Disclosure of Invention
The first purpose of the invention is to provide an insecticidal aerosol, which has scientific proportioning, mutual coordination of all components, obvious synergistic effect, obvious insecticidal activity, great reduction of drug resistance of vector pests, high efficiency, low toxicity, safety, economy and environmental protection.
The insecticidal aerosol comprises the following components in parts by mass: 0.1-1% of pyrethroid compounds, 10-20% of soy sauce residue glyceride, 1-5% of palmatine, 1-5% of surfactants, 0.5-2.5% of penetrants, 0.5-1.5% of essences, 20-30% of propellants, 40-50% of organic solvents and 10-20% of water.
Preferably, the insecticidal aerosol comprises the following components in parts by mass: 0.5% of pyrethroid compounds, 15% of soy sauce residue glyceride, 3% of palmatine, 4% of surfactant, 1.5% of penetrating agent, 1% of essence, 25% of propellant, 40% of organic solvent and 10% of water.
The pyrethroid compound is more than one selected from Es-bioallethrin, transfluthrin, d-metaflumethrin, permethrin, cyhalothrin, cypermethrin, deltamethrin or d-propynethrin.
Preferably, the pyrethroid compound is permethrin.
The surfactant is composed of tea saponin and tween-80 in a mass ratio of 1 (0.5-1).
Preferably, the surfactant is composed of tea saponin and tween-80 in a mass ratio of 1: 0.5.
The penetrating agent is laurocapram, 1-methyl-2-pyrrolidone or 5-methyl-2-pyrrolidone.
The organic solvent is more than one of absolute ethyl alcohol, propyl alcohol, isopropyl alcohol, n-butyl alcohol, ethylene glycol, n-pentane, isopentane, n-hexane, xylene, toluene, ethyl acetate, benzyl alcohol ester, phthalate or alcohol ether organic solvents.
The alcohol ether organic solvent includes but is not limited to ethylene glycol butyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol butyl ether, triethylene glycol butyl ether, tetraethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monoalkyl ether carboxylate and the like.
The essence includes, but is not limited to, orange flower essence, lavender essence, chrysanthemum essence, jasmine essence, sandalwood essence, costus root essence, lemon essence and the like.
The propellant is a conventional propellant including, but not limited to, compressed nitrogen, compressed carbon dioxide, compressed nitrogen oxide, compressed air, 1, 1-difluoroethane, heptafluoropropane, difluoromethane, pentafluoroethane, trifluoroethane, 1,1,1, 2-tetrafluoroethane, chlorodifluoromethane, dichlorodifluoroethane, dichloromonofluoromethane, propane, n-butane, isobutane, isopentane, pentane, dimethyl ether, and the like.
The soy sauce residue glyceride in the formula is prepared by taking the grease and the glycerol extracted from the waste soy sauce residues generated by soy sauce fermentation and brewing as raw materials and carrying out esterification reaction by using specific lipase, has the advantages of wide source and low cost, belongs to waste recovery, and accords with the concept of environmental protection. Specifically, the preparation of the soy sauce residue glyceride is obtained by referring to the technical scheme disclosed in the Chinese patent application with the publication number of CN 107751575A, and specifically comprises the following steps:
removing volatile impurities from the soy sauce residue grease under the conditions that the temperature is 70-85 ℃ and the vacuum degree is 0.08-0.1 MPa, and keeping for 30-60 min; when the temperature of the soy sauce residue oil is reduced to 50-70 ℃, adding 1-2% (m/m) of special lipase and 5-10% (m/m) of glycerol, continuously reacting under the conditions that the vacuum degree is 0.08-0.1 MPa and a certain amount of dry air or nitrogen is introduced, and when the acid value of the soy sauce residue oil is reduced to be below 4mg/g (calculated by KOH), separating out soy sauce residue glyceride by using a filter screen with the pore diameter of 100-200 meshes to obtain the soy sauce residue glyceride; wherein the specific lipase is any one of Novozym 40086, Novozym 435 and Lipozyme RM IM.
The second purpose of the invention is to provide a preparation method of the insecticidal aerosol, which comprises the following steps:
(1) mixing the pyrethroid compound, soy sauce residue glyceride, palmatine, a surfactant, a penetrant, essence, an organic solvent and water according to the formula ratio, and fully stirring for 1-2 hours to obtain aerosol liquid medicine;
(2) filling the aerosol liquid medicine into an aerosol tank, inserting a valve for sealing, and then filling the propellant into the aerosol tank filled with the aerosol liquid medicine under high pressure to obtain the insecticidal aerosol.
The third purpose of the invention is to provide the application of the insecticidal aerosol in the aspect of controlling vector pests, wherein the vector pests comprise mosquitoes, flies, cockroaches, termites, ants, fleas, mites, lice, bugs, ticks or mites and the like, and the mosquitoes comprise culex pipiens, culex trithinochiensis, culex fatigues, aedes albopictus, aedes aegypti, anopheles sinensis and the like; the fly comprises housefly, city fly, lucilia sericata, Chrysomya megacephala and the like; the cockroaches comprise German cockroach, American cockroach, Australia cockroach, Japanese cockroach, Periplaneta fuliginosa and the like; the termite includes Taiwan emulsion termite, large black wing termite, large yellow wing termite, white thorny termite, yellow thorny termite, sand stacking termite, etc.
Compared with the prior art, the invention has the following beneficial effects:
(1) the inventor discovers through a large number of experiments that the pyrethroid compound and soy sauce residue glyceride are used as effective components of the insecticidal aerosol, the compound palmatine is used as a synergist, the synergistic insecticidal composition has a remarkable synergistic insecticidal effect, the dosage of the pyrethroid compound is obviously reduced, the cost is reduced, the generation of drug resistance of disease-vector pests is delayed, the defects that the pyrethroid insecticide is easy to generate drug resistance when being used alone, the dosage is increased, and damage is caused to the ecological environment are effectively overcome, and the synergistic insecticidal composition has the characteristics of safety, high efficiency, quick effect and long lasting period.
(2) The insecticidal aerosol provided by the invention has certain antibacterial activity, and can effectively kill pathogenic microorganisms, control vector infectious diseases and protect the health of people while effectively preventing and treating vector pests.
(3) The insecticidal aerosol provided by the invention has the characteristics of simple preparation process, low production cost, sufficient raw materials, small influence on environment, safety and reliability to human bodies, no bad irritant odor, low toxicity, economy and environmental protection.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof.
The components of the formulations in the following examples are, unless otherwise specified, conventional commercial products, wherein palmatine is palmatine hydrochloride, which has a CAS number of 10605-02-4, available from carbofuran technologies, Inc.; permethrin CAS number is 52645-53-1, sourced from Kyokam limited; the CAS number of the Es-bioallethrin is 84030-86-4, and the source is Zhongshan Kai Co., Ltd; tetratransfluthrin CAS number is 118712-89-3, from Kyokam limited of Zhongshan; cyhalothrin (cyhalothrin) having CAS number of 91465-08-6, available from Kyoho Tech technologies, Inc. of Hubei; the CAS number of the dextro-hepta-fluoromethyl ether pyrethroid is 1208235-75-9, and the dextro-hepta-fluoromethyl ether pyrethroid is purchased from Shanghai Hao chemical Co., Ltd; the CAS number of tea saponin is 8047-15-2, and is purchased from Xinke chemical industry Co.
Example 1 preparation of glycerides of soy sauce pomace
The preparation method of the soy sauce residue glyceride comprises the following steps:
adding soy sauce residue oil into a reaction kettle, starting stirring, heating the reaction kettle to 85 ℃, starting a vacuum pump to enable the vacuum degree of the reaction kettle to reach 0.1MPa, and continuing for 30min to remove volatile impurities; when the temperature of the reaction kettle is reduced to 70 ℃, 1% (m/m) of lipase Novozym 435 (purchased from Hangzhou Chuangkeke Biotechnology Co., Ltd.) and 10% (m/m) of glycerol are added, the reaction is continued under the condition that the vacuum degree is 0.1MPa and nitrogen is introduced, and when the acid value of the soy sauce residue oil is reduced to be below 4mg/g (calculated by KOH), the soy sauce residue glyceride is separated by a filter screen with the pore size of 100 meshes, thus obtaining the soy sauce residue glyceride.
Example 2 preparation of glycerides of soy sauce pomace
The preparation method of the soy sauce residue glyceride comprises the following steps:
adding the soy sauce residue oil into a reaction kettle, starting stirring, heating the reaction kettle to 70 ℃, starting a vacuum pump to enable the vacuum degree of the reaction kettle to reach 0.08MPa, and continuing for 60min to remove volatile impurities; when the temperature of the reaction kettle is reduced to 50 ℃, 1% (m/m) of lipase Novozym 435 (purchased from Hangzhou Chuangke Biotech Co., Ltd.) and 5% (m/m) of glycerol are added; continuously reacting under the condition of introducing nitrogen gas at the vacuum degree of 0.08MPa, and separating out the glyceride of the soy sauce residue by using a filter screen with the pore size of 200 meshes when the acid value is reduced to be below 4mg/g (calculated by KOH).
EXAMPLE 3 preparation of insecticidal Aerosol
Example 3 an insecticidal aerosol comprises the following components in parts by mass: permethrin 0.5%, soy sauce residue glyceride (prepared in example 1) 15%, palmatine 3%, tea saponin 2.7%, tween-801.3%, laurocapram 1.5%, lemon essence 1%, dimethyl ether 25%, diethylene glycol monobutyl ether 40% and water 10%.
The preparation method comprises the following steps:
(1) mixing permethrin, soy sauce residue glyceride, palmatine, tea saponin, tween-80, azone, lemon essence, diethylene glycol monobutyl ether and water, and stirring for 2 hr to obtain aerosol medicinal liquid;
(2) filling the aerosol liquid medicine into an aerosol tank, inserting a valve for sealing, and then filling dimethyl ether into the aerosol tank filled with the aerosol liquid medicine under high pressure to obtain the insecticidal aerosol.
EXAMPLE 4 preparation of insecticidal Aerosol
Example 4 an insecticidal aerosol comprises the following components in parts by mass: permethrin 1%, soy sauce residue glyceride (prepared in example 1) 10%, palmatine 5%, tea saponin 1%, tween-801%, laurocapram 1%, neroli essence 1%, dimethyl ether 25%, diethylene glycol monobutyl ether 40% and water 15%.
The preparation method refers to example 3.
EXAMPLE 5 preparation of insecticidal Aerosol
Example 5 an insecticidal aerosol comprises the following components in parts by mass: permethrin 0.3%, soy sauce pomace glyceride (prepared in example 1) 20%, palmatine 4%, tea saponin 2%, tween-801%, laurocapram 1.5%, jasmine essence 1.2%, dimethyl ether 20%, diethylene glycol monobutyl ether 40% and water 10%.
The preparation method refers to example 3.
EXAMPLE 6 preparation of insecticidal Aerosol
Example 6 an insecticidal aerosol comprising the following components in mass fractions: 0.8% of Es-bioallethrin, 18% of soy sauce residue glyceride (prepared in example 1), 2% of palmatine, 1% of tea saponin, 1% of tween-801%, 1.2% of laurocapram, 1% of lemon essence, 20% of difluoromethane, 45% of triethylene glycol monobutyl ether and 10% of water.
The preparation method refers to example 3.
EXAMPLE 7 preparation of insecticidal Aerosol
Example 7 an insecticidal aerosol comprises the following components in parts by mass: 0.6% of transfluthrin, 14% of soy sauce residue glyceride (prepared in example 1), 5% of palmatine, 2% of tea saponin, 801% of tween, 2% of laurocapram, 1.4% of lemon essence, 20% of trifluoroethane, 40% of triethylene glycol monobutyl ether and 14% of water.
The preparation method refers to example 3.
EXAMPLE 8 preparation of insecticidal Aerosol
Example 8 the insecticidal aerosol comprises the following components in percentage by mass: cyhalothrin 0.9%, soy sauce residue glyceride (prepared in example 1) 16%, palmatine 2%, tea saponin 2%, tween-802%, laurocapram 1.1%, lemon essence 1%, isopentane 25%, butyl cellosolve 40% and water 10%.
The preparation method refers to example 3.
EXAMPLE 9 preparation of insecticidal Aerosol
Example 9 an insecticidal aerosol comprising the following components in mass fractions: 0.7% of dextro-heptafluoro-methothrin, 12% of soy sauce residue glyceride (prepared in example 1), 5% of palmatine, 2% of tea saponin, tween-801%, 1.3% of laurocapram, 1% of lemon essence, 25% of dimethyl ether, 40% of diethylene glycol monobutyl ether and 12% of water.
The preparation method refers to example 3.
Comparative example 1 preparation of insecticidal Aerosol
Comparative example 1 an insecticidal aerosol comprising the following components in mass percent: 0.5% of permethrin, 3% of palmatine, 2.7% of tea saponin, 801.3% of tween-tween, 1.5% of laurocapram, 1% of lemon essence, 25% of dimethyl ether, 50% of diethylene glycol monobutyl ether and 15% of water.
Comparative example 1 the formulation of an insecticidal aerosol formulation differs from that of example 3 in that soy sauce residue glyceride is not included and the amounts of diethylene glycol butyl ether and water are increased accordingly, the preparation process being referred to in example 3.
Comparative example 2 preparation of insecticidal Aerosol
Comparative example 2 an insecticidal aerosol comprising the following components in mass fraction: 15.5% of soy sauce residue glyceride (prepared in example 1), 3% of palmatine, 2.7% of tea saponin, 801.3% of tween-1, 1.5% of laurocapram, 1% of lemon essence, 25% of dimethyl ether, 40% of diethylene glycol monobutyl ether and 10% of water.
Comparative example 2 the formulation of an insecticidal aerosol formulation differs from that of example 3 in that permethrin is not included and the amount of soy sauce pomace glycerides is increased accordingly, the preparation process being referred to example 3.
Comparative example 3 preparation of insecticidal Aerosol
Comparative example 3 an insecticidal aerosol comprising the following components in mass fraction: permethrin 0.5%, soy sauce residue glyceride (prepared in example 1) 15%, tea saponin 2.7%, tween-801.3%, laurocapram 1.5%, lemon essence 1%, dimethyl ether 25%, diethylene glycol monobutyl ether 40% and water 13%.
Comparative example 3 the formulation of an insecticidal aerosol formulation differs from that of example 3 in that bamatin is not included and the amount of water is increased accordingly, the process being prepared according to example 3.
Comparative example 4 preparation of insecticidal Aerosol
Comparative example 4 an insecticidal aerosol comprising the following components in mass fraction: 1.5% of permethrin, 2.7% of tea saponin, 801.3% of tween-laurel azepinone, 1.5% of lemon essence, 25% of dimethyl ether, 50% of diethylene glycol monobutyl ether and 17% of water.
Comparative example 4 formulation composition of an insecticidal aerosol was different from that of example 3 in that soy sauce residue glyceride and palmatine were not contained, but the amount of permethrin was increased, and the amount of diethylene glycol monobutyl ether and water were increased, and the preparation method was referenced to example 3.
Test example I, Performance test of insecticidal Aerosol
The insecticidal aerosols prepared in examples 3-9 and comparative examples 1-4 were respectively subjected to atomization rate and internal pressure detection, wherein the atomization rate and the internal pressure are detected according to the methods specified in GB/T18419-2009 insecticidal aerosol for domestic hygienic products and GB24330-2009 general technical conditions for safety of domestic hygienic products, and the specific test results are shown in Table 1.
TABLE 1 insecticidal Aerosol Performance test results
The results show that the aerosol formulations of examples 3 to 9 of the present invention and comparative examples 1 to 4 were in compliance with the national standards in terms of atomization rate and internal pressure.
Test example II control Effect of insecticidal Aerosol on vector pests
Testing the vector pests: 1200 female imagoes which do not suck blood 3-5 days after eclosion, houseflies, 1200 imagoes which are male and female imagoes after eclosion 3-4 days, 1200 german cockroaches, 720 imagoes of two weeks and 720 male and female imagoes respectively are randomly divided into 12 groups which are respectively a test 1-7 group and a comparison 1-5 group, each group contains 100 light culex mosquitoes, 100 houseflies (female and male half) and 60 german cockroaches (female and male half). Of these, the insecticidal sprays prepared in examples 3 to 9 were used in test groups 1 to 7, the insecticidal sprays prepared in comparative examples 1 to 4 were used in comparative groups 1 to 4, and a commercially available insecticidal spray was used in comparative group 5. The spraying amount of each group of insecticidal spraying agent is 8.4 g.
The test conditions are as follows: the temperature is 26 +/-1 ℃, and the relative humidity is 65% +/-10%.
And (3) simulating a field: area of 10m2Height of 2.8m2The floor white ceramic tile, the ceiling and the surrounding walls are all sealed transparent glass.
The results are shown in tables 2-4.
TABLE 2 control Effect of insecticidal Aerosol on Culex pipiens pallens
As can be seen from the tests 1 to 7, the insecticidal aerosols prepared in examples 3 to 9 of the present invention have half the knock-down time (KT) against Culex pipiens pallens50) Within the range of 1.30-1.66 min, the death rate of culex pipiens pallens after 24 hours reaches more than 91.25%, the knockdown rate after 1 hour reaches more than 96.25%, and the product is obviously superior to that of a comparison group 1-4 and a commercial product group, which shows that the pyrethroid compound, the soy sauce residue glyceride and the palmatine in the insecticidal aerosol have a remarkable synergistic effect on killing culex pipiens pallens, and particularly the insecticidal aerosol prepared by the test group 1, namely the formula of the embodiment 3, has the best effect.
TABLE 3 control of fly by insecticidal aerosols
As can be seen from the tests 1 to 7, the insecticidal aerosols prepared in examples 3 to 9 of the present invention have half the knock-down time (KT) against houseflies50) Within the range of 1.62-1.90 min, the death rate of culex pipiens pallens after 24 hours reaches more than 90.00 percent, the knockdown rate after 1 hour reaches more than 95.00 percent, and the product is obviously superior to that of a comparison group 1-4 and a commercial product group, which shows that the combination of the pyrethroid compound, the soy sauce residue glyceride and the palmatine in the insecticidal aerosol has a remarkable synergistic and enhanced killing effect on houseflies, and particularly the insecticidal aerosol prepared by the test group 1, namely the formula of the embodiment 3, has the best effect.
TABLE 4 controlling effect of insecticidal aerosol on German cockroach
Group of
|
KT50(min)
|
Mortality rate (%) at 72h
|
1h knockdown (%)
|
Test 1 group
|
2.02
|
93.75
|
97.50
|
Test 2 groups
|
2.16
|
92.50
|
96.25
|
Test 3 groups
|
2.30
|
90.00
|
93.75
|
Test 4 groups
|
2.26
|
91.25
|
95.00
|
Test 5 groups
|
2.24
|
92.50
|
95.00
|
Test 6 groups
|
2.20
|
92.50
|
96.25
|
Test 7 groups
|
2.28
|
90.00
|
93.75
|
Comparative 1 group
|
3.68
|
82.50
|
87.50
|
Comparative 2 group
|
4.05
|
76.25
|
80.00
|
Comparative 3 group
|
2.76
|
87.50
|
91.25
|
Comparative 4 group
|
3.98
|
77.50
|
81.25
|
COMPARATIVE 5 GROUP (commercially available)
|
3.75
|
81.25
|
87.50 |
As can be seen from the tests 1-7, the insecticide aerosols prepared in the examples 3-9 of the present invention have half the knock-down time (KT) against Blattella germanica50) Within the range of 2.02-2.30 min, the death rate of culex pipiens pallens after 72h reaches over 90.00 percent,the knockdown rate of 1h reaches more than 93.75 percent, which is obviously superior to that of comparison groups 1-4 and commercial product groups, and shows that the pyrethroid compound, the glyceride of soy sauce residue and the palmatine in the insecticide aerosol are compounded, so that the insecticide aerosol has obvious synergistic and beneficial killing effect on Blattella germanica, and particularly, the insecticide aerosol prepared by experiment group 1, namely the formula of example 3, has the best effect.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.