CN101366388A - A kind of compound insecticide of fipronil and carbosulfan - Google Patents

Abstract

The invention discloses a compound insecticide of fipronil and carbosulfan, which belongs to the technical field of pesticide manufacture. The compound insecticide contains two active ingredients, fipronil and carbosulfan, in a weight ratio of 1:4 to 1:15. The preferred weight ratio is not less than 1:4 and not more than 1:9. Composition formulations can be prepared by conventional methods using effective doses of fipronil and carbosulfan, solid or liquid carriers, assistants and other additives. The insecticide has improved its co-toxicity coefficient through compounding, exerted a synergistic effect, expanded the insecticidal spectrum, and the control effect is above 90%, which is slightly better than the single agent effect of fipronil and carbosulfan. It is equivalent, but its control cost is reduced by 15% to 30%, and its quick-acting and long-lasting effects are better, and the generation of drug resistance is delayed, and its use is relatively safe. The insecticide can be applied in pesticide enterprises and agricultural production.

Description

A kind of compound insecticide of fipronil and carbosulfan

technical field

The invention relates to the technical field of pesticide manufacture, in particular to an insecticide pesticide compounded by fipronil and carbosulfan.

Background technique

With the long-term promotion and application of modern chemical insecticides and pesticides, the generation and enhancement of pest resistance, the application cycle of various new insecticides and pesticides has become shorter and shorter. In order to effectively deal with the increasingly rampant agricultural pests, in addition to continuous research and development In addition to developing various new types of insecticides and pesticides, efforts are made to improve and enhance the application technology of existing pesticides, such as rationally compounding several pesticides to improve their control effects, broaden their insecticidal spectrum, and reduce control costs. have achieved notable results.

Fipronil, common name is fipronil, chemical name: (RS)-5-amino-1-(26-dichloro-4a-trifluoromethylphenyl)-4-trifluoromethylsulfinylpyrazole- 3-Nitril, molecular formula: C12H4C12F6N4OS, molecular weight: 437.15, melting point: 195.5°C-203°C, the original drug is a crystalline powder, soluble in various organic solvents such as xylene and toluene. Fipronil is a kind of pests of Hemiptera, Lepidoptera, Thysanoptera, Coleoptera, etc., as well as pests that have developed resistance to cyclopentadiene, pyrethroids, and carbamate insecticides. Highly sensitive, broad-spectrum insecticides with good control effects. Suitable for rice, vegetables, soybeans, rapeseed, tea, sugar cane, fruit trees, ornamental plants, public health and ground buildings, etc. to prevent and control various crop pests and sanitary pests, such as rice planthopper, rice borer, rice borer, and rice vertical roll Leaf borer, diamondback moth, ants, etc.; however, the pesticide has problems such as large dosage and high price when used alone, and long-term single-dose use is likely to produce resistance.

Carbosulfan, English common name carbosulfan, chemical name: 2,3-dihydro-2,2-dimethylbenzofuran-7-yl (dibutylaminosulfur) methyl carbamate, molecular formula : C2OH32N2O3S, molecular weight: 380.55, boiling point (°C): 124-128, vapor pressure (25°C): 0.041mpa. Carbosulfan is a moderately toxic insecticide and acaricide. The acute oral LD50 of male and female rats is 250mg/kg and 185mg/kg respectively, and the acute percutaneous LD50 of rabbits is >2000mg/kg, highly toxic to birds and fish. Carbosulfan technical product is a brown to tan viscous oily liquid, soluble in various organic solvents such as xylene and toluene, and the solubility in water is 0.3mg/L (25°C). Stable under neutral or slightly alkaline conditions, unstable under acidic conditions. Carbosulfan is a low-toxic derivative of carbosulfan, an inhibitor of cholinesterase, with contact killing, stomach poisoning and systemic effects, and a long-lasting effect. It has a wide insecticidal spectrum, and has a high killing effect on aphids and citrus rust ticks; it has a quick effect, and it will take effect within 20 minutes after application, and has a long lasting effect. However, this pesticide also has problems such as large amount of single use, unsatisfactory effect, and long-term single-dose use is easy to produce drug resistance. There is no report on the composite application technology of fipronil and carbosulfan.

Contents of the invention

The object of the present invention is to propose a kind of pesticide with broad control spectrum and high control effect, aiming at the defects of large dosage, high cost and easy to produce drug resistance in the conventional single-dose application of the two pesticides, fipronil and carbosulfan. It is a compound insecticide and pesticide of fipronil and carbosulfan that is good, quick-acting and long-lasting, low-residue, low-cost, and delays drug resistance.

The object of the present invention is achieved through the following technical solutions.

A compound insecticide of fipronil and carbosulfan, the compound insecticide contains two active ingredients of fipronil and carbosulfan, and the weight ratio of the two is 1:4 to 1: 15.

A compound insecticide of fipronil and carbosulfan, the compound insecticide contains two active ingredients of fipronil and carbosulfan, and the weight ratio of the two is preferably not less than 1:4 , and not greater than 1:9.

The compound insecticide can be prepared as a composition emulsifiable concentrate or a wettable powder formulation by using effective doses of fipronil and carbosulfan, solid or liquid carrier, auxiliary agent and other additives through conventional methods.

The compound insecticide of fipronil and carbosulfan of the present invention can be used in rice, wheat, soybean, leafy vegetables, fruit vegetables, cotton, tobacco, citrus and other fruit trees and tea trees and other crops to prevent and control rice planthopper and whitefly , Bemisia tabaci, thrips, flea beetle and other pests.

The beneficial effects of the present invention are:

The present invention takes fipronil and carbosulfan as active ingredients, increases its co-toxicity coefficient to 153.0-252.8 through compounding, and exerts a synergistic effect, among which the synergistic effect of 1:4 and 1:9 is particularly obvious , and expanded the insecticidal spectrum of the compound agent, improved the flea beetle (see table 2), thrips (see table 3), bemisia tabaci (see table 4) and rice planthopper (see table 5) ), whitefly and other pests, the control effect is above 90%, which is better than the control chemical agents used in the original routine, slightly better or equivalent than the single agent effect of fipronil and carbosulfan, but its The control cost is 15%-30% lower than that of a single agent, can effectively control the severe damage of the above-mentioned major pests, has good quick-acting and long-lasting effects, delays the generation of drug resistance, and is relatively safe to use.

Detailed ways

The present invention is further described in detail through the following examples, but it should be understood that the content of the present invention is not limited to the following examples.

The materials involved in the following examples and test examples are:

5% fipronil (fipronil): German Bayer company, 5% suspending agent;

20% Carbosulfan (Hao Nian Dong): American FMC Company, 20% emulsifiable concentrate;

48% Lesben (chlorpyrifos) emulsifiable concentrate: Dow AgroSciences;

45% Malathion EC: Shandong Dezhou Hengdong Pesticide Chemical Co., Ltd.;

10% imidacloprid WP: produced by Zhejiang Taifeng Chemical Company;

25% Pidiling (buprofezin) WP: produced by Jiangsu Changnong Chemical Co., Ltd.;

1.8% insect mite emulsion: Guilin Jiqi Group.

Example 1: (16% fipronil, carbosulfan compound EC)

Formula by weight as follows: fipronil 1%, carbosulfan 15%, emulsifier 0204C 6%, emulsifier 2201 4%, xylene supplemented to 100%; specific preparation steps and process: dissolve the original drug in two Add emulsifiers 0204C and 2201 to toluene, mix and dissolve under stirring, and make a single-phase liquid compound emulsifiable concentrate; the emulsifiable concentrate preparation can prevent and control whitefly, and the drug effect can reach more than 90%.

Example 2: (10% fipronil, carbosulfan compound EC)

According to the following weight formula: fipronil 1%, carbosulfan 9%, emulsifier 0204C 3%, emulsifier 22011.0%, solvent xylene supplemented to 100%; After 1-3 days, the drug effect reaches more than 90%; the specific preparation steps and process are the same as in Example 1.

Example 3: (10% fipronil, carbosulfan compound EC)

According to the following weight formula: fipronil 2%, carbosulfan 8%, emulsifier 0204C 3%, emulsifier 22011.0%, solvent xylene supplemented to 100%; the emulsifiable concentrate preparation prevents and treats thrips, and the efficacy reaches 90% More than %; Concrete preparation steps, technology are with embodiment 1.

Example 4: (6% fipronil and carbosulfan compound wettable powder)

According to the following formula by weight: 1% fipronil, 5% carbosulfan, 10% alkyl polyoxyethyl ether, and kaolin to make up to 100%; the wettable powder preparation can control rice planthopper with a drug effect of 70% -91%; specific preparation steps and process: first mix the original drug of carbosulfan with the dispersant alkyl polyoxyethyl ether, then mix the original drug of fipronil with the filler kaolin, and then finely pulverize the drug, Then mix to obtain compound wettable powder.

Test Example 1: (Fipronil and Carbosulfan Compound Synergism Test)

Taking flea beetle as a test material, the combined effect of fipronil and carbosulfan after mixing was discussed to determine the optimal formulation between the two, which can replace highly toxic insecticides to control various pests. Production of practical applications to provide sufficient basis.

1 Materials and methods

1.1 Indoor toxicity test

1.1.1 Test materials The test insects are flea beetles, collected from green vegetables in Jianqiao Village, Jianggan District, Hangzhou City. The green vegetable seedlings are raised indoors. The temperature in the insect culture room is 25°C±1°C, the light is 16L/8D, and the light intensity is 2000lx ;

1.1.2 Test treatment The test set 5 treatments: 5% fipronil; 20% carbosulfan emulsifiable concentrate; fipronil + carbosulfan compound preparation, using Example 1——1:15, implementing Example 2—1:9, Example 3—2:8 (i.e. 1:4) are all self-prepared, and a blank control is also set up;

1.1.3 Test method The leaf soaking method introduced by the International Resistance Action Committee was used. The 48-hour toxicity of single agent and compound agent to adults of the flea beetle was determined. The specific steps are as follows: (1) collect the clean leaves of Shanghai green leaves that have not been polluted by pesticides; (2) prepare a certain concentration of pesticide solution with water for the test pesticide, immerse the vegetable leaves in the solution respectively, take them out after 10 seconds and dry them naturally (3) putting the dried leaves into plastic bioassay bottles, and inserting about 30 flea beetle adults. Three repetitions were set up, and water treatment was used as the control; (4) The bioassay bottle was placed in an air-conditioned room at 25°C and a relative humidity of 75%-85%, and the number of dead insects was checked after 48 hours to calculate the mortality rate. The control mortality rate was 0 during the experiment. Calculate the toxicity regression equation and LC50 (mg/L) according to the logarithmic value of the dose of the pesticide and the death probability value, and calculate the co-toxicity coefficient according to the calculation method of the combined toxicity of insecticides reported by Sun Yunpei et al. (1960).

2 Results and Analysis

     Table 1 Toxicity of the compound of fipronil and carbosulfan

deal with Virulence regression equation LC50(mg/L) Toxicity index theoretical virulence index co-toxicity coefficient Fipronil y=3.5279+1.5256x 9.2243 765.1 carbosulfan y=2.1314+1.5517x 70.5801 100 Fipronil + Carbosulfan (1:4) y=3.1963+1.6724x 11.9815 589.1 233.0 252.8 Fipronil + Carbosulfan (1:9) y=2.5638+1.7426x 25.0049 282.3 166.5 169.5 Fipronil + Carbosulfan (1:15) y=2.4234+1.7015x 32.6822 216.0 141.2 153.0

2.1 Indoor toxicity test results The co-toxicity coefficients of the three formulas compounded by fipronil and carbosulfan were 252.8, 169.5, and 153.0, respectively. It can be seen that the mixture of fipronil and carbosulfan has a significant synergistic effect, and the synergistic effect of 1:4 and 1:9 is particularly obvious (Table 1).

Test example 2: (test of fluorine and butyl compound emulsifiable agent for preventing and treating flea beetle)

Flea beetle often causes devastating damage to cruciferous vegetables at the seedling stage. During the growth period of vegetables, adults feed on the leaves and cause many small holes, which not only affects the yield, but also affects the quality of vegetables, greatly reducing the commodity value of vegetables . According to other reports, the drug resistance of flea beetle flea beetle has become more and more serious in the past ten years. In order to effectively inhibit the damage of flea beetle and the development of drug resistance, and provide a basis for rational drug use in the field, the following field efficacy tests were carried out.

1 Materials and methods

1.1 Chemical agents for testing 48% Lesben (chlorpyrifos) EC; 80% Dichlorvos EC; 20% Hawthorne; 5% Fipronil (Fipronil); 45% Malathion EC; Compound EC (Example 2, fluorine: butyl = 1:9 product).

1.2 Field efficacy test method The field test was carried out in June 2006 in the vegetable field of Yangjia Village, Shiqiao, Hangzhou. Refer to the determination method of the national standard "Guidelines for Field Efficacy Tests (2)". Use the Gongnong 16 backpack sprayer to evenly spray the front and back sides of the Shanghai green leaves, and the water consumption per hectare is 750 kg. During the blooming period of flea beetle adults, spray once. Each treatment was repeated 3 times, and the area of each experimental plot was 10 square meters, and the plots were arranged in random blocks. The number of live flea beetles on all the leaves of 20 plants of Haiqing was randomly investigated in each plot. Before the application of the pesticide, the base number of the insect population was investigated, and the number of live insects remaining on the flea beetle was investigated 1, 3, and 5 days after the application of the pesticide. According to the number of living insects of the flea beetle before and after spraying in the treatment area and the control area, the population reduction rate and corrected control effect were calculated, and the significant difference was tested by Duncan's new multiple range method.

2. Results and analysis Table 2 shows the results of field efficacy tests of different pesticides on adults of the flea beetle. One day after the application, four insecticides, such as flubutane mixture, 48% Lesben, 20% Haoniandong, and Ruijinte, had a good control effect on the adult flea beetle, and the control effect was 90.9%. All of the above can effectively control the damage of the flea beetle. 45% malathion, 80% dichlorvos, etc. have poor control effects on the adult flea beetle. There was a similar trend 3 days after the application, and the four insecticides including flubutane mixture, 48% Lesben, 20% Haoniandong, and Ruijint also had a good control effect on the flea beetle adults. The effects are all above 85%, and can effectively control the damage of the flea beetle. 45% malathion, 80% dichlorvos, etc. have poor control effects on the adult flea beetle. The control effects of different agents against flea beetle were all decreased 7 days after treatment. Both malathion and dichlorvos have poor quick-acting and long-lasting effects on flea beetle. The results showed that the control effect of fipronil and carbosulfan mixed with pesticides was excellent, which was better than that of single dose of carbosulfan, and also better than that of common pesticides such as chlorpyrifos, dichlorvos and malathion. Therefore, the chemical agents for the control of adults can choose 10% fipronil carbosulfan EC, 20% Haoniandong, Fipronil, 48% Lesben and other 4 kinds of insecticides. It is used for spraying control in season or when the number of insects in the field is large, but attention should be paid to alternate use.

       Table 2 Field efficacy of different pesticides against adult flea beetles

Test example 3: (Fluorine, butyl compound emulsifiable concentrate prevents and cures melon thrips test)

Melon thrips is very harmful to eggplant. In order to screen out some pesticides with high control effect, low toxicity and low residue, this experiment was carried out.

1 Materials and methods

1.1 Test medicaments 1.8% Chongmite emulsion, 20% Haoniandong EC, 5% fipronil (fipronil) EC, 10% fluoride, butyl compound EC (Example 3, fluoride: butyl = 2:8) .

1.2 Test method In the eggplant field of Jianqiao Village, Jianqiao Town, Hangzhou, the variety is Hangqi No. 1, and it is in the fruiting stage at the time of the test. Set up 1.8% 1000-fold solution of Chongmike, 20% Haoniandong 1000-fold solution, and 5% Regent 1500 times solution, 1500 times solution of fluorobutane mixture and clear water control 5 treatments, repeated 3 times, a total of 15 plots, each with an area of 66.6m2. Apply pesticides during the blooming stage of thrips nymphs, spray evenly with a knapsack manual sprayer, and it is advisable to spray until it is wet and does not drip.

1.3 Investigation method Investigate the number of insects before spraying, 3 days and 7 days after spraying, take samples at 5 points on the diagonal of each plot, and mark 2 plants at each point for a total of 10 plants. Count the number of insect populations on the third leaf from the bottom. Calculate its corrective effect.

2 Test results and analysis

Table 3 Field efficacy of different pesticides against Thrips melon

From the test results in Table 3, it can be seen that 7 days after the drug treatment, 1.8% 1000-fold solution of chrysanthemum, 1000-fold solution of 20% Haoniandong, 1500-fold solution of 5% fipronil, and 1500-fold solution of flubutane mixture The control effects reached 73.6%, 86, 5%, 85.3% and 87.9% respectively; the control effects of the three chemical treatments were all significantly better than the control, and the difference in the control effects among the treatments of Fipronil, Fluorbutane Mixture and Haoniandong Insignificant, at the same level, they are all obviously better than the treatment of insect mite. The control costs per mu of the above four pesticides were 5 yuan, 5.5 yuan, 5 yuan, and 4.5 yuan respectively, and the cost of fluorobutane mixture was the lowest. Tetrachloride and carbosulfan single doses are comparable, but the cost is lower than single doses, and the control effect is better than that of the commonly used pesticide, carbosulfan.

Test Example 4: (Test of fluorine and butyl compound emulsifiable agent to control Bemisia tabaci on eggplant)

In recent years, Bemisia tabaci has caused serious damage to eggplant. In order to screen out some pesticides with high control efficiency, low toxicity and low residue, this experiment was carried out.

1 Materials and methods

1.1 Test medicaments 1.8% Chongmite emulsion, 20% Haoniandong EC, 5% fipronil (fipronil) EC, 16% fluorine, butyl compound EC (Example 1, fluoride: butyl = 1:15 product ).

1.2 Test method In the eggplant field of Zhangjia Village, Cangqian Town, Yuhang District, Hangzhou, the eggplant variety is Hangqi No. 1, and it is in the fruiting stage at the time of the test. Set up 1000 times liquid of 1.8% Chongmike, 1000 times liquid of 20% Haoniandong, 5 5 treatments of 1500 times solution of Fiproxil, 1500 times solution of flubutadiene mixture and clear water control, repeated 3 times, 15 plots in total, each with an area of 40m2. In order to prevent each agent from interacting with each other, a plastic film is hung between each cell for temporary isolation every time the agent is sprayed. Apply pesticides during the blooming stage of Bemisia tabaci nymphs, spray evenly with Gongnong 16 knapsack manual sprayer, and it is advisable to spray until it is wet without dripping water.

1.3 Investigation method Investigate the number of insects before spraying and 3 days and 7 days after spraying, take samples at 5 points on the diagonal of each plot, and mark 2 plants at each point for a total of 10 plants, and investigate the adult insects on the upper 10 leaves of each plant Insect population. Calculate the rate of insect population decline and calculate its corrected control effect.

2 Test results and analysis From the test results in Table 4, it can be seen that 1 day after treatment, 1000 times of 1.8% chrysanthemum, 1000 times of 20% Haoniandong, 1500 times of 5% fipronil, and 1500 times of flubutane mixture The control effects of the 4 chemical treatments reached 78.5%, 77.5%, 69.0% and 82.5% respectively; the control effects of the 3 chemical treatments were all significantly better than the control. There was no significant difference in the control effect between the treatments of Niandong and Chongmike, both of which were significantly better than the treatment of Chongmike. There was a similar trend after 7 days of taking the drug, except that the effect of Fipronil increased, but the effect of Chromite decreased. The fluorobutane mixture still maintains a good effect. The control costs per mu of the above four agents were 5 yuan, 5.5 yuan, 5 yuan, and 4.5 yuan, respectively, and the cost of fluorobutane mixture was the lowest. The results showed that the control effect of 16% fipronil and carbosulfan mixed pesticides on Bemisia tabaci was good, which was equivalent to that of fipronil and carbosulfan alone, but the cost was lower than that of single doses. The control effect is also better than that of commonly used pesticides.

Table 4 Field efficacy of different pesticides on Bemisia tabaci

Test Example 5: (Test of controlling rice planthopper with fluorine and butyl compound wettable powder)

In order to verify the control effect of 6% fluorine and butyl compound wettable powder on rice planthopper and its application technology, in September 2007, 6% fluorine and butyl compound wettable powder was tested in the paddy field of Cangqian Town, Yuhang District, Zhejiang Province. Control rice planthopper test:

1 Materials and methods

1.1 Test agent 6% fluorine and butyl compound wettable powder (Example 4, fluorine: butyl = 1:5 product), 10% imidacloprid WP, 25% buprofen (buprofezin) WP, 5% sharp Special SC, 20% Haoniandong (Carbosulfan) EC.

1.2 Treatment and methods The test set 40g, 50g, 60g of 6% fluorine and butyl compound wettable powder per 666.7m2, 40ML of Haoniandong, 30g of imidacloprid, 50g of pibulin, and 30m1 of fipronil, and no drug control, a total of 8 Each treatment was repeated 4 times, randomly arranged, the area of the plot was 33.3m2, 75 kg of water was routinely sprayed evenly, and the water layer was kept in the field after spraying. When the pesticide is applied, it is sunny, the wind force is 2-3, and the growth period of rice planthopper is the peak period of the third and fourth instar nymphs. The rice variety used for the test was Xiushui 110, and the cultivation type was direct-seeding rice.

1.3 Investigation and Records Investigate the occurrence base of rice planthoppers before spraying, investigate the residual insects of rice planthoppers in each treatment plot 3, 7, 10, and 14 days after spraying, investigate 25 pots in each plot, 2 holes in each pot, and calculate the control The results were statistically analyzed to compare the differences in the control effects of each chemical treatment.

2 Results and analysis

2.1 The control effect of different pesticides such as flubutadiene powder It can be seen from the survey results of the third period after the treatment in Table 5 that the flubutadiene mixture has a better quick-acting effect on rice planthopper, and the control effect is obvious. Three days after application, the control effect of 40g~60g per 666.7m2 of flubutane mixture on rice planthopper was 70.7-75.1%, higher than that of imidacloprid (62.9%); It is close to the control effect of fipronil at 75.4%. 7 days after application, the control effect of flubutadiene mixture has increased, and the control effect of 40g~46g of flubutadiene mixture on planthoppers is 79.8-85.3%, which is higher than the control effect of 3 days after application, and is also higher than that of imidacloprid in the same period. The anti-efficacy of piproxil is high; but the anti-efficacy of 85.5% is slightly lower than that of fipronil. 10 days after application, the control effect of flubutane mixture was further improved, and its control effect reached 88.7-91.4%, both of which were higher than that of imidacloprid and chlorpyrin, and similar to that of fipronil at 91.0%. It can be seen that the flubutan mixture is an ideal agent for the control of rice planthoppers, and it is worthy of popularization and application on rice. It can be used alternately with imidacloprid, chlorpyrifos, and fiproxil to control rice planthoppers and other rice pests. The economical and effective dosage of fluorobutane mixture for controlling rice planthopper is 60g.

Table 5 Field effect of fluorobutane mixture on controlling rice planthopper

Claims (3)

1. fluorine worm nitrile and carbosulfan compounded pesticides, it is characterized in that: this compounded pesticides contains fluorine worm nitrile and two kinds of active components of carbosulfan, and both weight ratios were at 1: 4 to 1: 15.

2. by the described compounded pesticides of claim 1, it is characterized in that: this compounded pesticides contains fluorine worm nitrile and two kinds of active components of carbosulfan, and both weight ratios are for being not less than 1: 4, and is not more than 1: 9.

3. by claim 1 or 2 described compounded pesticides, it is characterized in that: this insecticide can make its composition missible oil or wettable powder agent formulation with fluorine worm nitrile and carbosulfan and solid or liquid-carrier, auxiliary agent and other additive of effective dose through conventional method.