CN115669667B - Composition containing 2-methyl-4-chloroisooctyl ester, fluroxypyr-meptyl ester and clopyralid, and preparation method and application thereof - Google Patents
Composition containing 2-methyl-4-chloroisooctyl ester, fluroxypyr-meptyl ester and clopyralid, and preparation method and application thereof Download PDFInfo
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- CN115669667B CN115669667B CN202211200751.9A CN202211200751A CN115669667B CN 115669667 B CN115669667 B CN 115669667B CN 202211200751 A CN202211200751 A CN 202211200751A CN 115669667 B CN115669667 B CN 115669667B
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- -1 2-methyl-4-chloroisooctyl ester Chemical class 0.000 title claims abstract description 73
- HUBANNPOLNYSAD-UHFFFAOYSA-N clopyralid Chemical compound OC(=O)C1=NC(Cl)=CC=C1Cl HUBANNPOLNYSAD-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000005500 Clopyralid Substances 0.000 title claims abstract description 44
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000000375 suspending agent Substances 0.000 claims abstract description 35
- 241000196324 Embryophyta Species 0.000 claims abstract description 31
- 239000005558 Fluroxypyr Substances 0.000 claims abstract description 17
- 239000003921 oil Substances 0.000 claims description 41
- 239000004480 active ingredient Substances 0.000 claims description 16
- 239000002270 dispersing agent Substances 0.000 claims description 14
- 239000003995 emulsifying agent Substances 0.000 claims description 14
- 239000002562 thickening agent Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 240000008042 Zea mays Species 0.000 claims description 11
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- 238000000034 method Methods 0.000 claims description 11
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- SFGBOBMTMFHZJH-UHFFFAOYSA-N 1-chloro-6-methylheptane Chemical compound CC(C)CCCCCCl SFGBOBMTMFHZJH-UHFFFAOYSA-N 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
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- 238000000227 grinding Methods 0.000 claims description 8
- OLZQTUCTGLHFTQ-UHFFFAOYSA-N octan-2-yl 2-(4-amino-3,5-dichloro-6-fluoropyridin-2-yl)oxyacetate Chemical group CCCCCCC(C)OC(=O)COC1=NC(F)=C(Cl)C(N)=C1Cl OLZQTUCTGLHFTQ-UHFFFAOYSA-N 0.000 claims description 8
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- OOCMUZJPDXYRFD-UHFFFAOYSA-L calcium;2-dodecylbenzenesulfonate Chemical compound [Ca+2].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O OOCMUZJPDXYRFD-UHFFFAOYSA-L 0.000 claims description 4
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- 238000004519 manufacturing process Methods 0.000 claims description 3
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 claims description 3
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- 239000003814 drug Substances 0.000 description 7
- 238000005507 spraying Methods 0.000 description 7
- MEFQWPUMEMWTJP-UHFFFAOYSA-N fluroxypyr Chemical compound NC1=C(Cl)C(F)=NC(OCC(O)=O)=C1Cl MEFQWPUMEMWTJP-UHFFFAOYSA-N 0.000 description 6
- 231100000419 toxicity Toxicity 0.000 description 6
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- 238000001556 precipitation Methods 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
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- 235000003092 Artemisia dracunculus Nutrition 0.000 description 2
- 240000001851 Artemisia dracunculus Species 0.000 description 2
- 240000006122 Chenopodium album Species 0.000 description 2
- 235000009344 Chenopodium album Nutrition 0.000 description 2
- 235000015493 Chenopodium quinoa Nutrition 0.000 description 2
- 231100000674 Phytotoxicity Toxicity 0.000 description 2
- 235000009754 Vitis X bourquina Nutrition 0.000 description 2
- 235000012333 Vitis X labruscana Nutrition 0.000 description 2
- 240000006365 Vitis vinifera Species 0.000 description 2
- 235000014787 Vitis vinifera Nutrition 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 230000032823 cell division Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 241001233957 eudicotyledons Species 0.000 description 2
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- 230000005764 inhibitory process Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002420 orchard Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011885 synergistic combination Substances 0.000 description 2
- 230000009885 systemic effect Effects 0.000 description 2
- 230000001018 virulence Effects 0.000 description 2
- RTYRHAFIKFDTFQ-UHFFFAOYSA-N 1-dodecyl-2-propan-2-ylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1C(C)C RTYRHAFIKFDTFQ-UHFFFAOYSA-N 0.000 description 1
- 241001060350 Acalypha Species 0.000 description 1
- 244000237956 Amaranthus retroflexus Species 0.000 description 1
- 235000013479 Amaranthus retroflexus Nutrition 0.000 description 1
- XMTDHFPEXKXPNY-UHFFFAOYSA-N CC(C)CC(CC(C)CCl)Cl Chemical compound CC(C)CC(CC(C)CCl)Cl XMTDHFPEXKXPNY-UHFFFAOYSA-N 0.000 description 1
- 208000003643 Callosities Diseases 0.000 description 1
- 241000217446 Calystegia sepium Species 0.000 description 1
- 235000001602 Digitaria X umfolozi Nutrition 0.000 description 1
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- 244000025670 Eleusine indica Species 0.000 description 1
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- 241001101998 Galium Species 0.000 description 1
- 102000018997 Growth Hormone Human genes 0.000 description 1
- 108010051696 Growth Hormone Proteins 0.000 description 1
- 206010020649 Hyperkeratosis Diseases 0.000 description 1
- 240000001140 Mimosa pudica Species 0.000 description 1
- 235000016462 Mimosa pudica Nutrition 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- 230000005540 biological transmission Effects 0.000 description 1
- 229920005551 calcium lignosulfonate Polymers 0.000 description 1
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 1
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- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
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- 150000002191 fatty alcohols Chemical class 0.000 description 1
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- 229910021485 fumed silica Inorganic materials 0.000 description 1
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- QIIPQYDSKRYMFG-UHFFFAOYSA-N phenyl hydrogen carbonate Chemical compound OC(=O)OC1=CC=CC=C1 QIIPQYDSKRYMFG-UHFFFAOYSA-N 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a composition containing 2-methyl-4-chloroisooctyl ester, fluroxypyr isooctyl ester and clopyralid, and a preparation method and application thereof, wherein the composition is prepared by compounding the 2-methyl-4-chloroisooctyl ester, fluroxypyr isooctyl ester and clopyralid, has remarkable synergistic effect on the aspect of weed control, enlarges the weeding spectrum, can complement synergistic effect, improves the weeding effect, reduces the product consumption, lowers the cost, improves the safety of crops, and has the characteristics of synergistic effect, delayed drug resistance and the like. The invention provides a dispersible oil suspending agent dosage form of 2-methyl-4-chloroisooctyl ester, fluroxypyr-meptyl ester and clopyralid, which improves the emulsification dispersibility, suspension rate and stability of the dispersible oil suspending agent through the selection of auxiliary agents, and the obtained dispersible oil suspending agent has the advantages of good emulsification dispersibility, high suspension rate, difficult layering or oil separation and good thermal storage stability.
Description
Technical Field
The invention relates to a composition containing 2-methyl-4-chloroisooctyl ester, fluroxypyr-meptyl ester and clopyralid, and a preparation method and application thereof, and belongs to the technical field of pesticides.
Background
2 Methyl 4 chloroisooctyl ester, chemical name: the 4-chloro-2-methyl phenoxyacetic acid isooctyl ester belongs to selective phenoxy carboxylic acid herbicide, has stronger systemic conductivity, can damage the transmission tissue of dicotyledon, leads the growth and development of dicotyledon to be interfered, and leads the stem and the leaf to be distorted, and leads the base of the stem to be enlarged and thickened or cracked. Currently, the main dosage forms of 2-methyl-4-chloroisooctyl ester are aqueous emulsion and emulsifiable concentrate.
Isooctyl fluroxypyr ester, chemical name: the 4-amino-3, 5-dichloro-6-fluoro-2-pyridyloxyacetic acid isooctyl ester belongs to pyridine systemic conduction type post-emergence stem and leaf treatment herbicide, and is quickly absorbed by weeds after application, so that sensitive plants react with typical hormone herbicide and are conducted to all parts of the whole plant, the plant is deformed, distorted and finally dead. At present, the main dosage forms of the fluroxypyr-meptyl are aqueous emulsion and emulsifiable concentrate.
Clopyralid, chemical name: the 3, 6-dichloropyridine-2-carboxylic acid belongs to pyridine raw materials, is an artificially synthesized plant growth hormone, is mainly absorbed by roots and leaves of plants and then is conducted in the plants, so that the conductivity is strong. After the herbicide is applied to weeds, the herbicide is absorbed by leaves or roots of plants and then conducted in the plants, so that cell division is out of control and disordered growth is caused, finally, vascular bundles are damaged, and cell division and growth can be inhibited. Currently, the main dosage forms of clopyralid are water aqua, soluble granules, soluble powder and the like.
Herbicide varieties containing a single active ingredient often suffer from varying degrees of deficiencies in agricultural pest control, such as: the weeding spectrum is narrow, weeds are easy to generate drug resistance after continuous use, and the pollution to the environment can be aggravated after the weeding composition is used for a plurality of times. The proper compound herbicide has the positive characteristics of strong complementation, obvious synergistic effect, wide control spectrum, reduced application amount, prolonged application period, high safety to crops, reduced environmental pollution and the like, and of course, if the active ingredients are improperly selected, the problems of antagonism, difficult performance of the preparation and the like are easily generated after the compound herbicide is compounded, and the more the types of the compound active ingredients, the more the research and development difficulty to the preparation is high. Most of the existing single-component or two-component compounds in the market are related active components, the three-component compound preparation is less, and no related report on the three-component compound composition of 2-methyl-4-chloroisooctyl ester, fluroxypyr-meptyl and clopyralid and the dosage forms thereof is available at present.
Disclosure of Invention
The invention aims to provide a composition containing 2-methyl-4-chloroisooctyl ester, fluroxypyr-meptyl ester and clopyralid, and the composition is used by compounding the 2-methyl-4-chloroisooctyl ester, the fluroxypyr-meptyl ester and the clopyralid, and has outstanding unexpected excellent effects in weeding through experimental verification.
In order to achieve the above object, the present invention provides the following technical solutions:
The active components of the composition are 2-methyl-4-chloroisooctyl ester, fluroxypyr and clopyralid, and the three components are compounded to have synergistic weeding effect, can improve the weeding effect, can expand the weeding spectrum and can improve the safety to crops. Within the mass ratio range, the mass ratio of the 2-methyl 4-chloroisooctyl acetate, the fluroxypyr-meptyl acetate and the clopyralid is 10-30:1-10:3, such as 10:1:3, 10:5:3, 10:10:3, 20:1:3, 20:5:3, 20:10:3, 26:6:3, 30:1:3, 30:5:3 and 30:10:3, wherein the three have a synergistic effect, and the synergistic effect is most obvious when the mass ratio of the 2-methyl 4-chloroisooctyl acetate, the fluroxypyr-acetate and the clopyralid is 26:6:3.
Furthermore, the invention also provides a dispersible oil suspending agent which comprises active ingredients, wherein the active ingredients are the compound composition of the 2-methyl-4-chloroisooctyl ester, the fluroxypyr-meptyl and clopyralid.
Further, in the above-mentioned dispersible oil suspension agent, the content of the active ingredient is 5 to 50% by weight, for example, 5% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, 50% by weight, preferably 5 to 30% by weight.
Further, the raw 2-methyl-4-chloroisooctyl ester is yellow to brown yellow liquid with a melting point of-48 ℃; the stock solution of the fluroxypyr is white or white-like powder with a melting point of 56-57 ℃; the clopyralid raw material is yellow or light yellow powder with a melting point of 151 ℃ and a log P value of-2.63. The 2-methyl-4-chloroisooctyl ester and the fluroxypyr-meptyl ester have higher lipophilicity, the melting point of the fluroxypyr-meptyl ester is lower, the fluroxypyr-meptyl ester is easy to generate creaming or recrystallization in the sanding or heat storage process, and the clopyralid has strong hydrophilicity, so that the 3 active ingredients are easy to generate problems of layering, oil separation, poor stability and the like when being prepared into a dispersible oil suspending agent, and the performance of the active ingredients is influenced. Aiming at the problem, the inventor researches and experiments an auxiliary agent system of the dispersible oil suspending agent according to the characteristics of the three medicinal active ingredients, and selects an emulsifying agent, a dispersing agent, a thickening agent and a dispersing medium as auxiliary agents, and through the synergistic combination of the auxiliary agents, especially the synergistic combination of 3 auxiliary agents of the emulsifying agent, the dispersing agent and the thickening agent, the processing difficulty of the dispersible oil suspending agent is greatly reduced, and the stability of the dispersible oil suspending agent is improved, so that the obtained dispersible oil suspending agent has the advantages of good emulsifying dispersibility, high suspension rate, difficult layering or oil precipitation, difficult creaming or recrystallization, good thermal storage stability, effectively solves or reduces the problems of creaming or recrystallization, layering, oil precipitation, poor thermal storage stability and the like of the preparation, and is more beneficial to the exertion of medicinal effects.
Further, in the dispersible oil suspending agent, the weight percentages of the active ingredients and the auxiliary agents are as follows: 5-50% of active ingredient, 5-20% of emulsifying agent, 1-6% of dispersing agent, 1-8% of thickening agent and 100% of dispersing medium.
Further, the emulsifier is one or more of castor oil polyoxyethylene ether, polyoxyethylene sorbitan monooleate, styrylphenol polyoxyethylene ether, calcium dodecyl benzene sulfonate, fatty alcohol polyoxyethylene ether and isopropyl dodecyl benzene sulfonate.
Further, the dispersing agent is one or more of polyoxyethylene-polyoxypropylene block copolymer, calcium lignosulfonate and alkyl naphthalene sulfonate formaldehyde condensate.
Further, the thickener is one or more of fumed silica, organic bentonite, attapulgite and urea.
Furthermore, the dispersion medium is one or more of soybean oil, methyl oleate, castor oil and methyl soyate, and the dispersion medium used in the invention is an environment-friendly green solvent, is more favorable for environmental protection, has good compatibility to each component and improves the stability of the product.
Preferably, in the dispersible oil suspending agent, the emulsifying agent is formed by mixing castor oil polyoxyethylene ether and calcium dodecyl benzene sulfonate according to the mass ratio of 3-6:1; the dispersing agent is formed by mixing alkyl naphthalene sulfonate formaldehyde condensate and polyoxyethylene-polyoxypropylene segmented copolymer according to the mass ratio of 1:1-2; the thickener is formed by mixing gas phase white carbon black and organic bentonite according to the mass ratio of 1-4:1; the dispersion medium is methyl oleate. The optimization of the performance of the dosage form and the efficacy exertion of the effective components are facilitated by the optimization of the auxiliary agents, and particularly, the optimization of the emulsifying agent, the dispersing agent and the thickening agent has better promotion effect on the performance and the efficacy exertion of the dosage form.
Further, in the above dispersible oil suspension, the content of the pharmaceutically active ingredient is 5 to 50wt%, for example, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%.
Further, in the above-mentioned dispersible oil suspending agent, the content of the emulsifier is 5 to 20% by weight, for example, 5% by weight, 10% by weight, 14% by weight, 17% by weight, 20% by weight.
Further, in the above-mentioned dispersible oil suspending agent, the content of the dispersant is 1 to 6% by weight, for example, 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight.
Further, in the above-mentioned dispersible oil suspending agent, the thickener content is 1 to 8% by weight, for example, 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight.
Further, the invention also provides a preparation method of the dispersible oil suspending agent, which comprises the following steps: and (3) uniformly mixing and dispersing a dispersing medium, an emulsifying agent and a dispersing agent, adding a thickening agent, fluroxypyr ester and clopyralid, fully shearing and uniformly mixing, grinding the mixture until the particle size D 90 is smaller than 4 mu m, finally adding 2 methyl 4 isooctyl chloride, and homogenizing to obtain the dispersible oil suspending agent.
Further, in the preparation method, the shearing speed is 1000-10000r/min, the full mixing and emulsification can be realized quickly under the shearing speed, and the shearing time is generally 10-30 minutes as the shearing speed is higher.
Further, in the preparation method, the 2-methyl-4-chloroisooctyl ester and other materials are fully and uniformly mixed by homogenization, and the homogenization time is generally 30-40 minutes.
Further, in the above preparation method, the grinding may be performed by any grinding method disclosed in the prior art, for example, grinding may be performed under a zirconia bead grinding medium. After grinding, the particles were measured by a laser particle size distribution analyzer until the particle diameter D 90 was smaller than 4. Mu.m.
The invention also provides the application of the composition containing the 2-methyl-4-chloroisooctyl ester, the fluroxypyr-meptyl ester and clopyralid or the dispersible oil suspending agent in weed control. The invention has wider application period on cereal crops, and can be used for preventing and killing broadleaf weeds in wheat, barley, corn, grape, orchards, pastures, forest lands and the like, wherein the broadleaf weeds comprise chenopodium quinoa, cleavers, bindweed, shepherd's purse, amaranth, chickweed, amaranth, purslane, copperleaf, tarragon, large nest, and the like.
The invention has the following beneficial effects:
1. The invention compounds the 2-methyl-4-chloroisooctyl ester, the fluroxypyr and the clopyralid, has obvious synergy in the aspect of preventing and controlling weeds, and the composition not only expands the weeding spectrum, but also can complement synergy, improves the weeding effect, reduces the product consumption, reduces the cost, improves the safety of crops, and has the characteristics of synergy, drug resistance delay and the like.
2. The invention provides a dispersible oil suspending agent formulation of 2-methyl-4-chloroisooctyl chloride, fluroxypyr-meptyl chloride and clopyralid, wherein the dispersible oil suspending agent selects an oil auxiliary agent with good adhesiveness and spreadability as a dispersing and diluting carrier, and is easy to adhere to waxy or smooth leaf surfaces, so that the dispersible oil suspending agent has the advantages of good adhesiveness and spreadability, strong permeability and conductivity, strong rain wash resistance and the like when in use. The dispersible oil suspending agent has no dust in the production and use processes, and the environment-friendly solvent oil is used, so that the dispersible oil suspending agent is not easy to pollute the environment and people and livestock, and has better drug effect and stronger environmental compatibility than the conventional dosage forms such as emulsifiable concentrate, aqueous agent and the like.
3. The invention improves the emulsification dispersibility, suspension rate and stability of the dispersible oil suspending agent by selecting the auxiliary agent, and the obtained dispersible oil suspending agent has the advantages of good emulsification dispersibility, high suspension rate, difficult layering or oil precipitation, difficult creaming or recrystallization, good heat storage stability, effectively solves or reduces the problems of creaming or recrystallization, layering, oil precipitation, poor heat storage stability and the like of the preparation, and is more beneficial to the exertion of the drug effect.
4. The invention further improves the performance of the dispersible oil suspending agent through optimizing the auxiliary agent components, the residue of the dispersible oil suspending agent after pouring can be lower than 1.0%, the suspending rate can reach more than 99%, the oil is not separated out after heat storage, the suspending rate is still more than 96%, and the performance is excellent.
5. The preparation process of the dispersible oil suspending agent is simple and convenient to operate, and the prepared dispersible oil suspending agent has excellent index performances, can tolerate different water qualities such as C water, D water and 3WHO water, meets the requirements of different countries and regions, and is beneficial to popularization and application in a large scale.
6. The compound composition of 2-methyl-4-chloroisooctyl, fluroxypyr and clopyralid or the dispersible oil suspending agent thereof has good application prospect in the aspects of preventing and controlling weeds such as wheat, barley, corn, grape, orchards, pastures, forests and the like, and can effectively prevent and remove broadleaf weeds such as chenopodium quinoa, galium, binet, shepherd's purse, amaranth, chickweed, amaranth, purslane, acalypha australis, tarragon, and the like.
Detailed Description
The following examples further illustrate the present invention, but the present invention is not limited to the following examples.
Example 1 indoor toxicity assay
The weeding synergistic effect of the 2-methyl-4-chloroisooctyl ester, the fluroxypyr-meptyl ester and the clopyralid adopts an indoor toxicity measurement method. According to the sun cloud Peel method, indoor toxicity measurement is carried out, and the co-toxicity coefficient (CTC) of the medicament compounded according to a certain proportion is determined, wherein CTC is smaller than 80 and equal to or less than 120 and is additive, and CTC is larger than 120 and is synergistic.
The test agents are all provided by Shandong Weifang Runfeng chemical industry Co., ltd.
And (3) test design: after the effective inhibition concentration range of each medicament is determined through pre-test, each medicament is respectively provided with a series of concentration treatments according to the content of the effective components, and clear water is used for comparison. The method is carried out by referring to herbicide of biological assay test rule in pesticide room, stem and leaf spraying is adopted to measure the concentration of the pesticide and inhibition after mixed use, and the co-toxicity coefficient of the pesticide is calculated by a method proposed by Sunyanpei et al (1960).
The calculation formula is as follows (2-methyl-4-chloroisooctyl ester is used as a standard medicament, and the toxicity index is 100)
Toxicity index of isooctyl fluroxypyr (TI) =2 ED 50 of methyl 4 isooctyl fluroxypyr/ED 50 ×100 of isooctyl fluroxypyr.
Toxicity index of clopyralid (TI) =2ed 50 of methyl 4 chloroisooctyl ester/ED 50 ×100 of clopyralid.
Actual virulence index of M (ATI) =2methyl 4 chloroisooctyl ester ED 50/M ED 50 ×100.
Theoretical virulence index (TTI) =2methyl 4 chloroisooctyl ti×p 2 Nail armor 4 isooctyl chloride +chlorofluoroxyacetic acid isooctyl ti×p Fluroxypyr isooctyl ester +clopyralid ti×p Clopyralid acid .
Wherein: m is a mixture of 2 methyl 4 isooctyl chloride, isooctyl fluroxypyr and clopyralid in different proportions;
P 2 Nail armor 4 isooctyl chloride is the proportion of 2-methyl-4-chloroisooctyl ester in the compound composition;
P Fluroxypyr isooctyl ester is the proportion of the fluroxypyr-meptyl in the compound composition;
P Clopyralid acid is the proportion of clopyralid in the compound composition.
The test results are shown in table 1:
Table 12 toxicity measurement results of Me 4-chloro-isooctyl ester, fluroxypyr-meptyl ester and clopyralid compounded with Chenopodium album
As is clear from Table 1, ED 50 of 2-methyl-4-chloroisooctyl ester, fluroxypyr-meptyl and clopyralid versus Chenopodium album are 141.33mg/L, 75.85mg/L and 50.98mg/L, respectively. When the mass ratio of the 2 methyl 4 isooctyl chloride, the fluroxypyr to the clopyralid is 10:1:3, 10:5:3, 10:10:3, 20:1:3, 20:5:3, 20:10:3, 26:6:3, 30:1:3, 30:5:3 and 30:10:3, the co-toxicity coefficients of the compound composition are 125.09, 127.74, 128.81, 128.99, 129.92, 130.28, 147.24, 135.78, 128.50 and 126.59 respectively and are all greater than 120, the synergistic effect is shown, and when the mass ratio of the 2 methyl 4 isooctyl chloride, the fluroxypyr and the clopyralid is 8:5:1, 55:15:5, the co-toxicity coefficients are only 109.97 and 116.85, and the synergistic effect is not shown. Wherein the synergy is most obvious when the mass ratio of the 2-methyl-4-chloroisooctyl ester, the fluroxypyr-meptyl ester and the clopyralid is 26:6:3.
Example 2
The formula of the dispersible oil suspending agent is shown in table 2, and the content of each component is (wt%): 5.3% of effective components, 4% of emulsifier castor oil polyoxyethylene ether, 1% of calcium dodecyl benzene sulfonate, 1% of dispersant polyoxyethylene-polyoxypropylene block copolymer, 8% of thickener gas-phase white carbon black and 100% of dispersion medium castor oil, wherein the effective components are a mixture of 2 methyl 4-chloroisooctyl ester, fluroxypyr-meptyl ester and clopyralid in a mass ratio of 4:0.8:0.5.
The preparation method of the dispersible oil suspending agent comprises the following steps: adding a dispersing medium, an emulsifying agent and a dispersing agent into a reaction kettle, and fully mixing and dispersing uniformly; adding a thickening agent, fluroxypyr-meptyl and clopyralid into a reaction kettle under a high-speed shearing state of 1000-5000r/min, shearing for 10-30 minutes, grinding until the particle size D 90 of the mixture is smaller than 4 mu m, adding 2 methyl 4-chloroisooctyl, and homogenizing for 30-40 minutes to obtain the dispersible oil suspending agent.
Examples 3 to 10 and comparative example 1
A series of dispersible oil suspensions were formulated according to the formulation in table 2, each oil suspension being prepared as described in example 2.
TABLE 2 dispersible oil suspension formulation (wt%)
Test example Performance detection
The properties of the dispersible oil suspensions prepared in the above examples and comparative examples were examined and the results are shown in Table 3 below. Wherein, the suspension rate is detected according to a GB/T14825-2006 pesticide suspension rate measuring method, the pourability is detected according to a GB/T31737-2015 pesticide pourability measuring method, the dispersion stability is detected according to the International pesticide analysis Cooperation Commission CIPAC MT 180 "suspension emulsion dispersion stability measuring", and the heat storage stability is detected according to a GB/T19136-2003 pesticide heat storage stability measuring method.
TABLE 3 dispersible oil suspending agent product Properties
As shown in Table 3, the formulations can maintain the better performance in the range of 5-50% of the active ingredient content of the drugs as shown in examples 2-10. The products of examples 3, 4, 5 and 6 using the preferred additives were stable in quality before and after heat storage, maintained high suspension rate, low dumping residue and good dispersion stability, and the products of examples 2, 7 and 10 using the non-preferred additives were less stable in dispersion and heat storage stability than examples 3 to 6, but also excellent in performance, whereas the comparative example 1 was poor in dispersion stability of the preparation, low in suspension rate, greatly reduced in stability after heat storage due to improper selection of the emulsifier, dispersant and thickener, had more oil precipitation, and had the problem of crystallization after heat storage.
Field test example: field test corn field annual broadleaf weed efficacy test
The test is arranged in a field suburban in a frigid pavilion area of a city in Shandong province, has flat land, complete irrigation and drainage facilities, consistent field management level and even fertility, and is suitable for the field. Corn is sowed in 6-10 days of 2020, the cultivation mode is direct seeding, and main weeds in a test field are amaranthus retroflexus, crabgrass, purslane, barnyard grass, quinoa, acalypha australis and the like.
And (5) carrying out stem and leaf spraying treatment on the corn in the 4-5 leaf stage. The pesticide is applied by a worker pesticide-16 knapsack manual sprayer for 1 time, 450kg of water is added according to the dosage of each hectare preparation to prepare the pesticide, and the pesticide is uniformly sprayed according to the amount of the pesticide in a converted district. With a random block arrangement, 4 replicates, cell area 30m 2. The test period is good in weather, the application day is rain-free, and the drug is not rained within 10 days after the drug is applied. A total of 5 treatments were set up, each: treatment 1: spraying clear water and blank control; treatment 2: examples 4, 7 and comparative example 1; treatment 3:85wt% of 2-methyl-4-chloroisooctyl ester emulsifiable concentrate; treatment 4:200g/L of fluroxypyr-meptyl ester emulsifiable concentrate; treatment 5:30wt% clopyralid aqueous solution.
Wherein, the dispersible oil suspending agents of examples 4, 7 and comparative example 1 were subjected to the stem and leaf spraying treatment at an effective component amount of 350 g/hectare, the stem and leaf spraying treatment at an effective component amount of 750 g/hectare was performed at a treatment 3, the stem and leaf spraying treatment at an effective component amount of 150 g/hectare was performed at a treatment 4, and the stem and leaf spraying treatment at an effective component amount of 225 g/hectare was performed at a treatment 5.
30 Days after application, the fresh weight control effect of each treatment on weeds and the safety of each treatment on corns are investigated. The results are shown in Table 4.
The investigation method for the fresh weight control effect of weeds comprises the following steps:
And after the pesticide is applied, randomly taking 4 points from each district, wherein each point is 0.25m 2, pulling out annual broadleaf weeds to classify and call the fresh weight of the weeds, and calculating the fresh weight control effect of the weeds.
Table 4 results of annual broadleaf weed efficacy test in corn fields for each treatment agent
As can be seen from the test results in the table, the combination of the 2-methyl-4-chloroisooctyl ester, the fluroxypyr-meptyl ester and the clopyralid has good control effect on annual broadleaf weeds in corn fields, and the control effect of the example 4 using the preferred auxiliary agent is obviously better than that of the example 7, the comparative example 1 and the comparative agent, and the synergistic effect is shown. From the comparison of the drug effects of the examples and the comparative examples, the selection of the auxiliary agent has an important influence on the exertion of the active ingredients, and the improper selection of the auxiliary agent can influence the compounding effect of the 2-methyl-4-chloroisooctyl ester, the fluroxypyr-meptyl ester and the clopyralid.
In addition, according to the whole-course observation of field experiments, the corn field grows well within the range of the experimental dosage, and no phytotoxicity phenomenon appears, which indicates that the compound preparation has no phytotoxicity to corn.
Claims (8)
1. A dispersible oil suspension agent characterized by: the composite material consists of the following components in percentage by weight: 5-50% of active ingredient, 5-20% of emulsifying agent, 1-6% of dispersing agent, 1-8% of thickening agent and 100% of dispersing medium; the active ingredients are 2 methyl 4 isooctyl chloride, fluroxypyr-meptyl and clopyralid, and the mass ratio of the 2 methyl 4 isooctyl chloride, fluroxypyr-meptyl to clopyralid is 10-30:1-10:3; the emulsifier is formed by mixing castor oil polyoxyethylene ether and calcium dodecyl benzene sulfonate according to the mass ratio of 3-6:1; the dispersing agent is formed by mixing alkyl naphthalene sulfonate formaldehyde condensate and polyoxyethylene-polyoxypropylene segmented copolymer according to the mass ratio of 1:1-2; the thickener is formed by mixing gas phase white carbon black and organic bentonite according to the mass ratio of 1-4:1; the dispersion medium is methyl oleate.
2. The dispersible oil suspension agent according to claim 1, characterized in that: the mass ratio of the 2-methyl-4-chloroisooctyl ester, the fluroxypyr-meptyl ester and the clopyralid is 26:6:3.
3. A process for preparing the dispersible oil suspension of claim 1 or 2 comprising the steps of: and (3) uniformly mixing and dispersing a dispersing medium, an emulsifying agent and a dispersing agent, adding a thickening agent, fluroxypyr ester and clopyralid, fully shearing and uniformly mixing, grinding the mixture until the particle size D 90 is smaller than 4 mu m, finally adding 2 methyl 4 isooctyl chloride, and homogenizing to obtain the dispersible oil suspending agent.
4. A method of manufacture according to claim 3, characterized in that: the shearing speed is 1000-10000r/min.
5. Use of the dispersible oil suspension agent according to claim 1 or 2 for controlling weeds.
6. The use according to claim 5, characterized in that: the weeds are weeds in wheat fields, barley fields, corn fields, garden fields, pastures and forest fields.
7. The use according to claim 5, characterized in that: the weeds are broadleaf weeds.
8. The use according to claim 5, characterized in that: the weeds are quinoa, cleavers, herba aristolochiae, shepherd's purse, amaranth, chickweed, amaranth, purslane, acalypha australis, descurainia sophia, and herba Violae.
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