Disclosure of Invention
The invention aims to provide an environment-friendly insecticidal aerosol and a preparation method thereof. The environment-friendly insecticidal aerosol is a homogeneous O/W type water-based microemulsion system with stable thermodynamics, has the advantages of nano-scale particle size, no layering after long-term storage, good stability, direct spraying without shaking, and quick killing effect on mosquitoes, flies and cockroaches.
The invention is realized by the following technical scheme:
the environment-friendly insecticidal aerosol is characterized by comprising the following components in percentage by mass:
the synergist is one of synergistic ether, synergistic amine and synergistic ester.
Preferably, the synergistic ether is piperonyl butoxide oxide, octachlorodipropyl ether or 3, 4-methylenedioxy-6-n-propylbenzyl-n-butyldiglycol ether; the synergistic amine is N- (2-ethylhexyl) bicyclo (2.2.1) hept-5-ene-2, 3-dicarboximide or N- (2-ethylhexyl) -1-isopropyl-4-methylbicyclo (2.2.2) hept-5-ene-2, 3-dicarboximide; the synergistic ester is isobornyl thiocyanoacetate or butyl ethyl acetaminopropionate.
The plant essential oil is selected from one of lemon essential oil, bergamot oil, mint essential oil, lavender oil and orange flower essential oil.
The surfactant is composed of mannitol erythritol ester and surfactant peptide in a mass ratio of 1: 0.01-0.1.
Preferably, the surfactant is composed of mannitol erythritol lipid and surfactant peptide in a mass ratio of 1: 0.01-0.05.
More preferably, the surfactant is composed of mannitol erythritol lipid and surfactant peptide in a mass ratio of 1: 0.02.
The propellant is selected from one of dimethyl ether, propane, n-butane, isobutane, n-pentane and propane-butane.
The invention also provides a preparation method of the environment-friendly insecticidal aerosol, which comprises the following steps:
s1: mixing natural pyrethroid, synergist, plant essential oil, neopentyl glycol dicaprylate/caprate, surfactant and water in proportion, and fully stirring until the mixture is clear to obtain liquid medicine;
s2: filling the medicinal liquid into an aerosol container, inserting a valve and sealing;
s3: injecting a propellant into the aerosol container under high pressure, and pressing an aerosol cover to obtain the environment-friendly insecticidal aerosol.
In experiments, the invention discovers that the water-based insecticidal aerosol prepared by using surfactants such as alkylphenol ethoxylates (emulsifier OP-10), polyoxyethylene sorbitan monooleate (Tween 80) and the like can form a homogeneous O/W emulsion system, but after standing for a period of time, the solution is layered, the aerosol needs to be shaken when being used again, and the aerosol prepared from the emulsifier has larger fog drops and shorter retention time in space, is not beneficial to the contact of insecticidal components and winged insects, greatly reduces the drug effect, and simultaneously, the aerosol using the emulsifier is easy to foam when being sprayed, has poorer atomization effect and is not beneficial to the remote spraying of the aerosol. Furthermore, in order to overcome the defects, the inventor tries to add n-propanol serving as an alcohol cosurfactant, and as a result, the combination of the n-propanol and an emulsifier OP-10 or Tween 80 can inhibit the layering of an aerosol solution system, but the viscosity of the aerosol solution is relatively high, the particle size of formed droplets is large, the droplets are quickly settled, the spatial residence time is short, a nozzle is easy to foam during spraying, and the foaming phenomenon of the system is not inhibited.
Therefore, the present inventors have tried to use mannosylerythritol lipids as an emulsifier, which is a glycolipid biosurfactant, and have found that a solution system is likely to be sticky when a surfactant having a high hydrophilicity such as emulsifiers OP-10 and tween 80 is used, although a phenomenon that a solution system is likely to be sticky when a surfactant having a high hydrophilicity such as mannitol lipids is used can be avoided because mannosylerythritol lipids have an HLB value of about 8.7 and have a certain degree of lipophilicity, and at the same time, it has also been found that it is difficult to form an O/W type emulsified composition by using only mannosylerythritol lipids. Unexpectedly, the present inventors have found through extensive experiments that in the present invention, by using a small amount of a surface active peptide (Surfactin) as a co-emulsifier on the basis of a mannosylerythritol lipid as an emulsifier, the stable O/W type water-based microemulsion system can be obtained, the Surfactin is formed by combining a peptide ring containing 7 amino acid residues and beta-hydroxy fatty acid containing 13-16 carbon atoms by an inner ester bond, the arrangement of the amino acid is Leu-Leu-Asp-Val-Leu-Leu-Glu, the side chain hydrophilic property of the amino acid and the hydrophobicity of beta-hydroxy fatty acid ensure that the side chain hydrophilic property and the hydrophobicity of beta-hydroxy fatty acid compete with the mannose erythritol ester at a water/oil interface, the mannitol erythritol lipid molecules repel each other, and the instantaneous negative surface tension formed on the interface is favorable for forming the microemulsion. The O/W type water-based microemulsion system has the advantages that the particle size is within the range of 10-100 nm, the appearance is transparent, the layering is avoided after the system is placed for a long time, the stability is good, the direct spraying can be realized without shaking, the viscosity of the emulsion is small, the particle size of formed droplets is small, the retention time in space is long, the bubbling is not easy, the atomization is easy, the long-distance spraying is facilitated, the quick killing effect on winged insect pests such as mosquitoes and flies and crawling insect pests such as cockroaches is realized, the insect killing effect is close to that of oil-based products, and the unexpected technical effect is obtained.
The natural pyrethroid is an active ingredient with insecticidal effect separated and extracted from pyrethrum, contains six insecticidal substances, has the advantages of broad spectrum, high efficiency, environmental protection, low toxicity, difficult generation of drug resistance of insects and the like, and is an internationally recognized safe insecticide. The natural pyrethroid and the synergist are combined, so that the insecticidal effect of the insecticidal aerosol can be obviously improved. The plant essential oil with pest repelling effect is further added, so that the contact killing, repelling and sterilizing effects of the insect aerosol can be improved, the fragrance of the aerosol can be adjusted, and the aerosol has natural fragrance of plants.
The neopentyl glycol dicaprylate/caprate has the product name: liponate NPGC-2 is neutral non-ionic liquid, low in viscosity, colorless, tasteless and nontoxic, is branched chain oil ester with a cross structure, has good compatibility with insect surface wax, excellent air permeability and excellent adsorption property, can promote the absorption of insecticidal active ingredients, and obviously improves the insecticidal effect of the water-based insecticidal aerosol.
Compared with the prior art, the invention has the following beneficial effects:
(1) the environment-friendly insecticidal aerosol is a homogeneous O/W type water-based microemulsion system with stable thermodynamics, is not layered after being placed for a long time, has good stability, can be directly sprayed without shaking, is convenient to use, has small particle size of formed fog drops, long residence time in space, difficult bubbling and easy atomization, is beneficial to remote spraying, has quick killing effect on flying insect pests such as mosquitoes and flies and crawling insect pests such as cockroaches and the like, and has the insecticidal effect close to that of oil-based products.
(2) The environment-friendly insecticidal aerosol provided by the invention is simple in preparation process, is not limited by the type of the propellant, can form a transparent homogeneous microemulsion system, and is easy for large-scale production.
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.
Example 1
An environment-friendly insecticidal aerosol comprises the following components in percentage by mass:
1% of natural pyrethroid, 0.5% of oxidized piperonyl butoxide, 1.5% of lemon essential oil, 2% of neopentyl glycol dicaprylate/caprate, 0.98% of mannoerythritols, 0.02% of surface active peptide, 40% of dimethyl ether and 54% of water.
The preparation method comprises the following steps:
s1: mixing natural pyrethroid, piperonyl butoxide oxide, lemon essential oil, neopentyl glycol dicaprylate/caprate, mannosylerythritol ester, surfactant peptide and water in proportion, and stirring thoroughly to clarify to obtain medicinal liquid;
s2: filling the medicinal liquid into an aerosol container, inserting a valve and sealing;
s3: and (3) injecting dimethyl ether into the aerosol container under high pressure, and pressing an aerosol cover to obtain the environment-friendly insecticidal aerosol.
Example 2
An environment-friendly insecticidal aerosol comprises the following components in percentage by mass:
natural pyrethroid 1.5%, piperonyl butoxide oxide 0.3%, bergamot oil 1.2%, neopentyl glycol dicaprylate/caprate 1%, mannosylerythritol esters 0.98%, surface active peptide 0.02%, propyl butane 35% and water 60%.
The preparation procedure is as in example 1.
Example 3
An environment-friendly insecticidal aerosol comprises the following components in percentage by mass:
2% of natural pyrethroid, 0.2% of piperonyl butoxide oxide, 0.8% of neroli essential oil, 3% of neopentyl glycol dicaprylate/caprate, 0.98% of mannosylerythritol esters, 0.02% of surface active peptide, 40% of n-butane and 53% of water.
The preparation procedure is as in example 1.
Example 4
An environment-friendly insecticidal aerosol comprises the following components in percentage by mass:
0.5% of natural pyrethroid, 0.6% of piperonyl butoxide oxide, 1.2% of mint essential oil, 1% of neopentyl glycol dicaprylate/caprate, 0.67% of mannosylerythritol lipid, 0.03% of surface active peptide, 45% of isobutane and 51% of water.
The preparation procedure is as in example 1.
Example 5
An environment-friendly insecticidal aerosol comprises the following components in percentage by mass:
0.5% of natural pyrethroid, 0.5% of piperonyl butoxide oxide, 0.5% of bergamot oil, 2% of neopentyl glycol dicaprylate/caprate, 0.48% of mannosylerythritol esters, 0.02% of surface active peptide, 40% of propane-butane and 56% of water.
The preparation procedure is as in example 1.
Example 6
An environment-friendly insecticidal aerosol comprises the following components in percentage by mass:
1% of natural pyrethroid, 0.6% of oxidized piperonyl butoxide, 1.4% of lavender oil, 1% of neopentyl glycol dicaprylate/caprate, 0.98% of mannosylerythritol ester, 0.02% of surface active peptide, 45% of dimethyl ether and 50% of water.
The preparation procedure is as in example 1.
Comparative example 1
An environment-friendly insecticidal aerosol comprises the following components in percentage by mass:
1% of natural pyrethroid, 0.5% of oxidized piperonyl butoxide, 1.5% of lemon essential oil, 2% of neopentyl glycol dicaprylate/caprate, 801% of tween, 40% of dimethyl ether and 54% of water.
The preparation procedure is as in example 1.
Comparative example 2
An environment-friendly insecticidal aerosol comprises the following components in percentage by mass:
1% of natural pyrethroid, 0.5% of oxidized piperonyl butoxide, 1.5% of lemon essential oil, 2% of neopentyl glycol dicaprylate/caprate, an emulsifier OP-101%, 40% of dimethyl ether and 54% of water.
The preparation procedure is as in example 1.
Comparative example 3
An environment-friendly insecticidal aerosol comprises the following components in percentage by mass:
1% of natural pyrethroid, 0.5% of oxidized piperonyl butoxide, 1.5% of lemon essential oil, 2% of neopentyl glycol dicaprylate/caprate, 801% of tween, 4% of n-propanol, 40% of dimethyl ether and 50% of water.
The preparation procedure is as in example 1.
Comparative example 4
An environment-friendly insecticidal aerosol comprises the following components in percentage by mass:
1% of natural pyrethroid, 0.5% of piperonyl butoxide oxide, 1.5% of lemon essential oil, 2% of neopentyl glycol dicaprylate/caprate, 4% of n-propanol, 40% of dimethyl ether and 50% of water.
The preparation procedure is as in example 1.
Comparative example 5
An environment-friendly insecticidal aerosol comprises the following components in percentage by mass:
1% of natural pyrethroid, 0.5% of piperonyl butoxide oxide, 1.5% of lemon essential oil, 2% of neopentyl glycol dicaprylate/caprate, 1% of mannosylerythritol ester, 40% of dimethyl ether and 54% of water.
The preparation procedure is as in example 1.
Comparative example 6
An environment-friendly insecticidal aerosol comprises the following components in percentage by mass:
1% of natural pyrethroid, 0.5% of piperonyl butoxide, 1.5% of lemon essential oil, 0.98% of mannosylerythritol ester, 0.02% of surfactant peptide, 40% of dimethyl ether and 56% of water.
The preparation procedure is as in example 1.
Test example I, physical and chemical stability test
(1) Room temperature stability test: the environment-friendly pesticidal aerosols prepared in examples 1 to 6 and comparative examples 1 to 6 (for easy observation, the aerosol container is a transparent glass container) were allowed to stand at room temperature for 24 hours, and whether or not the aerosols were layered was observed, and the results are shown in table 1.
(2) High temperature stability test: the environment-friendly pesticidal aerosol prepared in examples 1 to 6 and comparative examples 1 to 6 were placed in a high-temperature environment of 50 ℃ for 24 hours, respectively, and an accelerated test was carried out to observe whether the aerosol was delaminated, the results of which are shown in table 1.
(3) Detecting the particle size change of the fogdrops: the particle size change of the aerosol formulations prepared in examples 1 to 6 and comparative examples 1 to 6 was measured by using a spray laser particle size analyzer after standing at room temperature for 24 hours before the test, and the results are shown in Table 2.
TABLE 1 stability test results
Group of
|
Standing at room temperature for 24h
|
Standing at 50 deg.C for 24h
|
Example 1
|
Without delamination
|
Without delamination
|
Example 2
|
Without delamination
|
Without delamination
|
Example 3
|
Without delamination
|
Without delamination
|
Example 4
|
Without delamination
|
Without delamination
|
Example 5
|
Without delamination
|
Without delamination
|
Example 6
|
Without delamination
|
Without delamination
|
Comparative example 1
|
Layering
|
Layering
|
Comparative example 2
|
Layering
|
Layering
|
Comparative example 3
|
Without delamination
|
Layering
|
Comparative example 4
|
Without delamination
|
Layering
|
Comparative example 5
|
Layering
|
Layering
|
Comparative example 6
|
Without delamination
|
Without delamination |
Table 1 shows that the environment-friendly insecticidal aerosols prepared in examples 1 to 6 are homogeneous transparent liquids, and no delamination occurs when the aerosols are placed at room temperature for 24 hours or at a high temperature of 50 ℃ for 24 hours. As can be seen from comparative examples 1-2, when Tween 80 or emulsifier OP-10 was used as the emulsifier, the resulting aerosol was layered at room temperature or at high temperature, and the solution system was unstable. As can be seen from comparative examples 3-4, when Tween 80 or emulsifier OP-10 was used as the emulsifier and n-propanol was used as the co-emulsifier, the aerosol prepared was stable at room temperature but did not resist high temperature and was delaminated at high temperature. As can be seen from comparative example 5, the aerosol only contains the emulsifier mannitol ester, does not contain the coemulsifier surface active peptide, the solution system is unstable at room temperature and high temperature, and layering occurs, which shows that the stable O/W type emulsification system is difficult to form by using the mannitol erythritol ester alone, the surface active peptide has an important effect on improving the stability of the aerosol solution, and the stable O/W type water-based microemulsion system can be promoted to form by using the mannitol erythritol ester together. From comparative example 6, it is clear that neopentyl glycol dicaprylate/caprate does not affect the stability of the aerosol solution.
TABLE 2 detection results of the change in droplet size
Table 2 shows that the environmental protection type aerosol insecticides prepared in examples 1-6 were used for 24 hours at room temperature or 24 hours at 50 deg.C, the average droplet size was not significantly increased, the system stability was good, and the formed droplets were of nanometer size and smaller size. As can be seen from comparative examples 1-2, the aerosol prepared by using Tween 80 or emulsifier OP-10 as emulsifier has large and micron-sized droplet size, and is placed at room temperature for 24h or at high temperature of 50 ℃ for 24h, and the average droplet size is obviously increased and the system stability is poor compared with that before the test. As can be seen from comparative examples 3-4, when Tween 80 or emulsifier OP-10 is used as an emulsifier and n-propanol is added as a co-emulsifier, the particle size of the droplets formed by the prepared aerosol is larger than that of the aerosol prepared in examples 1-6, and the aerosol is placed at a high temperature of 50 ℃ for 24 hours, so that the average particle size of the droplets is obviously increased compared with that before the test, and the system stability is poor. As can be seen from comparative example 5, the aerosol only contains the emulsifier mannitol erythritol ester and does not contain the coemulsifier surface active peptide, the particle size of the droplets formed by the prepared aerosol is larger and micron-sized, and the aerosol is placed at room temperature for 24 hours or at high temperature of 50 ℃ for 24 hours, so that the average particle size of the droplets is obviously increased compared with that before the test, and the system stability is poor. From comparative example 6, it is clear that the absence of neopentyl glycol dicaprylate/caprate has little effect on the average aerosol droplet size.
Test example two, detection of insecticidal Effect
According to GB/T13917.2-2009 indoor pesticide effect test and evaluation part 2 of pesticide registration and hygiene pesticides: aerosol analysis, the environmental protection insecticidal aerosols prepared in examples 1-6 and comparative examples 1-6 were tested for their mosquito, fly, and cockroach killing effects, and the results are shown in Table 3.
TABLE 3 insecticidal Effect test results
Table 3 shows 50% Knockdown Time (KT) of the eco-friendly insecticidal aerosol prepared in examples 1 to 6 against Culex pipiens pallens50) 1.28-1.54 min, the mortality rate of 24h is 100 percent, and the knock-down time (KT) of the housefly is 50 percent50) 1.44-1.84 min, the mortality rate of 24h is 100%, and the 50% knock-down time (KT) of the German cockroach is50) Is 1.87-2.36 min, has a mortality rate of 94.90-98.24% after 24h, and is obviously superior to the environment-friendly insecticidal aerosol prepared in the comparative examples 1-6. As can be seen from comparative examples 1-2, the aerosol prepared by using Tween 80 or emulsifier OP-10 as emulsifier has a reduced killing effect on Culex pipiens, Musca domestica, and Blattella germanica, which is presumed to be caused by the instability of the aerosol solution system, resulting in insufficient effect of the active ingredient on the pests. As shown in comparative examples 3-4, the insecticidal effect of the aerosol prepared by using Tween 80 or emulsifier OP-10 as an emulsifier and adding n-propanol as a co-emulsifier is slightly reduced. From comparative example 5It is known that the aerosol containing only the emulsifier mannosylerythritol lipids and not containing the co-emulsifier surfactant peptide significantly reduced the insecticidal effect of the resulting aerosol, and it is presumed that the insecticidal effect is reduced because it is difficult to form an O/W type emulsified composition using only the mannosylerythritol lipids as the emulsifier. As can be seen from comparative example 6, the absence of neopentyl glycol dicaprylate/caprate significantly reduced the insecticidal effect of the insecticidal aerosol, indicating that neopentyl glycol dicaprylate/caprate has an important effect on enhancing the insecticidal effect of the aerosol.
Test example III atomization Effect test
The atomization effect of the environment-friendly insecticidal aerosol prepared in example 1 and comparative examples 1 to 6 was measured, and it was observed whether the nozzle was easily foamed during spraying, and the results are shown in table 4.
TABLE 4 results of the atomization Effect test
Table 4 shows that the environment-friendly insecticidal aerosol prepared in example 1 has an excellent atomization effect, and the nozzle does not easily foam during spraying, which is beneficial to increase the spray distance, and the effect is superior to that of the environment-friendly insecticidal aerosols prepared in comparative examples 1 to 6.
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.