhibiting the growth of cotton and causing cotton yield loss. The main weeds are barnyard grass, crabgrass, Amaranthus retroflexus, Setaria viridis, etc. Pyrithione is an effective herbicide for controlling weeds in cotton fields. It can control most dicotyledonous weeds and some monocotyledonous weeds. It has a good control effect on well-known difficult-to-control weeds such as various morning glories, Xanthium sibiricum, Ramie, Prickly yellow flowered mulberry, Sesbania sesbania, Arab sorghum, etc. In addition to the extremely small amount used, the high safety to cotton is the main reason for its popularity.

[0003] Pyrithione is a pyrimidine salicylic acid compound and an acetolactate synthase (ALS) inhibitor. By preventing the biosynthesis of amino acids, mitosis cannot be completed, protein synthesis is blocked, and sensitive weeds stagnate and yellow, and then gradually dry up and die. Traditional pyrithione herbicides have poor water solubility and are usually water-dispersible granules or wettable powders with low effective utilization rates. In addition, during agricultural production, repeated spraying or use of large doses of herbicides will cause a large amount of pesticides or organic solvents to remain in cotton fields, causing problems such as excessive pesticide residues and water pollution. Appropriate structural modification of pyrithione can reduce the amount of pesticides used and improve the weed control effect, which is in line with the "reducing the amount and increasing the efficiency" concept advocated by modern agriculture.

[0004] Ionic liquids are a type of salt composed of organic cations and organic or inorganic anions with a melting point of less than 100°C. Ionic liquids have the advantages of low saturated vapor pressure, good solubility, thermal stability, adjustable physical properties, and structural designability, and are used in microemulsion systems, extraction separation, electrochemistry, and catalytic synthesis. The prior art has not yet disclosed a herbicide ionic liquid composed of pyrithione as an anion. The physicochemical properties and herbicidal activity of the herbicide ionic liquids obtained by combining different cation structures, functional groups, carbon chain lengths with pyrithione anions are difficult to predict. Therefore, it is necessary to conduct targeted research on pyrithione herbicide ionic liquids, hoping that the reasonable design and effective modification of organic cations can improve the herbicidal activity of pyrithione ionic liquids. Summary of the invention

[0005] Purpose of the invention: The first purpose of the present invention is to provide a pyrimithiopyralid ionic liquid, the second purpose of the present invention is to provide a method for preparing the pyrimithiopyralid ionic liquid, the third purpose of the present invention is to provide a pyrimithiopyralid ionic liquid microcapsule suspension prepared using the pyrimithiopyralid ionic liquid, the fourth purpose of the present invention is to provide a method for preparing the pyrimithiopyralid ionic liquid microcapsule suspension, and the fifth purpose of the present invention is to provide the use of the pyrimithiopyralid ionic liquid or the pyrimithiopyralid ionic liquid microcapsule suspension in weed control.

[0006] Technical solution: The present invention discloses a pyrimthiosulfuron ionic liquid, the general structural formula of which is shown in (I):

[0007]

[0008] Wherein, A is a tertiary amine cation.

[0009] Further, the tertiary amine cation A is selected from any one of 3-hexadecyl-1-methyl-1H-imidazole-3-onium, 4-hexadecyl-4-methylmorpholinium-4-onium, 4-hydroxy-1-methyl-1-hexadecylpiperidin-1-ammonium, and N,N-diethyl-N-(2-hydroxyethyl)hexadecyl quaternary ammonium, and their structures are shown below:

[0010]

[0011] Further, the pyrimthiosulfate-based ionic liquid is selected from any one of 3-hexadecyl-1-methyl-1H-imidazole-[2-chloro-6-(4,6-dimethoxypyrimidine-2-sulfenyl)benzoic acid] salt, 4-hexadecyl-4-methylmorpholine-[2-chloro-6-(4,6-dimethoxypyrimidine-2-sulfenyl)benzoic acid] salt, N,N-diethyl-N-(2-hydroxyethyl)hexadecyl ammonium-[2-chloro-6-(4,6-dimethoxypyrimidine-2-sulfenyl)benzoic acid] salt or 4-hydroxy-1-methyl-1-hexadecylpiperidinium-[2-chloro-6-(4,6-dimethoxypyrimidine-2-sulfenyl)benzoic acid] salt, and their structural formulas are shown below:

[0012]

[0013]

[0014] The method for preparing the pyrithiobac-butyl ionic liquid of the present invention comprises the following steps:

[0015] (A1) Preparation of brominated ammonium salt: a tertiary amine compound, 1-bromohexadecane and a solvent are mixed, heated under reflux for reaction, rotary evaporated, and vacuum dried to obtain brominated ammonium salt;

[0016] (A2) Preparation of pyrifos-butyl herbicide ionic liquid: dissolving ammonium bromide in water, passing through an anion exchange resin to obtain an aqueous solution of ammonium hydroxide, and then mixing with 2-chloro-6-(4,6-dimethoxypyrimidine-2-thio)benzoic acid, performing an acid-base neutralization reaction, and drying to obtain a pyrifos-butyl ionic liquid;

[0017] Alternatively, the ammonium bromide salt is dissolved in ethanol, silver oxide is added, the reaction is stirred in an ice-water bath, and suction is filtered. The filtrate is a solution of the required ammonium hydroxide salt, which is then mixed with 2-chloro-6-(4,6-dimethoxypyrimidine-2-thio)benzoic acid, an acid-base neutralization reaction is carried out, and the mixture is dried to obtain a pyrimidinesulfuron ionic liquid.

[0018] Furthermore, in step (A1), the tertiary amine compound is one of 1-methyl-1H-imidazole, 4-methylmorpholine, 2-[ethyl(propyl)amino]hexan-1-ol or 1-methylpiperidin-4-ol.

[0019] Furthermore, in step (A1), the molar ratio of the tertiary amine compound to 1-bromohexadecane is 1.3 to 2:1.

[0020] Furthermore, in step (A1), the solvent is one or more of water, methanol, acetonitrile and acetone.

[0021] Furthermore, in step (A1), the temperature of the heating reflux reaction is 65 to 95° C., and the time of the heating reflux reaction is 48 to 72 hours.

[0022] Further, in step (A2), the activated anion exchange resin is Anion exchange resin.

[0023] Furthermore, in step (A2), the concentration of the bromammonium salt after being dissolved in water is 0.6-1 mol / L, the concentration of the bromammonium salt after being dissolved in ethanol is 0.26-0.32 mol / L, and the dosage ratio of the bromammonium salt alcohol solution to silver oxide is 2:1-2.

[0024] Furthermore, in step (A2), the stirring reaction time in the ice-water bath is 1-2 h.

[0025] Furthermore, in step (A2), the molar ratio of ammonium hydroxide salt to 2-chloro-6-(4,6-dimethoxypyrimidine-2-thio)benzoic acid is 1:1 to 1.1.

[0026] Furthermore, in step (A2), the temperature of the acid-base neutralization reaction is 20-50° C., and the time of the acid-base neutralization reaction is 10-25 hours.

[0027] Further, in step (A2), the ammonium hydroxide salt is any one of 3-hexadecyl-1-methylimidazole ammonium hydroxide salt, 4-hexadecyl-4-methylmorpholine ammonium hydroxide salt, N,N-diethyl-N-(2-hydroxyethyl)hexadecyl ammonium hydroxide salt or 1-hexadecyl-4-hydroxy-1-methylpiperidinium ammonium hydroxide salt.

[0028] A pyrithiobac-butyl ionic liquid microcapsule suspension prepared by using the pyrithiobac-butyl ionic liquid of the invention.

[0029] A method for preparing pyrithiobac-butyl ionic liquid microcapsule suspension using the pyrithiobac-butyl ionic liquid of the present invention comprises the following steps:

[0030] (B1) adding an emulsifier, a defoamer and a dispersant to water in sequence, stirring and heating the mixture for later use to obtain an aqueous phase;

[0031] (B2) heating and melting the oil phase capsule wall material and the pyrifos-butyl ionic liquid of the present invention in a solvent, stirring to obtain an oil phase molten mixture, and keeping the mixture warm for later use;

[0032] (B3) adding the molten oil phase mixture to the water phase under vigorous stirring, emulsifying and stirring to obtain an O / W type emulsion;

[0033] (B4) using microfluidics technology to drop the capsule wall material into the emulsion, solidify it, add a thickener and an antifreeze agent, and stir evenly to obtain a pyrifos-butyl ionic liquid microcapsule suspension.

[0034] Furthermore, in step (B1), the emulsifier is Atlox TM One of CS100A, Triton X-100, calcium dodecylbenzene sulfonate, fatty alcohol polyoxyethylene ether or Tween-80.

[0035] Furthermore, in step (B1), the defoaming agent is one or both of an organosilicon defoaming agent and a polyether defoaming agent.

[0036] Furthermore, in step (B1), the dispersant is sp-3936, Atlox TM One of CS100B or polyvinyl alcohol.

[0037] Furthermore, in step (B1), the mass ratio of the emulsifier, the defoamer, the dispersant and the water is 3-4: 0.8-1.5: 3-4: 32-33.

[0038] Furthermore, in step (B1), the stirring and heating temperature is 70 to 85°C.

[0039] Furthermore, in step (B2), the solvent is one or more of S-200#, S-150#, and S-100# solvent oil.

[0040] Furthermore, in step (B2), the oil phase capsule wall material is one of toluene-2,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate or hexamethylene diisocyanate.

[0041] Furthermore, in step (B2), the mass ratio of the oil phase capsule wall material, the thiosulfuron ionic liquid and the solvent is 1-2:39-40:14-15.

[0042] Furthermore, in step (B2), the heating and melting temperature is 70-85°C, and the heating and melting time is 25-45 minutes. Furthermore, in step (B3), the capsule wall material is one of 1,6-hexanediamine aqueous solution, ethyl cellulose, sodium polystyrene sulfonate, diethylenetriamine, triethylenetetramine, and toluene 2,4-diisocyanate.

[0043] Furthermore, in step (B3), the mass ratios of the capsule wall material, the emulsion, the thickener and the antifreeze agent are 0.5-1, 3-4, 0.1-0.3, and 1-2.

[0044] Furthermore, in step (B3), the curing temperature is 55-65° C., and the curing time is 1.5 to 2.5 hours.

[0045] Application of the pyrithiobac-butyl herbicide ionic liquid of the present invention or the pyrithiobac-butyl herbicide ionic liquid microcapsule suspension of the present invention in weeding.

[0046] Compared with the commercially available pyrithiobac-butyl herbicide, the pyrithiobac-butyl herbicide ionic liquid microcapsule suspension of the present invention exhibits superior thermal stability, water solubility, and surface activity due to the combination of functionally modifiable cations, and also improves the herbicidal activity. At the same time, under the premise of ensuring the same herbicidal effect, the microcapsule can control the slow release of the active ingredient, effectively reduce the dosage of pesticides, protect the environment, and is of great significance to the sustainable development of agricultural production.

[0047] Beneficial effects: Compared with the existing hydrogen sulfide absorption method, the present invention has the following significant advantages:

[0048] (1) The present invention uses pyrithiobacillus as an anion and a structure-modified tertiary amine cation to form a herbicide ionic liquid, and the ionic liquid exhibits excellent thermal stability;

[0049] (2) After the structure of the pyrithiobacill herbicide is transformed into an ionic liquid microcapsule suspension, the present invention shows superior thermal stability, water solubility, and surface activity compared to conventional commercially available pyrithiobacill preparations due to the combination of functionally modifiable cations, and also improves the herbicidal activity. At the same time, under the premise of ensuring the same herbicidal effect, the microcapsule can control the slow release of the active ingredient, effectively reduce the dosage of pesticides, protect the environment, and is of great significance for the sustainable development of agricultural production.

[0050] (3) The present invention transforms the structure of pyrithiobacillus into a herbicide ionic liquid. This ionic liquid exhibits high surface activity and can be used as an active ingredient and emulsifier in the preparation of microcapsule suspensions, thereby optimizing the formulation.

[0051] (4) The present invention uses this type of ionic liquid as an active ingredient and emulsifier to successfully prepare a pesticide microcapsule suspension, thereby controlling the ineffective loss and volatilization of the pesticide, allowing the pesticide to slowly release an effective dose, greatly enhancing the effective period, and improving the utilization rate of the pesticide; at the same time, it can reduce the use of organic solvents, reduce environmental pollution and pesticide damage to crops. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 For Example 5 [C 16 IM][PTB] Statistical graph of growth inhibition rate and fresh weight inhibition rate in the activity test of microcapsule suspension;

[0053] Figure 2 For Example 5 [C 16 Statistical graph of growth inhibition rate and fresh weight inhibition rate in the herbicidal activity test of Mor][PTB] microcapsule suspension;

[0054] Figure 3 For Example 5 [C 16 Statistical graph of growth inhibition rate and fresh weight inhibition rate in the herbicidal activity test of DEAEt][PTB] microcapsule suspension concentrate;

[0055] Figure 4 For Example 5 [C 16 Statistical graph of growth inhibition rate and fresh weight inhibition rate in the herbicidal activity test of NMPipP][PTB] microcapsule suspension concentrate. DETAILED DESCRIPTION

[0056] The technical solution of the present invention is further described below in conjunction with the accompanying drawings.

[0057] Example 1

[0058] The following examples are intended to further illustrate the present invention, but should not be construed as limiting the present invention. Any modification and replacement of the methods, steps or conditions described in the present invention, without departing from the essence of the present invention, are within the scope of the present invention.

[0059] Example 1

[0060] 3-Hexadecyl-1-methylimidazole-3-ammonium hydroxide-[2-chloro-6-(4,6-dimethoxypyrimidine-2-thio)benzoic acid] salt ([C 16 The preparation route of IM][PTB]) is as follows:

[0061]

[0062] (1) Preparation of brominated ammonium salt: 0.036 mol of imidazole, 0.03 mol of 1-bromohexadecane and 60 mL of acetonitrile were added to a 250 mL round-bottom flask equipped with a reflux condenser and a magnetic rod, heated and stirred under reflux, the temperature was controlled at 80° C., reacted for 60 hours, the solvent was removed by rotary evaporation, and vacuum dried at 60° C. for 48 hours to obtain 10.68 g of imidazole-N-hexadecyl ammonium bromide ([C 16 IM][Br]), yield 95.3%.

[0063] (2) Preparation of ammonium hydroxide salt: weigh 0.024 mol [C 16 IM][Br] is dissolved in 30 mL of distilled water and passed through an anion exchange resin. When the pH test paper turns alkaline, the exchange solution is collected and the collection is stopped when the pH test paper turns neutral. The collected solution is titrated with 0.015 mol / L standard hydrochloric acid solution to determine its concentration. At this time, the collected solution is imidazole-N-hexadecyl ammonium hydroxide ([C 16 IM][OH]) aqueous solution.

[0064] (3) Preparation of pyrifos-butyl herbicidal ionic liquids: 0.014 mol of 2-chloro-6-(4,6-dimethoxypyrimidine-2-thio)benzoic acid was weighed and added to the collected imidazole-N-hexadecyl ammonium hydroxide ([C 16 IM][OH]) aqueous solution in a round-bottom flask, add a magnetic bar, stir at room temperature for 24 hours, remove the solvent by rotary evaporation, and vacuum dry at 60°C for 48 hours to obtain 3-hexadecyl-1-methylimidazole-3-ammonium hydroxide-[2-chloro-6-(4,6-dimethoxypyrimidine-2-sulfenyl)benzoic acid] salt ([C 16 IM][PTB]), a total of 7.74 g of product was obtained, with a yield of 89.32%.

[0065] The obtained product 3-hexadecyl-1-methylimidazole-3-ammonium hydroxide-[2-chloro-6-(4,6-dimethoxypyrimidine-2-sulfenyl)benzoic acid] salt was analyzed by nuclear magnetic hydrogen spectrum, and the results were as follows:

[0066] 1 H NMR(300MHz,Chloroform-d)δ10.49(s,1H),7.54(dd,J=7.8,1.1Hz,1H),7.32(dd,J=8.1,1.1Hz,1H),7.21(d,J=25.9Hz,2H),7.13(d,J =7.9Hz,1H),5.68(s,1H),4.26(s,2H),4.03(s,3H),3.72(s,6H),3.02(s,3H),1.83(s,2H),1.25(d,J=8.2Hz,26H),0.94–0.83(m,3H).

[0067] From the above analysis, it can be seen that the structure of 3-hexadecyl-1-methylimidazole-3-ammonium hydroxide-[2-chloro-6-(4,6-dimethoxypyrimidine-2-sulfenyl)benzoic acid] salt is as follows:

[0068]

[0069] (4) Preparation of ionic liquid microcapsule suspension:

[0070] [C 16 IM][PTB] 40.0g, water 40g, S-200# solvent oil 15.0g, Atlox TM CS100A3.5g, SP-39363.5g, toluene 2,4-diisocyanate 2.0g, hexamethylenediamine 1.0g, silicone defoamer 0.8g, magnesium aluminum silicate 0.1g, xanthan gum 0.1g, propylene glycol 1g.

[0071] Add 3.5g Atlox TM CS100A, 0.8g silicone defoamer and 3.5g sp-3936 were dissolved in water, stirred and heated to 80°C to obtain a water phase;

[0072] According to the prescription, 2.0g toluene-2,4-diisocyanate, 40.0g [C 16 IM][PTB] is placed in a flask, 15.0 g of S-200# solvent oil is added and heated to 80°C, stirred evenly and kept warm for later use to obtain an oil phase molten mixture;

[0073] Under vigorous stirring, the above-mentioned molten oil phase mixture was added to the water phase, emulsified and stirred to obtain an O / W emulsion. The O / W emulsion was transferred to another beaker, and 1.0 g of hexamethylenediamine was added dropwise using a microfluidic injection pump, and stirred while adding. After the addition was completed, the temperature was slowly raised to 60°C and solidified for 2 hours. After solidification, 0.1 g of magnesium aluminum silicate, 0.1 g of xanthan gum and 1 g of propylene glycol were added and stirred evenly to obtain [C 16 IM][PTB] ionic liquid microcapsule suspension;

[0074] Example 2

[0075] The preparation process is the same as in Example 1

[0076] 4-Hexadecyl-4-methylmorpholine-4-ammonium hydroxide-[2-chloro-6-(4,6-dimethoxypyrimidine-2-thio)benzoic acid] salt ([C 16 The preparation route of Mor [PTB]) is as follows:

[0077]

[0078] (1) Preparation of brominated ammonium salt: 0.060 mol of morpholine, 0.05 mol of 1-bromohexadecane and 60 mL of acetonitrile were added to a 250 mL round-bottom flask equipped with a reflux condenser and a magnetic rod, heated and stirred under reflux, the temperature was controlled at 80° C., reacted for 60 hours, the solvent was removed by rotary evaporation, and vacuum dried at 60° C. for 48 hours to obtain 19.47 g of the product morpholine-N-hexadecyl ammonium bromide ([C 16 Mor][Br]), yield 95.82%.

[0079] (2) Preparation of ammonium hydroxide salt: weigh 0.03 mol [C 16 Mor][Br] was dissolved in 30 mL of ethanol and placed in ice water. The bottle was wrapped with tin foil. After the temperature dropped, 3.5 g of silver oxide was added and stirred in an ice water bath for three hours. After the solid turned white (gray), it was filtered and the collected solution was titrated with 0.02 mol / L standard hydrochloric acid solution to determine the concentration. At this time, the collected solution was morpholine-N-hexadecyl ammonium hydroxide ([C 16 Mor][OH]) aqueous solution.

[0080] (3) Preparation of pyrifos-butyl herbicidal ionic liquids: 0.026 mol of 2-chloro-6-(4,6-dimethoxypyrimidine-2-thio)benzoic acid was weighed and added to the collected morpholine-N-hexadecyl ammonium hydroxide ([C 16Mor][OH]) aqueous solution in a round-bottom flask, add a magnetic bar, stir at room temperature for 24 hours, remove the solvent by rotary evaporation, and vacuum dry at 60°C for 48 hours to obtain 4-hexadecyl-4-methylmorpholine-4-ammonium hydroxide-[2-chloro-6-(4,6-dimethoxypyrimidine-2-sulfenyl)benzoic acid] salt ([C 16 Mor][PTB]) product 16.61g, yield 97.91%.

[0081] The obtained product, 4-hexadecyl-4-methylmorpholine-4-ammonium hydroxide-[2-chloro-6-(4,6-dimethoxypyrimidine-2-sulfenyl)benzoic acid] salt, was analyzed by nuclear magnetic hydrogen spectrum, and the result was:

[0082] 1 H NMR(300MHz,Chloroform-d)δ7.55(d,J=7.8Hz,1H),7.31(d,J=7.9Hz,2H),7.13(t,J=7.9Hz,1H),5.70(s,1H),4.05(s,1H),3.99–3.89(m,2H) ,3.83(d,J=12.0Hz,2H),3.74(s,6H),3.69(d,J=7.0Hz,2H),3.55(s,3H ),2.70(s,3H),1.71(s,2H),1.34–1.21(m,26H),0.89(t,J=6.5Hz,3H).

[0083] From the above analysis, it can be seen that the structure of 4-hexadecyl-4-methylmorpholine-4-ammonium hydroxide-[2-chloro-6-(4,6-dimethoxypyrimidine-2-sulfenyl)benzoic acid] salt is as follows:

[0084]

[0085] (4)[C 16 Preparation of Mor][PTB] ionic liquid microcapsule suspension: [C 16 Mor][PTB]40.0g, water 40g, S-200# solvent oil 15.0g, Atlox TM CS100A3.5g, SP-3936 3.5g, toluene 2,4-diisocyanate 2.0g, hexamethylenediamine 1.0g, silicone defoamer 0.8g, magnesium aluminum silicate 0.1g, xanthan gum 0.1g, propylene glycol 1g.

[0086] Add 3.5g Atlox TM CS100A, 0.8g silicone defoamer and 3.5g sp-3936 were dissolved in water, stirred and heated to 80°C to obtain a water phase;

[0087] According to the prescription, 2.0g toluene-2,4-diisocyanate, 40.0g [C 16 Mor][PTB] is placed in a flask, 15.0 g of S-200# solvent oil is added and heated to 80°C, stirred evenly and kept warm for later use to obtain an oil phase molten mixture;

[0088] Under vigorous stirring, the above-mentioned molten oil phase mixture was added to the water phase, emulsified and stirred to obtain an O / W emulsion. The O / W emulsion was transferred to another beaker, and 1.0 g of hexamethylenediamine was added dropwise using a microfluidic injection pump, and stirred while adding. After the addition was completed, the temperature was slowly raised to 60°C and solidified for 2 hours. After solidification, 0.1 g of magnesium aluminum silicate, 0.1 g of xanthan gum and 1 g of propylene glycol were added and stirred evenly to obtain [C 16 Mor][PTB] ionic liquid microcapsule suspension;

[0089] Embodiment 3:

[0090] The preparation process is the same as in Example 1

[0091] 4-Hexadecyl-4-methylmorpholine-4-ammonium hydroxide-[2-chloro-6-(4,6-dimethoxypyrimidine-2-thio)benzoic acid] salt ([C 16 The preparation route of DEAEt [PTB]) is as follows:

[0092]

[0093] (1) Preparation of brominated ammonium salt: 0.036 mol of diethylaminoethanol, 0.03 mol of 1-bromohexadecane and 60 mL of acetonitrile were added to a 250 mL round-bottom flask equipped with a reflux condenser and a magnet, and the mixture was heated and stirred under reflux. The temperature was controlled at 80° C. and the reaction was carried out for 65 hours. The solvent was removed by rotary evaporation and the mixture was dried under vacuum at 60° C. for 48 hours to obtain 11.93 g of the product diethylaminoethanol-N-hexadecyl ammonium bromide ([C 16 DEAEt][Br]), yield 94.1%.

[0094] (2) Preparation of ammonium hydroxide salt: weigh 0.023 mol [C 16 DEAEt][Br] was dissolved in 30 mL of ethanol and placed in ice water. The bottle was wrapped with tin foil. After the temperature dropped, 2.7 g of silver oxide was added and stirred in an ice water bath for three hours. After the solid turned white (gray), it was filtered and the collected solution was titrated with 0.02 mol / L standard hydrochloric acid solution to determine the concentration. At this time, the collected solution was diethylaminoethanol-N-hexadecyl ammonium oxide ([C 16 DEAEt][OH]) aqueous solution.

[0095] (3) Preparation of pyrifos-butyl herbicidal ionic liquids: 0.012 mol of 2-chloro-6-(4,6-dimethoxypyrimidine-2-thio)benzoic acid was weighed and added to a mixture containing diethylaminoethanol-N-hexadecyl ammonium oxide ([C 16 DEAEt][OH]) aqueous solution was added to a round-bottom flask, and a magnetic bar was added. The mixture was stirred at room temperature for 24 hours, and the solvent was removed by rotary evaporation. The mixture was vacuum dried at 60°C for 48 hours to obtain 4-hexadecyl-4-methylmorpholine-4-ammonium hydroxide-[2-chloro-6-(4,6-dimethoxypyrimidine-2-thio)benzoic acid] salt ([C 16 DEAEt][PTB]) product 7.13g, yield 88.91%.

[0096] The obtained product 4-hexadecyl-4-methylmorpholine-4-ammonium hydroxide-[2-chloro-6-(4,6-dimethoxypyrimidine-2-sulfenyl)benzoic acid] salt was analyzed by nuclear magnetic hydrogen spectrum, and the result was:

[0097] 1 H NMR(300MHz,Chloroform-d)δ7.57(d,J=7.8Hz,1H),7.33(d,J=7.9Hz,1H),7.12(td,J=8.9,8.4,5.5Hz,1H),5.69(s,1H),4. 15(s,2H),3.75(s,6H),3.56(dd,J=16.7,9.9Hz,6H),3.36–3.24(m,2H),1.64(s,2H),1.39–1.17(m,32H),0.95–0.84(m,3H).

[0098] From the above analysis, it can be seen that the structure of 4-hexadecyl-4-methylmorpholine-4-ammonium hydroxide-[2-chloro-6-(4,6-dimethoxypyrimidine-2-sulfenyl)benzoic acid] salt is as follows:

[0099]

[0100] (3) Preparation of ionic liquid microcapsule suspension:

[0101] [C 16 DEAEt][PTB] 40.0g, water 40g, S-200# solvent oil 15.0g, Atlox TM CS100A3.5g, SP-3936 3.5g, toluene 2,4-diisocyanate 2.0g, hexamethylenediamine 1.0g, silicone defoamer 0.8g, magnesium aluminum silicate 0.1g, xanthan gum 0.1g, propylene glycol 1g.

[0102] Add 3.5g Atlox TMCS100A, 0.8g silicone defoamer and 3.5g sp-3936 were dissolved in water, stirred and heated to 80°C to obtain a water phase;

[0103] According to the prescription, 2.0g toluene-2,4-diisocyanate, 40.0g [C 16 DEAEt][PTB] is placed in a flask, 15.0 g of S-200# solvent oil is added and heated to 80°C, stirred evenly and kept warm for later use to obtain an oil phase molten mixture;

[0104] Under vigorous stirring, the above-mentioned molten oil phase mixture was added to the water phase, emulsified and stirred to obtain an O / W emulsion. The O / W emulsion was transferred to another beaker, and 1.0 g of hexamethylenediamine was added dropwise using a microfluidic injection pump, and stirred while adding. After the addition was completed, the temperature was slowly raised to 60°C and solidified for 2 hours. After solidification, 0.1 g of magnesium aluminum silicate, 0.1 g of xanthan gum and 1 g of propylene glycol were added and stirred evenly to obtain [C 16 DEAEt][PTB] ionic liquid microcapsule suspension;

[0105] Embodiment 4:

[0106] The preparation process is the same as in Example 1

[0107] 1-Hexadecyl-4-hydroxy-1-methylpiperidinium-1-hydroxide-[2-chloro-6-(4,6-dimethoxypyrimidine-2-thio)benzoic acid] salt ([C 16 The synthetic route of NMPipP][PTB]) is as follows:

[0108]

[0109] (1) Preparation of brominated ammonium salt: 0.060 mol of N-methyl-4-piperidinol, 0.05 mol of 1-bromohexadecane and 60 mL of acetonitrile were added to a 250 mL round-bottom flask equipped with a reflux condenser and a magnetic rod, and the mixture was heated and stirred under reflux. The temperature was controlled at 80° C. and the reaction was carried out for 65 hours. The solvent was removed by rotary evaporation and the mixture was dried under vacuum at 60° C. for 48 hours to obtain 19.20 g of the product N-methylpiperidinol-N-hexadecyl ammonium bromide ([C 16 NMPipP][Br]), yield 91.3%.

[0110] (2) Preparation of ammonium hydroxide salt: weigh 0.023 mol [C 16 DEAEt][Br] was dissolved in 30 mL of ethanol and placed in ice water. The bottle was wrapped with tin foil. After the temperature dropped, 2.7 g of silver oxide was added and stirred in an ice water bath for 3 h. After the solid turned white (gray), it was filtered and the filtrate was N-methylpiperidinol-N-hexadecyl ammonium hydroxide salt ([C 16NMPipP][OH]).

[0111] (3) Preparation of pyrifos-butyl herbicidal ionic liquids: 0.012 mol of 2-chloro-6-(4,6-dimethoxypyrimidine-2-thio)benzoic acid was weighed and added to the collected N-methylpiperidinol-N-hexadecylammonium hydroxide salt ([C 16 NMPipP][OH]) in a round-bottom flask, add a magnetic bar, stir at room temperature for 24 hours, remove the solvent by rotary evaporation, and vacuum dry at 50°C for 48 hours to obtain 1-hexadecyl-4-hydroxy-1-methylpiperidinium-1-ammonium hydroxide-[2-chloro-6-(4,6-dimethoxypyrimidine-2-sulfenyl)benzoic acid] salt ([C 16 NMPipP][PTB]) product 14.22g, yield 92.8%.

[0112] The obtained product 1-hexadecyl-4-hydroxy-1-methylpiperidinium-1-ammonium hydroxide-[2-chloro-6-(4,6-dimethoxypyrimidine-2-thio)benzoic acid] salt was analyzed by nuclear magnetic hydrogen spectrum, and the results were as follows:

[0113] 1 H NMR (300MHz, Chloroform-d) δ7.56 (d, J = 7.8 Hz, 1H), 7.33 (s, 1H), 7.12 (t, J = 7. 9Hz,1H),5.70(s,1H),4.06(d,J=15.5Hz,1H),3.80(s,1H),3.75(s,6H),3.70(t ,J=7.0Hz,2H),3.45(s,2H),3.31(s,2H),3.15(d,J=35.8Hz,3H),2.00(d,J=32. 3Hz, 4H), 1.63 (d, J = 23.0Hz, 2H), 1.25 (d, J = 8.2Hz, 26H), 0.89 (t, J = 6.4Hz, 3H).

[0114] From the above analysis, it can be seen that the structure of 1-hexadecyl-4-hydroxy-1-methylpiperidinium-1-hydroxide ammonium-[2-chloro-6-(4,6-dimethoxypyrimidine-2-sulfenyl)benzoic acid] salt is as follows:

[0115]

[0116] (3) Preparation of ionic liquid microcapsule suspension:

[0117] [C 16 NMPipP][PTB] 40.0g, water 40g, S-200# solvent oil 15.0g, Atlox TMCS100A3.5g, SP-3936 3.5g, toluene 2,4-diisocyanate 2.0g, hexamethylenediamine 1.0g, silicone defoamer 0.8g, magnesium aluminum silicate 0.1g, xanthan gum 0.1g, propylene glycol 1g.

[0118] Add 3.5g Atlox TM CS100A, 0.8g silicone defoamer and 3.5g sp-3936 were dissolved in water, stirred and heated to 80°C to obtain a water phase;

[0119] According to the prescription, 2.0g toluene-2,4-diisocyanate, 40.0g [C 16 NMPipP][PTB] was placed in a flask, 15.0 g of S-200# solvent oil was added and heated to 80°C, stirred evenly and kept warm for later use to obtain an oil phase molten mixture;

[0120] Under vigorous stirring, the above-mentioned molten oil phase mixture was added to the water phase, emulsified and stirred to obtain an O / W emulsion. The O / W emulsion was transferred to another beaker, and 1.0 g of hexamethylenediamine was added dropwise using a microfluidic injection pump, and stirred while adding. After the addition was completed, the temperature was slowly raised to 60°C and solidified for 2 hours. After solidification, 0.1 g of magnesium aluminum silicate, 0.1 g of xanthan gum and 1 g of propylene glycol were added and stirred evenly to obtain [C 16 NMPipP][PTB] ionic liquid microcapsule suspension;

[0121] Example 5

[0122] Performance Test:

[0123] 1. Experiment on herbicidal activity of ionic liquid microcapsule suspension

[0124] The grass plant barnyard grass (Echinochloa crusgalli (L.) Beauv) was used as the herbicidal activity test object. The seeds of barnyard grass were soaked in distilled water for 4 hours for activation. 2 ) to cultivate barnyard grass seeds, put nutrient soil into a seedling box, bury ten barnyard grass seeds in nutrient soil (home gardening nutrient soil, Shi Ke De Sera (China) Co., Ltd.) 2-3 cm, and sprinkle a certain mass (see Table 1-4) of [C prepared in Example 1-Example 4] on the surface of the nutrient soil. 16 IM][PTB] ionic liquid microcapsule suspension, [C 16 Mor][PTB] ionic liquid microcapsule suspension, [C 16 DEAEt][PTB] ionic liquid microcapsule suspension and [C 16NMPipP][PTB] ionic liquid microcapsule suspension, the control group was the same concentration of commercially available pyrifos-butyl herbicide (PTB, sodium 2-chloro-6-(4,6-dimethoxypyrimidin-2-yl)sulfanylbenzoate, San Chemical Technology (Shanghai) Co., Ltd.), and the blank group was added with the same volume of distilled water in the nutrient soil. The plants were cultured at room temperature of 25±2℃ for 20 days, and the average aboveground height and average fresh weight of the plants were calculated. The formula for calculating the plant growth inhibition rate was growth inhibition rate = (average height of blank group plants - average height of test plants) / average height of blank plants; the formula for calculating the fresh weight inhibition rate was fresh weight inhibition rate = (average fresh weight of blank group plants - average fresh weight of test plants) / average fresh weight of blank group plants. Commercially available herbicides and [C 16 The herbicidal activity test results of IM][PTB] ionic liquid microcapsule suspension are shown in Tables 1-4 and Figure 1-4 As shown:

[0125] Table 1[C 16 IM][PTB] Herbicidal Activity Results of Ionic Liquid Microcapsule Suspension

[0126]

[0127] The pyrithiobacillus equivalent in Table 1 represents the mass of the active ingredient in the microcapsule suspension.

[0128] Figure 1 For Example 5 [C 16 Statistical graph of growth inhibition rate and fresh weight inhibition rate in the activity test of IM][PTB] microcapsule suspension, where A is the growth inhibition rate and B is the fresh weight inhibition rate. Figure 1 It can be seen that at the concentration of 15-35g / mu of pyrithione equivalent, [C 16 The growth inhibition rate and fresh weight inhibition rate of the IM][PTB] ionic liquid microcapsule suspension were higher than those of the commercially available pyrithione herbicide, indicating that the pyrithione herbicide [C 16 IM][PTB] ionic liquid microcapsule suspension can effectively remove barnyard grass in the field.

[0129] Table 2[C 16 Herbicidal Activity Results of Mor][PTB] Ionic Liquid Microcapsule Suspension

[0130]

[0131]

[0132] The pyrithiobacillus equivalent in Table 2 represents the mass of the active ingredient in the microcapsule suspension.

[0133] Figure 2 For Example 5 [C 16Statistical chart of growth inhibition rate and fresh weight inhibition rate in the activity test of Mor][PTB] microcapsule suspension, where A is the growth inhibition rate and B is the fresh weight inhibition rate. Figure 2 It can be seen that at a concentration of 15-35g / mu, [C 16 The growth inhibition rate and fresh weight inhibition rate of Mor][PTB] microcapsule suspension are higher than those of the commercially available pyrithione herbicide, indicating that the pyrithione ionic liquid microcapsule suspension herbicide prepared by the present application can effectively remove barnyard grass in the field.

[0134] Table 3[C 16 Results of herbicidal activity of DEAEt][PTB] ionic liquid microcapsule suspension

[0135]

[0136] The pyrithiobacillus equivalent in Table 3 represents the mass of the active ingredient in the microcapsule suspension.

[0137] Figure 3 For Example 5 [C 16 Statistical chart of growth inhibition rate and fresh weight inhibition rate in the activity test of DEAEt][PTB] microcapsule suspension, where A is the growth inhibition rate and B is the fresh weight inhibition rate. Figure 3 It can be seen that at a concentration of 15-35g / mu, [C 16 The growth inhibition rate and fresh weight inhibition rate of DEAEt][PTB] microcapsule suspension are higher than those of the commercially available pyrithione herbicide, indicating that the pyrithione ionic liquid microcapsule suspension herbicide prepared by the present application can effectively remove barnyard grass in the field.

[0138] Table 4[C 16 Herbicidal Activity Results of NMPipP][PTB] Ionic Liquid Microcapsule Suspension

[0139]

[0140] The pyrithiobacillus equivalent in Table 4 represents the mass of the active ingredient in the microcapsule suspension.

[0141] Figure 4 For Example 5 [C 16 Statistical chart of growth inhibition rate and fresh weight inhibition rate in the activity test of NMPipP][PTB] microcapsule suspension, where A is the growth inhibition rate and B is the fresh weight inhibition rate. Figure 4 It can be seen that at a concentration of 15-35g / mu, [C 16 The growth inhibition rate and fresh weight inhibition rate of the NMPipP][PTB] microcapsule suspension are higher than those of the commercially available pyrithione herbicide, indicating that the pyrithione ionic liquid microcapsule suspension herbicide prepared by the present application can effectively remove barnyard grass in the field.

[0142] 2. Solubility test

[0143] Referring to the method in Vogel's Textbook of Practical Organic Chemistry, the solubility of herbicidal ionic liquids in 9 solvents was determined. The 9 solvents were arranged according to Snyder polarity, namely: water 9.0, methanol 6.6, DMSO 6.5, acetonitrile 6.5, acetone 5.4, isopropanol 4.3, ethyl acetate 4.3, chloroform 4.1, and n-hexane 0.0.

[0144] Weigh 0.1 g of the ionic liquid microcapsule suspension prepared in Examples 1 to 4 and 2-chloro-6-(4,6-dimethoxypyrimidine-2-thio)benzoic acid (PTB), respectively, place in a centrifuge tube, add a certain volume of the above solvent, and vortex. Evaluate the solubility of the herbicidal ionic liquid based on the volume of the added solvent and the dissolution condition of the sample. If 0.1 g of the sample is completely dissolved in 1 mL of the solvent, it is "soluble" and represented by "+", if 0.1 g of the sample is completely dissolved in 3 mL of the solvent, it is "partially soluble" and represented by "±", if 0.1 g of the sample cannot be completely dissolved in 3 mL of the solvent, it is "insoluble" and represented by "-". The results are shown in Table 5.

[0145] Table 5 Dissolution of different herbicides in different solvents

[0146]

[0147]

[0148] It can be seen from the test statistical results in Table 5 that, except for n-hexane and ethyl acetate, the ionic liquids prepared in Examples 1 to 4 are soluble in other solvents of different polarities, and their solubility is significantly greater than that of the commercially available pyrifos-butyl herbicide.

[0149] 3. Thermal stability test

[0150] Using a thermogravimetric analyzer, 5-10 mg of the ionic liquid samples prepared in Examples 1 to 4 were weighed, and heated at a temperature increase rate of 10°C / min in the range of 35-400°C to determine the decomposition temperatures of the four ionic liquids. The results are shown in Table 6 below:

[0151] Table 6 Thermal stability results of different ionic liquid microcapsule suspensions

[0152] HIL Initial decomposition temperature (℃) <![CDATA[[C 16 IM][PTB]]]> 236.1 <![CDATA[[C 16 Mor][PTB]]]> 210.1 <![CDATA[[C 16 DEAEt][PTB]]]> 199.8 [C16NMPipP][PTB] 237.3

[0153] From the statistical results in Table 6, it can be seen that the initial decomposition temperatures of the ionic liquids prepared in Examples 1 to 4 are all greater than 185° C., indicating that the ionic liquids have high thermal stability and are not easy to decompose.

[0154] The above shows and describes the basic principles, main features and advantages of the present invention. The above is only a specific embodiment of the present invention, and the technical features of the present invention are not limited thereto. Any other implementation methods derived by any technician in the field without departing from the technical solution of the present invention should be included in the patent scope of the present invention.

Claims

1. A pyrithione ionic liquid, characterized in that: The general structural formula of the pyrithione ionic liquid is shown in (I): Wherein, A is a tertiary amine cation.

2. The pyrithione ionic liquid according to claim 1, characterized in that The tertiary amine cation is selected from any one of 3-hexadecyl-1-methyl-1H-imidazole-3-ium, 4-hexadecyl-4-methylmorpholinium-4-ium, 4-hydroxy-1-methyl-1-hexadecylpiperidin-1-ammonium, and N,N-diethyl-N-(2-hydroxyethyl)hexadecyl quaternary ammonium.

3. The pyrimidinesulfuron ionic liquid according to claim 1, characterized in that The pyrimthiosulfate ionic liquid is selected from any one of 3-hexadecyl-1-methyl-1H-imidazole-[2-chloro-6-(4,6-dimethoxypyrimidine-2-sulfenyl)benzoic acid] salt, 4-hexadecyl-4-methylmorpholine-[2-chloro-6-(4,6-dimethoxypyrimidine-2-sulfenyl)benzoic acid] salt, N,N-diethyl-N-(2-hydroxyethyl)hexadecylammonium-[2-chloro-6-(4,6-dimethoxypyrimidine-2-sulfenyl)benzoic acid] salt or 4-hydroxy-1-methyl-1-hexadecylpiperidinium-[2-chloro-6-(4,6-dimethoxypyrimidine-2-sulfenyl)benzoic acid] salt.

4. The method for preparing the pyrithiobacillus ionic liquid according to any one of claims 1 to 3, characterized in that: The following steps are involved: (A1) Preparation of brominated ammonium salt: a tertiary amine compound, 1-bromohexadecane and a solvent are mixed, heated under reflux for reaction, rotary evaporated, and vacuum dried to obtain brominated ammonium salt; (A2) Preparation of pyrifos-butyl herbicide ionic liquid: dissolving ammonium bromide in water, passing through an anion exchange resin to obtain an aqueous solution of ammonium hydroxide, and then mixing with 2-chloro-6-(4,6-dimethoxypyrimidine-2-thio)benzoic acid, performing an acid-base neutralization reaction, and drying to obtain a pyrifos-butyl ionic liquid; Alternatively, the ammonium bromide salt is dissolved in ethanol, silver oxide is added, the reaction is stirred in an ice-water bath, and suction is filtered. The filtrate is a solution of the required ammonium hydroxide salt, which is then mixed with 2-chloro-6-(4,6-dimethoxypyrimidine-2-thio)benzoic acid, an acid-base neutralization reaction is carried out, and the mixture is dried to obtain a pyrimidinesulfuron ionic liquid.

5. The method for preparing the pyrithiobacillus ionic liquid according to claim 4, characterized in that: In step (A1), the tertiary amine compound is one of 1-methyl-1H-imidazole, 4-methylmorpholine, 2-[ethyl(propyl)amino]hexan-1-ol or 1-methylpiperidin-4-ol, and the molar ratio of the tertiary amine compound to 1-bromohexadecane is 1.3 to 2:1; the solvent is one or more of water, methanol, acetonitrile and acetone; the temperature of the heating reflux reaction is 65 to 95° C., and the heating reflux reaction time is 48 to 72 hours.

6. The method for preparing the pyrithiobacillus ionic liquid according to claim 5, characterized in that: In step (A2), the activated anion exchange resin is IRN-78 anion exchange resin, the concentration of ammonium bromide salt after being dissolved in water is 0.6-1 mol / L, the concentration of ammonium bromide salt after being dissolved in ethanol is 0.26-0.32 mol / L, the dosage ratio of ammonium bromide alcohol solution to silver oxide is 2:1-2, and the stirring reaction time in an ice-water bath is 1-2 hours; the molar ratio of ammonium hydroxide salt to 2-chloro-6-(4,6-dimethoxypyrimidine-2-thio)benzoic acid is 1:1-1.1, the temperature of acid-base neutralization reaction is 20-50°C, and the time of acid-base neutralization reaction is 10-25 hours.

7. A pyrithiobac-butyl ionic liquid microcapsule suspension, characterized in that: The method is prepared using the pyrifos-butyl ionic liquid described in any one of claims 1 to 4.

8. A method for preparing pyrithiobac-butyl ionic liquid microcapsule suspension using the pyrithiobac-butyl ionic liquid according to any one of claims 1 to 4, characterized in that: The following steps are involved: (B1) adding an emulsifier, a defoamer and a dispersant to water in sequence, stirring and heating the mixture for later use to obtain an aqueous phase; (B2) heating and melting the oil phase capsule wall material and the pyrifos-butyl ionic liquid according to any one of claims 1 to 4 in a solvent, stirring to obtain an oil phase molten mixture, and keeping the mixture warm for later use; (B3) adding the molten oil phase mixture to the water phase under vigorous stirring, emulsifying and stirring to obtain an O / W type emulsion; (B4) using microfluidics technology to drop the capsule wall material into the emulsion, solidify it, add a thickener and an antifreeze agent, and stir evenly to obtain a pyrifos-butyl ionic liquid microcapsule suspension.

9. The method for preparing the pyrithione herbicide ionic liquid microcapsule suspension according to claim 8, characterized in that In step (B1), the emulsifier is Atlox TM CS100A, Triton X-100, calcium dodecylbenzene sulfonate, fatty alcohol polyoxyethylene ether, or Tween-80; the defoamer is one or two of silicone defoamer and polyether defoamer; the dispersant is sp-3936, Atlox TM CS100B or polyvinyl alcohol, the mass ratio of emulsifier, defoamer, dispersant and water is 3-4: 0.8-1.5: 3-4: 32-33, the stirring temperature is 70-85°C, in step (B2), the solvent is one or more of S-200#, S-150#, S-100# solvent oil; the oil phase capsule wall material is one of toluene-2,4 diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate or hexamethylene diisocyanate, the oil phase capsule wall material, pyrithione ionic liquid The mass ratio of the aqueous solution to the solvent oil is 1-2:39-40:14-15, the heating and melting temperature is 70-85°C, and the heating and melting time is 25-45 minutes. In step (B4), the capsule wall material is one of 1,6-hexanediamine aqueous solution, ethyl cellulose, sodium polystyrene sulfonate, diethylenetriamine, and triethylenetetramine. The mass ratios of the aqueous capsule wall material, the emulsion, the thickener, and the antifreeze agent are 0.5-1, 3-4, 0.1-0.3, and 1-2. The curing temperature is 55-65°C, and the curing time is 1.5-2.5 hours.

10. Use of the pyrithiobac-butyl herbicide ionic liquid according to any one of claims 1 to 4 or the pyrithiobac-butyl herbicide ionic liquid microcapsule suspension according to claim 7 in weeding.

Images