Micro-capsule suspending agent containing spinetoram and lambda-cyhalothrin

Abstract

The invention discloses a microcapsule suspending agent containing spinetoram and lambda-cyhalothrin and a preparation method thereof.Capsule cores of spinetoram and lambda-cyhalothrin are wrapped by a polymer formed by a titanium-containing precursor to form microcapsules, and the microcapsules are stably dispersed and suspended in water and are milk white homogeneous suspension liquid in appearance; the titanium-containing precursor polymer used in the preparation method can overcome the problem of heat storage transposition of lambda-cyhalothrin when a micro-capsule suspending agent is prepared from spinetoram and lambda-cyhalothrin in the prior art, and the prepared product preparation is high in encapsulation efficiency and good in stability.

Description

Technical Field

[0001] The invention relates to the technical field of pesticides, and in particular to a microcapsule containing spinetoram and high-efficiency cyhalothrin and a preparation method thereof. Background Art

[0002] Ethyl spinosad is a new type of insecticide obtained by chemically modifying two spinosad compounds, spinosyn J and spinosyn L, produced by fermentation in the presence of catalysts, reactants and solvents. Its mechanism of action is different from that of traditional organophosphorus and pyrethroid insecticides, which act on acetylcholinesterase and Na + Channel, it acts on nicotinic acetylcholine receptors, and is also different from nicotinic insecticides such as imidacloprid. Ethyl spinetoram was launched in 2007, with molecular formula: Ethyl spinetoram J: C42H69N010, Ethyl spinetoram L: C43H69N010. It is a new member of the spinosad insecticides and is obtained by chemical modification of the natural product spinosad. Ethyl spinetoram is a new and unique active ingredient, which has the same mechanism of action as spinosad; but compared with spinosad, Ethyl spinetoram has higher activity against certain pests, higher safety in use, and is more environmentally friendly. It decomposes rapidly in soil and natural water bodies without residue; it has strong binding ability with soil and organic matter, weak mobility, and will not pollute groundwater and surface water; it is non-volatile. Ethyl spinetoram can effectively control lepidopteran pests such as vegetable diamondback moth, beet armyworm, rice leaf roller, and vegetable thrips.

[0003] The appearance of highly effective chlorfenapyr is white to cream-colored crystals, which are easily soluble in aromatic hydrocarbons, ketones and alcohols. Toxicity: acute oral LD50 of rats: 649mg / kg, acute percutaneous LD50>5000mg / kg, slight skin and eye irritation to rabbits. It is not sensitizing to guinea pigs. Acute inhalation LC50 of rats>1.97mg / L (hour). This product is highly toxic to bees, fish, silkworms and birds. When using it, care should be taken to avoid polluting water sources, avoiding the flowering period of nectar crops, and avoiding polluting mulberry gardens. This product is a non-systemic insecticide with contact and stomach poisoning effects. It destroys the function of the nervous system by interacting with the sodium channels of pests. It is used in public health and animal husbandry to control a variety of pests such as flies, cockroaches, mosquitoes, fleas, lice, bedbugs, and animal external parasites such as ticks, mites, and Ceratidae.

[0004] Although insecticide compositions containing spinetoram and high-efficiency cyhalothrin have been reported in the prior art, there are few literature reports that spinetoram and high-efficiency cyhalothrin can be made into microcapsule suspensions.

[0005] The applicant's research found that in the process of preparing microcapsule suspensions of spinetoram and cyhalothrin, cyhalothrin translocation often occurs, causing degradation of the active ingredients and making it impossible to guarantee product quality. Summary of the invention

[0006] In order to solve the problem of translocation in the process of preparing microcapsule suspension of ethyl spinetoram and high-efficiency cyhalothrin composition, which causes degradation of effective ingredients and leads to the defect that product quality cannot be guaranteed, the purpose of the present invention is to provide a microcapsule suspension of ethyl spinetoram and high-efficiency cyhalothrin with reliable quality and a preparation method thereof. The preparation method of the microcapsule suspension containing ethyl spinetoram and high-efficiency cyhalothrin provided by the present invention has a high encapsulation rate and good stability of the obtained microcapsule suspension containing ethyl spinetoram and high-efficiency cyhalothrin, and effectively inhibits the translocation problem of high-efficiency cyhalothrin.

[0007] In a first aspect, the present invention provides a microcapsule suspension containing spinetoram and cyhalothrin, comprising microcapsules, adjuvants and water, wherein the microcapsules include capsule walls and capsule cores, wherein: the capsule cores are composed of spinetoram and cyhalothrin technical materials and a solvent; and the capsule walls are high molecular polymers containing titanium precursors.

[0008] Secondly, the present invention also provides a method for preparing the microcapsule suspension containing spinetoram and high-efficiency cyhalothrin, which comprises the following steps:

[0009] (1) mixing spinetoram and cyhalothrin technical, a solvent and a titanium-containing precursor to obtain a first material;

[0010] (2) mixing water, a defoaming agent, and an emulsifier to obtain a second material;

[0011] (3) pouring the first material into the second material and shearing it with a shearing machine to obtain a third material;

[0012] (4) adding potassium hydroxide to the third material to adjust the pH of the system to 9-10, heating, and keeping warm to obtain a fourth material;

[0013] (5) Add a thickener, an antifreeze agent and a dispersant to the fourth material to obtain spinetoram and high-efficiency chlorflucythrinate capsule suspension.

[0014] Finally, the present invention also provides spinetoram and high-efficiency cyhalothrin microcapsule suspension prepared by the above preparation method.

[0015] Beneficial Effects

[0016] 1. The microcapsule suspension containing ethyl spinetoram and high-efficiency chlorfenapyr of the present invention contains a high-molecular titanium-containing precursor polymer, and the ethyl spinetoram and high-efficiency chlorfenapyr microcapsule suspension prepared by using the high-molecular titanium-containing precursor polymer as the capsule wall has high encapsulation efficiency and good stability, and can effectively inhibit the translocation of high-efficiency chlorfenapyr. DETAILED DESCRIPTION

[0017] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Unless otherwise expressly stated, throughout the specification and claims, the term "including" or its variations such as "comprising" or "including" will be understood to include the stated components without excluding other components.

[0018] In the present invention, unless otherwise specified, percentage refers to mass percentage.

[0019] In addition, in order to better illustrate the present invention, numerous specific details are given in the following detailed description.

[0020] Those skilled in the art will appreciate that the present invention can be implemented without certain specific details. In some embodiments, raw materials, methods, means, etc. that are well known to those skilled in the art are not described in detail in order to highlight the main purpose of the present invention.

[0021] In a first aspect, the present invention provides a microcapsule suspension containing spinetoram and cyhalothrin, comprising microcapsules, an auxiliary agent and water, wherein the microcapsules comprise a capsule wall and a capsule core, wherein: the capsule core is composed of spinetoram and cyhalothrin technical materials and a solvent; and the capsule wall is a high molecular polymer containing a titanium precursor.

[0022] Preferably, the microcapsule suspension containing spinetoram and cyhalothrin of the present invention is composed of the following ingredients:

[0023]

[0024] Preferably, the titanium-containing precursor is one or more of tetrabutyl titanate, isopropyl titanate and isopropyl triisophthaloyl titanate;

[0025] Preferably, the solvent is selected from one or more of xylene, methanol, cyclohexanone, methyl oleate, sec-butyl acetate, mineral oil, soybean oil, etc.;

[0026] Preferably, the emulsifier is one or more of Nongru 505, 602, BY110, NP-7, Tween20 and the like.

[0027] Preferably, the thickener is one or more of xanthan gum, magnesium aluminum silicate, kaolin, etc. Preferably, the antifreeze agent is one or more of ethylene glycol, sodium chloride, glycerol, etc.

[0028] Preferably, the mass ratio of the total mass of spinetoram and cyhalothrin technical to the mass ratio of the titanium-containing precursor is 1:0.2-1. Studies have shown that within the above preferred range, the obtained product has better properties and better stability.

[0029] The second aspect of the present invention provides a method for preparing a microcapsule suspension containing the above-mentioned spinetoram and lambda-cyhalothrin, the preparation method comprising the following steps:

[0030] (1) mixing spinetoram and cyhalothrin technical, a solvent and a titanium-containing precursor to obtain a first material;

[0031] (2) mixing water, a defoaming agent, and an emulsifier to obtain a second material;

[0032] (3) pouring the first material into the second material and shearing it with a shearing machine to obtain a third material;

[0033] (4) adding potassium hydroxide to the third material to adjust the pH of the system to 9-10, heating, and keeping warm to obtain a fourth material;

[0034] (5) Add a thickener, an antifreeze agent and a dispersant to the fourth material to obtain a microcapsule suspension of spinetoram and high-efficiency chlorflucythrinate.

[0035] The mass of spinetoram and cyhalothrin in step (1) of the above preparation method is 1%-20% of the total mass fraction, optionally 10%-20%; further optionally 10-15%.

[0036] The solvent is selected from one or more of xylene, methanol, cyclohexanone, methyl oleate, ethyl acetate, solvent oil, mineral oil, soybean oil, etc.;

[0037] In step (2) of the above preparation method, the titanium-containing precursor is selected from one or more of tetrabutyl titanate, isopropyl titanate and isopropyl triisophthaloyl titanate;

[0038] In the above preparation method, the emulsifier includes one or more of alkyl sulfate, alkylbenzene sulfonate, phosphate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, sorbitan monostearate polyoxyethylene ether, and castor oil polyoxyethylene ether;

[0039] In step (3) of the above preparation method, the shear rate of the shearing machine is 5000-15000 r / min, and the shear time is 1-10 min; optionally, the shear rate is 5000-15000 r / min, and the shear time is 2-5 min; further optionally, the shear rate is 8000 r / min, and the shear time is 5 min.

[0040] In step (4) of the above preparation method, potassium hydroxide is added dropwise to the third material under stirring at a rate of 100-500 r / min; further optionally, the stirring rate is 300 r / min.

[0041] In step (5) of the above preparation method, the heating temperature is 30-60°C and the insulation time is 1-5h; alternatively, the heating temperature is 30-50°C and the insulation time is 3-5h; further alternatively, the heating temperature is 40°C and the insulation time is 4h, and the pH is adjusted to 9-10. Studies have found that the pH value affects the quality of the product, and within the preferred range, the product performance is better.

[0042] In the above preparation method, the defoaming agent includes one or more of a polyether defoaming agent and a polyether-modified silicone defoaming agent.

[0043] In the above preparation method, the dispersant includes one or more of silicate dispersants, polyether dispersants, lignin sulfonates, polycarboxylates, block copolymers, and phosphate dispersants.

[0044] In the above preparation method, the thickener includes one or more of magnesium aluminum silicate, xanthan gum and white carbon black.

[0045] In the above preparation method, the antifreeze agent includes one or more of ethylene glycol, propylene glycol, and glycerol.

[0046] The present invention is further described in detail below in conjunction with the embodiments, but the protection scope of the present invention is not limited thereto.

[0047] In the following examples, all raw materials are commercially available.

[0048] Among them, the CAS number of spinetoram is 187166-40-18;

[0049] The CAS number of cyhalothrin is 52315-07-8;

[0050] The CAS number of tetrabutyl titanate is 5593-70-4;

[0051] The CAS number of isopropyl titanate is 546-68-9;

[0052] The CAS number of isopropyl triisophthaloyl titanate is 61417-55-8

[0053] The organic silicon defoamer used was SAG-630 defoamer from Momentive Advanced Materials, USA;

[0054] Block polyether, purchased from Croda, UK, model 5002L;

[0055] Polycarboxylates were purchased from Croda, UK, model number Atlox 4913;

[0056] Fatty alcohol polyoxyethylene ether was purchased from Nanjing Taihua Chemical Co., Ltd., model AEO-5;

[0057] Alkylphenol polyoxyethylene ether was purchased from Nantong Deyi Chemical Co., Ltd., model NP-7;

[0058] Castor oil polyoxyethylene ether was purchased from Nanjing Taihua Chemical Co., Ltd., model BY110.

[0059] Example 115% Spinetoram and High-efficiency Cyhalothrin Microcapsule Suspension

[0060] (1) 5 g of ethyl spinetoram, 10 g of high-efficiency chlorflucythrinate technical, 25 g of xylene and 7.5 g of tetrabutyl titanate were mixed to obtain a first material;

[0061] (2) 38 g of water, 0.2 g of defoamer, and 4 g of block polyether were mixed to obtain a second material;

[0062] (3) turning on the high-speed shearing machine, adding the first material obtained in step (1) to the second material obtained in step (2) at a speed of 10000 r / min, and shearing for 5 minutes to obtain a third material;

[0063] (4) The third material was stirred at a speed of 300 r / min, potassium hydroxide was added to adjust the pH to 9-10, and the mixture was kept at 40-45° C. for 4 h to obtain the fourth material.

[0064] (5) Add 0.1 g of xanthan gum, 5 g of ethylene glycol, 2 g of polycarboxylate and the balance of water to the fourth material to obtain spinetoram and cyhalothrin microcapsule suspension.

[0065] Example 2 15% Spinetoram and High-efficiency Cyhalothrin Microcapsule Suspension

[0066] The preparation method is the same as that of Example 1, except that the titanium-containing precursor used isopropyl titanate.

[0067] Example 3 15% Spinetoram and High-efficiency Cyhalothrin Microcapsule Suspension

[0068] The preparation method is the same as that of Example 1, except that the titanium-containing precursor used is isopropyl triisophthaloyl titanate.

[0069] Example 4 15% Spinetoram and High-efficiency Cyhalothrin Microcapsule Suspension

[0070] The preparation method is the same as that of Example 1, except that 3 g of tetrabutyl titanate is used.

[0071] Example 5 15% Spinetoram and High-efficiency Cyhalothrin Microcapsule Suspension

[0072] The preparation method is the same as that of Example 1, except that 15 g of tetrabutyl titanate is used.

[0073] Example 6 10% spinetoram and highly effective cyhalothrin microcapsule suspension

[0074] The preparation method is the same as that in Example 1, except that the amount of high-efficiency chlorfenapyr technical drug used is 5 g and the amount of tetrabutyl titanate used is 5 g.

[0075] Comparative Example 1 15% spinetoram and high-efficiency cyhalothrin microcapsule suspension After screening various parameters, spinetoram and high-efficiency cyhalothrin microcapsule suspension were prepared by interfacial polymerization, and the method included the following steps:

[0076] (1) 5 g of ethyl spinetoram, 10 g of cyhalothrin technical, 25 g of ethyl acetate, and 2 g of toluene diisocyanate were mixed evenly until dissolved, and 4 g of block polyether was obtained to obtain a first material;

[0077] (2) 44 g of water and 0.5 g of organosilicon defoamer were added to obtain a second material;

[0078] (3) turning on the high-speed shearing machine, adding the first material obtained in step (1) to the second material obtained in step (2) at a speed of 8000 r / min, and shearing for 3 minutes to obtain a third material;

[0079] (4) Start stirring the third material at a stirring speed of 300 r / min, add 0.3 g of diethyltoluenediamine dropwise and stir for 5 min;

[0080] (5) Add 0.1 g of xanthan gum, 4 g of block polyether, and 5 g of propylene glycol to the fifth material in step (4) to obtain a microcapsule suspension of ethyl spinetoram and highly effective chlorfenapyr.

[0081] Comparative Example 2 15% spinetoram and high-efficiency cyhalothrin microcapsule suspension After screening various parameters, spinetoram and high-efficiency cyhalothrin microcapsule suspension were prepared by in-situ polymerization method, and the method included the following steps:

[0082] (1) 5 g of urea-formaldehyde resin prepolymer and 45 g of water were uniformly mixed to obtain a urea-formaldehyde resin prepolymer aqueous solution;

[0083] (2) 5 g of spinetoram, 10 g of cyhalothrin original drug, and 25 g of methyl oleate were mixed uniformly, and stirred to fully dissolve, to obtain an oil suspension of spinetoram and cyhalothrin;

[0084] (3) uniformly mixing the obtained urea-formaldehyde resin prepolymer aqueous solution and the spinetoram and cyhalothrin oil suspension to obtain a first material;

[0085] (4) adding hydrochloric acid to the first material at a uniform rate within 0.5 h, mixing at a stirring speed of 300 r / min, and adjusting the pH value to 4.3 to obtain a second material;

[0086] (6) The third material is cured and polycondensed at 45° C. for 3 h to obtain a cured polycondensation product; 0.1 g of xanthan gum, 4 g of block polyether, 5 g of propylene glycol and the balance of water are added to obtain ethyl spinetoram and highly effective chlorfenapyr microcapsule suspension.

[0087] Comparative Example 3 15% ethyl spinetoram and highly effective chlorfenapyr suspension

[0088] After screening various parameters, spinetoram and high-efficiency cyhalothrin suspensions were prepared:

[0089] 5 g of spinetoram, 10 g of high-efficiency chlorflucythrinate technical, 5 g of block polyether, 0.5 g of xanthan gum, 1 g of kaolin, 5 g of propylene glycol, 0.5 g of silicone defoamer, and 73 g of water were uniformly mixed to obtain a spinetoram and high-efficiency chlorflucythrinate suspension.

[0090] Comparative Example 4 15% ethyl spinetoram and highly effective chlorfenapyr microcapsule suspension

[0091] The preparation method is the same as that of Example 1, except that 15.1 g of tetrabutyl titanate is used.

[0092] Comparative Example 5 15% ethyl spinetoram and highly effective chlorfenapyr microcapsule suspension

[0093] The preparation method is the same as that of Example 1, except that 2.9 g of tetrabutyl titanate is used.

[0094] Comparative Example 6

[0095] The preparation method of 15% spinetoram and high-efficiency cyhalothrin microcapsule suspension is the same as that in Example 1, except that the sodium hydroxide used is used to adjust the pH to 10.1.

[0096] Comparative Example 7

[0097] The preparation method of 15% spinetoram and high-efficiency cyhalothrin microcapsule suspension is the same as that in Example 1, except that the pH value is adjusted to 8.9 by using sodium hydroxide.

[0098] Test Example 1

[0099] 1. Determination of microcapsule encapsulation efficiency and translocation efficiency: Liquid chromatography was used to determine the high-polyploid and low-polyploid and encapsulation efficiency of the preparations of each embodiment and comparative example.

[0100] Encapsulation rate (%) = (amount of original drug added - amount of free original drug) / amount of original drug added * 100%

[0101] X = high ploidy / (high ploidy+low ploidy)*100%

[0102] Translocation rate (%) = X1-X2

[0103] Note: X1 is the normal temperature test result, X2 is the hot storage test result, and the transfer rate > 5% is unqualified.

[0104] 2. Thermal storage stability determination: The preparations of each embodiment and comparative example were placed in a container, sealed, and placed in a constant temperature oven at (54±2)°C. After standing for 14 days, the containers were taken out and the appearance was observed.

[0105] 3. Freeze-thaw stability determination: The preparations of the examples and comparative examples were placed in containers; sealed and placed at -18°C for 18 hours, and then at room temperature for 8 hours; the cycle was repeated 4 times; and the appearance was observed after the cycle was completed.

[0106] The encapsulation efficiency, translocation rate and storage stability test results of the examples of the present invention and the comparative examples are shown in Table 1.

[0107] Table 1 Encapsulation efficiency, translocation rate and storage stability test data

[0108]

[0109]

[0110] From the above experimental results, it can be seen that Examples 1-6 have good stability to spinetoram and high-efficiency chlorfenapyr, high encapsulation efficiency, and low translocation rate of high-efficiency chlorfenapyr, which meet the national standard requirements. However, although Comparative Examples 1-2 have good heat storage stability and freeze-thaw stability and high encapsulation efficiency, the translocation of high-efficiency chlorfenapyr is more obvious. Comparative Examples 3-7 have not only low encapsulation efficiency but also large translocation rate, which do not meet the conventional requirements. That is, the products made within the scope of this embodiment are qualified.

[0111] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technologies or solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A microcapsule suspension containing spinetoram and high-efficiency cyhalothrin, comprising microcapsules, adjuvants and water, wherein the microcapsules comprise capsule walls and capsule cores, characterized in that: The capsule core is composed of spinetoram and high-efficiency cyhalothrin original drugs and a solvent; the capsule wall is a high-molecular polymer containing a titanium precursor.

2. The microcapsule suspension according to claim 1, characterized in that The following ingredients composition:

3. A method for preparing a microcapsule suspension according to claim 1 or 2, characterized in that: The steps include: (1) mixing spinetoram and cyhalothrin technical, a solvent and a titanium-containing precursor to obtain a first material; (2) mixing water, a defoaming agent, and an emulsifier to obtain a second material; (3) pouring the first material into the second material and shearing it with a shearing machine to obtain a third material; (4) adding potassium hydroxide to the third material to adjust the pH value of the system to 9-10, heating, and keeping warm to obtain a fourth material; (5) Add a thickener, an antifreeze agent and a dispersant to the fourth material to obtain a microcapsule suspension of spinetoram and high-efficiency chlorflucythrinate.

4. The preparation method according to claim 3, characterized in that: The titanium-containing precursor is selected from one or more of tetrabutyl titanate, isopropyl titanate and isopropyl triisophthaloyl titanate, and the mass ratio of the total mass of the ethyl spinetoram and highly effective chlorflucythrinate technical to the titanium-containing precursor is 1:0.2-1.

5. The preparation method according to claim 3, characterized in that: The solvent is selected from one or more of xylene, NN dimethylformamide, cyclohexanone, isophorone, ethyl acetate, sec-butyl acetate, mineral oil, soybean oil and the like.

6. The preparation method according to claim 3, characterized in that: The defoamer is selected from one or more of polyether defoamers and polyether-modified silicone defoamers; and / or the dispersant is selected from one or more of polyether dispersants, lignin sulfonates, polycarboxylates, block copolymers, and phosphate dispersants; and / or the thickener is selected from one or more of magnesium aluminum silicate, xanthan gum, and white carbon black; and / or the antifreeze is selected from one or more of ethylene glycol, sodium chloride, and glycerol; and / or the emulsifier is selected from one or more of alkyl sulfates, alkylbenzene sulfonates, phosphates, fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, and castor oil polyoxyethylene ethers.

7. The preparation method according to claim 3, characterized in that: In step (3), the shear rate is 5000-10000 r / min, and the shear time is 1-5 min; and / or, in step (4), potassium hydroxide is added dropwise to the third material under stirring at a stirring rate of 100-500 r / min.

8. A microcapsule suspension containing spinetoram and lambda-cyhalothrin prepared according to the preparation method according to any one of claims 3 to 7.

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