CN110024803B - Spirotetramat-containing insecticidal composition and preparation thereof - Google Patents

Abstract

The invention relates to a spirotetramat-containing insecticidal composition and a preparation thereof, wherein the active ingredients of the spirotetramat-containing insecticidal composition are spirotetramat and veratrine, and the proportion of the spirotetramat to the veratrine is 1 (0.2-0.5). According to the invention, the spirotetramat and the veratrine are subjected to binary compounding, so that the composition has an obvious synergistic effect, is good in quick-acting property and persistence, reduces the production cost and the use cost, and is particularly suitable for preventing and treating thrips.

Description

Spirotetramat-containing insecticidal composition and preparation thereof

Technical Field

The invention relates to the technical field of pesticide compounding, in particular to an insecticidal composition containing spirotetramat and a preparation thereof.

Background

Spirotetramat is a novel quaternary acid derivative pesticide, causes larva death by interfering fat synthesis of insects, and can reduce reproductive capacity of adults. The spirotetramat can be absorbed and conducted in the xylem and phloem in two directions, can move upwards and downwards in the whole plant body and reach leaf surfaces and barks, so that pests hidden as pests can be effectively prevented and treated. The spirotetramat is suitable for various crops, and has good control effect on various piercing-sucking and filing-sucking pests.

Veratrine is a botanical pesticide, and has contact poisoning and stomach poisoning effects on insects. The agent can cause local stimulation after entering digestive system via insect epidermis or sucking, and cause reflex insect excitation, and inhibit insect sensory nerve ending first and central nerve later to cause insect death.

The application of chemical agents is the most effective means for controlling plant pests, but the problems of agent residue, environmental pollution, pest resistance and the like are easily caused by continuously applying a single chemical bactericide with high dosage for a long time. The development of novel insecticides is often difficult, high in cost and long in cycle, so that the achievement of synergistic effect through reasonable compounding on the basis of the existing products is one of the fastest and efficient methods at present. The development of a novel compound insecticide with good insecticidal action, quick action and lasting effect is the goal of technicians, but certain technical difficulties exist.

Disclosure of Invention

Based on the situation, the invention aims to provide the insecticidal composition containing the spirotetramat and the preparation thereof, and the insecticidal composition is particularly suitable for controlling thrips.

The technical scheme of the invention is realized by the following measures:

the invention provides a spirotetramat-containing insecticidal composition, which comprises spirotetramat and veratrine, wherein the mass ratio of spirotetramat to veratrine is 1 (0.2-0.5). Wherein the synergistic effect is obvious when the mass ratio of the spirotetramat to the veratrine is 1: 0.3.

The insecticidal composition can be prepared into various formulations such as missible oil, suspending agent, wettable powder, aqueous emulsion, microemulsion and the like. The suspending agent containing lemongrass essential oil, bamboo leaf essential oil, 2500 emulsifier, 4894 emulsifier, xanthan gum, magnesium aluminum silicate, glycol, organic silicone, kasong and other auxiliaries has good quick-acting property and lasting property. The suspending agent comprises the following components in percentage by mass: 20-26% of spirotetramat, 4-13% of veratrine, 3-5% of lemon grass essential oil, 1-6% of bamboo leaf essential oil, 2% of 2500 emulsifier, 1-2% of 4894 emulsifier, 0.1-0.3% of xanthan gum, 0.2-0.8% of magnesium aluminum silicate, 4-8% of ethylene glycol, 0.3-0.6% of organic silicone, 0.2-0.6% of kasong and the balance of water.

The invention also specifically provides a preparation method of the bamboo leaf essential oil, which comprises the following steps:

1) pulverizing bamboo leaves to 20 meshes to obtain bamboo leaf powder; adding 50mL of ethanol with the mass concentration of 70% into each gram of bamboo leaf powder, and stirring for 1 hour at 65 ℃; cooling, filtering, collecting filtrate, and removing ethanol to obtain extract;

2) adding 200mL of mixed solution of ethyl acetate and water with the mass ratio of 1:3 into each gram of extract, stirring for 60 minutes, standing for layering, collecting an organic layer, and concentrating.

The lemongrass essential oil can be purchased in the market and also can be prepared by adopting the following method:

crushing the lemon grass to 20-30 meshes, and adding 20mL of 2.5-5 wt% sodium chloride solution per gram; distilling for 100-130 minutes by water vapor, and controlling the steam pressure to be 0.1-0.30 Mpa; condensing to obtain the fraction of the oil-water mixture; allowing the fraction of the oil-water mixture to pass through an oil-water separator, standing, layering oil and water, and collecting the oil-water mixture through the oil-water separator to obtain essential oil;

the composition of the invention has obvious effect of killing thrips.

The specific implementation scheme of the pesticide formulation prepared by the insecticidal composition is as follows:

the insecticidal composition is an emulsifiable concentrate preparation, and the mass percent of each component is as follows: 20-26% of spirotetramat, 4-13% of veratrine, 8-13% of emulsifier, 1-5% of synergist and solvent. The specific production steps of the missible oil preparation are that the spirotetramat and the veratrine which are effective components are added into a solvent to be completely dissolved, then an emulsifier and a synergist are added to be uniformly stirred to form uniform and transparent oily liquid, and the uniform and transparent oily liquid is filled to prepare the missible oil preparation of the composition.

The insecticidal composition is a suspending agent and comprises the following components in percentage by mass: 20-26% of spirotetramat, 4-13% of veratrine, 2-4% of emulsifier, 1-8% of antifreezing agent, 0.1-5% of thickener, 0.1-1% of defoaming agent, 0.1-0.8% of preservative, 4-11% of essential oil and the balance of solvent. The specific production steps of the suspending agent are that other auxiliary agents are mixed firstly, the mixture is sheared and mixed evenly at a high speed, the active ingredients of the spirotetramat and the veratrine are added, and the mixture is sanded in a sand mill for 2 to 3 hours, so that the particle diameter is below 5mm, and the suspending agent preparation of the composition can be prepared.

The insecticidal composition is wettable powder and comprises the following components in percentage by mass: 20-26% of spirotetramat, 4-13% of veratrine, 3-10% of a dispersing agent, 1-5% of a wetting agent and a filler. The wettable powder has the specific production steps as follows: the components are mixed according to the formula, evenly stirred in a stirring kettle, evenly mixed through a jet mill, and then the wettable powder of the composition can be prepared.

The insecticidal composition is an aqueous emulsion, and comprises the following components in percentage by mass: 20-26% of spirotetramat, 4-13% of veratrine, 3-25% of emulsifier, 5-15% of solvent, 2-10% of stabilizer, 1-5% of anti-freezing agent, 0.1-8% of defoaming agent, 0.2-2% of thickening agent and water. The specific production steps of the aqueous emulsion are as follows: firstly, adding spirotetramat, veratrine, a solvent and an emulsifier together to dissolve the spirotetramat, the veratrine, the solvent and the emulsifier into a uniform oil phase; mixing part of water, an antifreezing agent and other pesticide auxiliaries together to form a uniform water phase; adding the oil phase into the water phase while stirring at a high speed in a reaction kettle, slowly adding water until a phase inversion point is reached, starting a shearing machine to carry out high-speed shearing, adding the rest water, and shearing for about half an hour to form an oil-in-water emulsion, thus preparing the composition in the form of the emulsion in water.

The insecticidal composition is microemulsion, and comprises the following components in percentage by mass: 20-26% of spirotetramat, 4-13% of veratrine, 10-35% of emulsifier, 1-3% of synergist, 20-28% of cosolvent, 2-8% of solvent and water. The spirotetramat, the veratrine cosolvent and the solvent are completely dissolved, other components such as an emulsifier, a synergist and the like are added, the mixture is uniformly mixed, and finally, water is added, and the microemulsion can be prepared after full stirring.

The emulsifier is selected from one or a combination of more of calcium dodecyl benzene sulfonate, fatty acid polyoxyethylene ether, alkylphenol polyoxyethylene ether sulfosuccinate, styryl phenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, fatty acid polyoxyethylene ester, polyoxyethylene fatty alcohol ether, 2201 emulsifier, 700 emulsifier, 604 emulsifier, 2500 emulsifier and 4894 emulsifier.

The solvent is one or more of xylene, toluene, methanol, ethanol, n-butanol, isopropanol, rosin-based vegetable oil (with the code number of ND-60), solvent oil, dimethylformamide, dimethyl sulfoxide, water, etc.

The cosolvent is one or more of cyclohexanone, alcohols (methanol, ethanol, etc.), phenols (phenol, mixed cresol, etc.), ethyl acetate, dimethyl sulfoxide, etc.

The dispersing agent is selected from one or more of polycarboxylate (with the code numbers of YUS-WG5, TERSPERSE 2700 and TERSPERSE2500), lignosulfonate (with the code numbers of YUS-WG4, YUS-207K, WLNOK, WLNO100 and TERSPERSE2020), alkylphenol polyoxyethylene ether methyl ether condensate sulfate, calcium alkyl sulfonate, naphthalene sulfonic acid formaldehyde condensate sodium salt, alkylphenol polyoxyethylene, fatty acid polyoxyethylene ester, fatty amine polyoxyethylene ether and glycerin fatty acid ester polyoxyethylene ether.

The humectant is selected from one or more of sodium dodecyl sulfate, calcium dodecyl benzene sulfonate, nekal BX, TERWET1004, YUS-LXC, TERSPERSE 4894, TERSPERSE2288, alkyl benzene sulfonate polyoxyethylene triphenyl phenyl phosphate, fructus Gleditsiae Abnormalis powder, faeces Bombycis, and fructus Sapindi Mukouossi powder.

The thickening agent is selected from one or more of xanthan gum, carboxymethyl cellulose, carboxyethyl cellulose, methyl cellulose, magnesium aluminum silicate and polyvinyl alcohol.

The stabilizer is selected from one or a combination of more of sodium citrate, resorcinol, epoxidized soybean oil and epichlorohydrin.

The antifreezing agent is one of ethylene glycol and glycerol.

The synergist is one or more of SP-4078, organosilicon, hypertonic anesthetic, wax removing agent, and transdermal agent.

The defoaming agent is selected from one or more of silicone oil, silicone compounds, C10-20 saturated fatty acid compounds and C8-10 fatty alcohol.

The filler is selected from one or more of kaolin, diatomite, bentonite, attapulgite, white carbon black, starch and light calcium carbonate.

The invention has the following advantages:

the compound pesticide taking the spirotetramat and the veratrine as the effective components has obvious synergistic effect, good quick-acting property and lasting property, reduces the production cost and the use cost, and is particularly suitable for killing thrips.

The invention also researches the formula of the suspending agent, and the addition of the compound essential oil can increase the quick action and the persistence of the preparation, thereby being suitable for popularization and use.

In the embodiment of the invention, the operation method of the virulence test comprises the following steps:

adopts a leaf tube drug film method. And (4) bundling a plurality of small holes on a tube cover and a tube bottom of a 4mL centrifugal tube, wherein the hole diameter is based on the prevention of thrips escaping. Then diluting the reagent to be tested into 5 concentrations with water, adding about 1mL of liquid medicine into a centrifuge tube, turning upside down, shaking for several times, pouring out the liquid medicine, opening a tube cover, and naturally airing indoors; then cutting fresh and tender cowpea pod into pieces with length of about 2cm by a small knife, soaking in the test solution for 10s, naturally drying, clamping into a centrifuge tube, sucking 20 heads of cowpea thrips (leguminous setose thistle) adults by a pest sucker, and then ejecting into the centrifuge tube; the centrifuge tubes were then placed in a climatic chamber at a temperature of (25 ± 2) ° c, with lighting settings L: D14 h:10h, and examined for mortality after 48h (subjects were palpated with a small writing brush tip, and immobilized subjects were considered dead). Each tube was 1 replicate, 3 replicates per concentration. Clear water was used as a blank control. The toxicity equation and the lethal middle concentration LC50 are calculated by a least square method, and the toxicity index and the mixed toxicity coefficient (namely the CTC value) of the medicament are calculated.

The synergistic effect of the mixed medicament is evaluated according to the co-toxicity coefficient (CTC), namely the CTC is less than or equal to 80 and is antagonistic, the CTC is more than 80 and less than 120 and is additive, and the CTC is more than or equal to 120 and is synergistic.

Observed virulence index (ATI) ═ (LC 50 for standard agent/LC 50 for test agent) × 100;

the theoretical virulence index TTI is the virulence index × of the A medicament and the percentage of the A medicament in the mixture plus the virulence index × of the B medicament in the mixture;

the cotoxicity coefficient (CTC) ═ × 100 [ measured virulence index (ATI)/theoretical virulence index (TTI) of the mixture ].

Detailed Description

In order to make the technical solution, purpose and advantages of the present invention more clearly understood, the present invention is illustrated by the following specific examples, which take the example of killing thrips of thysanoptera insects.

The preparation method of the bamboo leaf essential oil in the embodiments 2-6 of the invention comprises the following steps:

1) pulverizing bamboo leaves to 20 meshes to obtain bamboo leaf powder; adding 50mL of ethanol with the mass concentration of 70% into each gram of bamboo leaf powder, and stirring for 1 hour at 65 ℃; cooling, filtering, collecting filtrate, and removing ethanol to obtain extract;

2) adding 200mL of mixed solution of ethyl acetate and water with the mass ratio of 1:3 into each gram of extract, stirring for 60 minutes, standing for layering, collecting an organic layer, and concentrating.

EXAMPLE 1 thrips virulence test

Toxicity tests were carried out according to the formulation shown in Table 1, and the results are shown in Table 1.

TABLE 1

Composition (I)	Proportioning	LC50(ug/ml)	ATI	TTI	CTC
						Spirotetramat	-	6.03	100	-	-
Veratrine	-	13.13	45.93	-	-
						Spirotetramat: veratrine	1:0.1	5.68	106.16	95.08	111.65
Spirotetramat: veratrine	1:0.2	4.53	133.11	90.99	146.30
						Spirotetramat: veratrine	1:0.3	4.10	147.07	87.52	168.04
Spirotetramat: veratrine	1:0.5	5.71	105.60	81.98	128.82
						Spirotetramat: veratrine	1:1	7.29	82.72	72.96	113.37

Table 1 the results show that spirotetramat: the proportion of veratrine is 1: (0.2-0.5), the CTC is more than 120, which shows that in the range of the mixture ratio, the insecticidal composition has a synergistic interaction effect, shows an obvious poisoning effect on thrips, and has an obvious synergy effect when the mixture ratio is 1: 0.3.

Example 224% Spirotetramat veratrine suspension

Example 339% Spirotetramat veratrine suspension

Example 439% Spirotetramat veratrine suspension

Example 539% Spirotetramat veratrine microemulsion

The weight ratio is as follows:

example 639% spirotetramat veratrine emulsifiable concentrate

The weight ratio is as follows:

example 7

The bamboo leaf essential oil of example 3 was replaced with the essential oil prepared by the following method:

1) pulverizing bamboo leaves to 20 meshes to obtain bamboo leaf powder; adding 50mL of ethanol with the mass concentration of 50% into each gram of bamboo leaf powder, and stirring for 1 hour at 85 ℃; cooling, filtering, collecting filtrate, and removing ethanol to obtain extract;

2) adding 200mL of mixed solution of n-hexane and water with the mass ratio of 1:3 into each gram of extract, stirring for 60 minutes, standing for layering, collecting an organic layer, and concentrating.

Comparative example 124% Spirotetramat suspension

Example 7 field efficacy test for controlling thrips

Design of test cells according to the Standard of pesticide field efficacy test guidelines (1) of State administration of quality and technology, wherein the area of each cell is 20m²Totally, 32 cells are arranged, and 1.2m isolation zones are arranged among the cells. The application method adopts a spraying method, and the electric sprayer is used for uniformly spraying for 1 time.

And (3) reference to test crops: cowpea

Reagent to be tested: examples 2-7, comparative example 1, clear water control. Each set of treatments was set to 4 replicates.

The dosage of the effective components is as follows: 75g/hm²

Meteorological conditions: the weather is sunny or cloudy, breeze is slight, and the temperature is 23-32 ℃.

The investigation method comprises the following steps: the population base number of insects is investigated before pesticide application, sampling is carried out at 5 points on the diagonal line of each cell, and 10 cowpeas are fixedly investigated and marked at each point. The number of live insects on 50 cowpeas was determined. After the administration, the numbers 1d, 3d, 7d and 14d were examined in the same manner, and the efficacy was calculated.

TABLE 2 field efficacy test for prevention and treatment of thrips

As can be seen from table 2: under the condition of using the same dosage, the average control effect of the medicament of the embodiment reaches 85 percent after being applied for 3 days, which is higher than that of a contrast medicament, and shows that the formula of the embodiment of the invention has quick-acting property; after the medicines in the embodiment are applied for 7 days, the average control effect reaches over 90 percent, which is higher than that of other control medicines, and the medicines in the embodiment have synergistic action; after 14d of the medicaments in the example 2 and the example 3, the drug effect still reaches over 90 percent, and the suspending agents in the examples 2 to 3 have remarkable lasting effect. The overall result shows that the control effect of the formula of the embodiment of the invention on thrips is obviously higher than that of a comparative medicament, and the formula has excellent control effect.

The foregoing is a more detailed description of the present invention that is presented in conjunction with specific embodiments, and the practice of the invention is not to be considered limited to those descriptions. It will be apparent to those skilled in the art that a number of simple derivations or substitutions can be made without departing from the inventive concept.

Claims (2)

1. The thrips-killing suspending agent containing spirotetramat is characterized in that: the suspending agent comprises the following components in percentage by mass: 20-26% of spirotetramat, 4-13% of veratrine, 3-5% of lemon grass essential oil, 1-6% of bamboo leaf essential oil, 1-2% of 2500 emulsifier, 1-2% of 4894 emulsifier, 0.1-0.3% of xanthan gum, 0.2-0.8% of magnesium aluminum silicate, 4-8% of ethylene glycol, 0.3-0.6% of organic silicone, 0.2-0.6% of kasong and the balance of water.

2. The thrips-killing suspension containing spirotetramat according to claim 1, wherein: the bamboo leaf essential oil is prepared by the following method:

1) pulverizing bamboo leaves to 20 meshes to obtain bamboo leaf powder; adding 50mL of ethanol with the mass concentration of 70% into each gram of bamboo leaf powder, and stirring for 1 hour at 65 ℃; cooling, filtering, collecting filtrate, and removing ethanol to obtain extract;

2) adding 200mL of mixed solution of ethyl acetate and water with the mass ratio of 1:3 into each gram of extract, stirring for 60 minutes, standing for layering, collecting an organic layer, and concentrating.