CN109258652A - A kind of wheat paddock Synergistic herbicide compositions containing clodinafop-propargyl - Google Patents

A kind of wheat paddock Synergistic herbicide compositions containing clodinafop-propargyl Download PDF

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CN109258652A
CN109258652A CN201811053858.9A CN201811053858A CN109258652A CN 109258652 A CN109258652 A CN 109258652A CN 201811053858 A CN201811053858 A CN 201811053858A CN 109258652 A CN109258652 A CN 109258652A
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propargyl
clodinafop
tam
fluorophenyl
thioacetamide
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詹庆明
王志文
夏川栖
杨维清
张园园
张燕
彭昌荣
赵正权
律娅婧
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Xihua University
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Xihua University
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention discloses a kind of synergistic herbicidal pesticide composites, using 2- (the fluoro- 2- pyridine acyloxy of 6-)-N- (4- fluorophenyl)-N- (1- Methylethyl) thioacetamide (TAM-5) and clodinafop-propargyl as effective component, it is collectively constituted with acceptable auxiliary element in pesticide, wherein TAM-5 and clodinafop-propargyl weight ratio are 5:1 to 1.25:1.Synergistic effect is formed after two kinds of combination of active principles, and can expand degrass spectrum, while without antagonism, crop safety is improved.Synergistic herbicidal pesticide composite can effectively prevent and kill off the weeds such as wheat paddock rat-tail amur foxtail, tall oat grass, rye grass, rough stalked blue grass herba setariae viridis, while to industrial crops wheat safety.

Description

A kind of wheat paddock Synergistic herbicide compositions containing clodinafop-propargyl
Technical field
The present invention relates to a kind of weeding class composition pesticides, are especially used for wheat paddock weeding.
Background technique
Clodinafop-propargyl, Chinese nickname alkynes oxalate, Full Name in English Propynyl (R) -2- [4- [(5-chloro-3- Fluoro-2-pyridinyl) oxy] phenoxy] propanoate, English abbreviation Clodinafop-propargyl.Alkynes grass Ester Chinese chemical name is known as (R) -2- [4- (the fluoro- 2- pyridine oxygroup of the chloro- 3- of 5-) phenoxy group] propionic acid propargyl ester, molecular formula C17H13ClFNO4, molecular weight 349.74, CAS 105512- 06-9, structural formula is as shown in Equation 1.Outside clodinafop-propargyl raw medicine sterling Seeing is white crystalline powder, 53-57 DEG C of fusing point, it is neutral and 25 DEG C under the conditions of, be insoluble in water (4 mg/L, pH=7), be soluble in third The organic solvents such as ketone (880g/L), ethyl alcohol (98g/L), toluene (690g/L).Clodinafop-propargyl is fragrant phenoxy phenoxy propionic acid herbicide, It is a kind of auxiliary quick A hydroxylase inhibitors of acetyl, by inhibiting the biosynthesis of class ester to have the function that management of weeds.Clodinafop-propargyl It is mainly used for preventing and treating wheat paddock gramineae weed, especially to rat-tail amur foxtail, tall oat grass, rye grass, rough stalked blue grass herba setariae viridis Etc. there is excellent preventive effect effect.Clodinafop-propargyl is a kind of high-efficiency low-toxicity herbicide, and usual dosage is few: 5-6g (clodinafop-propargyl raw medicine)/ Mu, common formulations have 15% missible oil, 15% aqueous emulsion, 15% wettable powder etc..Clodinafop-propargyl synthesis route is more, mainly has Three kinds of synthesis technologies, the first is by the way that with hydroquinone and 2,3- difluoro-5-chloropyridine is raw material, through etherified and chiral Ester condensation, acidification, is finally esterified to obtain clodinafop-propargyl with propargyl alcohol hydrolysis, and total recovery is generally in 40-45%;Second is: with (R) -2- (4- hydroxyphenoxy) propionic acid alkynes propyl ester and 2,3- difluoro-5-chloropyridine are Material synthesis clodinafop-propargyl, yield 70- 72%;The third is: (S) -2- chloropropionic acid and product (R) -2- (4- hydroxyphenoxy) propionic acid of hydroquinone reaction are raw material, It is etherified first with chloro- 2, the 3- difluoro pyridine of 5-, then reacts synthesis clodinafop-propargyl, yield 80-85% with propargyl chloride.
China is one of yield wheat big country of the world, and wheat yield is sure to occupy the first in the world for many years.However China's weeds of wheat is numerous, It is easy to influence wheat yield and quality.The main weeds of wheat paddock have Descurainia sophia, barnyard grass, wild avena sativa, willow leaf thorn smartweed, sorrel Knotweed, volume stem smartweed, Chenopodiaceae, Amaranthus retroflexus, Siberian cocklebur, bur beggar-ticks, dayflower, weasel hemp nettle, artemisia, sowthistle, field thistle, setose thistle, garden sorrel etc.. China's wheat field herbicide passes through years of researches, has had very more kinds to occur, has mainly had: 69g/L essence oxazole dogstail Clever EW, 69 grams per liter fenoxapropPethyls+safener, 3% mesosulfuron WP, 3.6% iodosulfuron-methyl-sodium mesosulfuron WDG(0.6:3), the grand WDG(5:1.25 of the phonetic methiodide of 6.25% acyl), 70% flucarbazone WDG, 75% tribenuron-methyl DF, 50 grams per liter azoles Quinoline grass ester alkynes oxalic acid EC(2.5:2.5), 480 grams per liter dicamba AS, 15% alkynes oxalic acid WP, 20% fluroxypyr EC, 58g/ rises double phonetic sulphur SC(25:33 of fluorine azoles), 559g/ rise florasulam 2,4-D isobutyl ester SC(0.6:45.3), 7.5% pyridine sulphur Careless amine WDG, the different monooctyl ester SC of 43% florasulam dimethyl tetrachloride, 15% couple of fluorine fluroxypyr SC(0.5:14.5), still Due to weeds drug resistance, the factors such as phytotoxicity are all carried out in a deep going way and are more effectively applied there is an urgent need to research.These factors, all So that wheat field herbicide needs constantly release effect is more preferable, the wider array of new varieties of degrass spectrum.
China is one of Chan Mian big country of the world, wherein with provinces and regions such as Shandong, Ji, Henan, Soviet Union, Hubei Province, new, Anhui for main cotton growing area. Weed in cotton field mainly has 24 sections about more than 60, wherein with the herba digitariae in gramineae weed, herba eleusines indicae, semen euphorbiae, non-irrigated barnyard grass, dog tail It is maximum that density occurs for grass, Paspalum distichum, Bermuda grass etc.;Broadleaf weeds is with Eclipta prostrata, Amaranthus retroflexus, argy wormwood, chenopodium glaucum linn, Acalypha-austratis-L, piemarker Based on fiber crops etc.;Sedge weed is based on the rhizome of nutgrass flatsedge.In Yellow River basin cotton region, with the rise of temperature, cotton field after sowing cotton seed A variety of weeds start rudiment successively, until mid or late May forms first emergence peak in field, at this time with herba setariae viridis, herba digitariae, drought Based on barnyard grass, Chenopodiaceae etc., with rainfall and pour water later it may also occur that primary small germination peak;To July, with the arrival in rainy season, The weeds such as the rhizome of nutgrass flatsedge are largely unearthed, and second germination peak is formed, and at the same time, the weeds that early period is unearthed enter growth most flower Phase, thus easily cotton is caused seriously to cause harm.China cotton field is widely distributed, and different cotton region weed communities and dominant population are not Together.Yangtze river basin cotton region has a moderate climate with heavy rainfall, is suitable for weed growth, and dominant weed is with herba digitariae, herba eleusines indicae and the rhizome of nutgrass flatsedge It is main.To like to form various weed communities based on cool resistance to early weeds, common weed mainly has herba digitariae, Bermuda grass, dish etc. for North china It is a variety of.Since the herbicide kind of single type is used for a long time, the variation of farmland weed population and the succession of community accelerate, certain secondary Weeds are increasingly becoming main weeds, and intractable weed harm is got worse, and increase chemical weed control difficulty.The chemical weed control of China cotton field There are the problem of be that method of administration is improper first.The distribution of China cotton field is wide, after the generation of planted in different ecological areas weeds and spraying herbicide Primary and secondary wants the succession of herbaceous of weeds still to lack further investigation, not formed targetedly to prevent and kill off the section's general education being formulated to numerous cotton growers Educate deficiency, the not perfectly flat weighing apparatus of various regions application technology level, because selecting medicament and administration time, dosage method etc. no in practice When often resulting in phytotoxicity.The chemical weed control of China cotton field starting late, fundamental research is weaker, cotton field chemical weed control kind compared with It is few, it carries out in a deep going way and more effectively applies there is an urgent need to research.These factors all make cotton field herbicide need constantly to release Effect is more preferable, the wider array of new varieties of degrass spectrum.
In addition, the farmlands such as Soybean Field, sugarcane field, corn field, Rapeseed Field, tea place and bare place weeding equally have it is numerous miscellaneous Grass.By taking common soybean weeds as an example, soybean weeds can be divided into three categories in the sense that preventing and kill off, i.e. annual gramineae Weeds, annual broadleaf weed and perennial weeds.Soybean Field annual gramineous weed mainly has barnyard grass, herba setariae viridis, golden dog Tail grass, wild broomcorn millet, herba digitariae, wild avena sativa etc..Soybean Field annual broadleaf weed mainly has Amaranthus retroflexus, Siberian cocklebur, black nightshade (black star), iron Three-coloured amaranth, Chenopodiaceae (Chenopodium album), bog marshcress herb, piemarker, water spine pin, willow leaf thorn smartweed, herba stellariae mediae, wolf tail grass (ghost fork), salsola collina, elscholtiza (open country Soviet Union Son), purslane, pale persicaria, dayflower (orchid dish), Semen Cuscutae etc..Soybean Field perennial weeds mainly has sowthistle, meadow pine (section bone grass), field thistle (field thistle), setose thistle (cottonsedge-like thistle herb), reed, alkali grass etc..From in recent years, in most of China Area is all presented a kind of trend, dayflower, wolf tail grass, pale persicaria, Siberian cocklebur, black nightshade, bog marshcress herb, piemarker, sowthistle, field thistle, big The broadleaf weeds such as Ji have gradually replaced the gramineae weeds such as barnyard grass, wild avena sativa, herba setariae viridis and have become Soybean Field main weeds.It is small Ji, sowthistle, dayflower are more known as Soybean Field " three dishes ", become the difficult point that soybean weeds are prevented and kill off.Soybean Field chemistry removes Careless agent usage mode is generally taken and broadcasts preceding or soil treatment before seedling sowing and stem and leaf treatment after seedling two ways.Before broadcasting or after broadcasting It is management of weeds the advantages of soil treatment before seedling in the budding period and before causing damages, herbicidal effect is more stable, dispenser cost It is relatively low, even if management of weeds is bad compared with fruit, can also be remedied after seedling.Disadvantage: first is that pH value, by soil types, organic Matter content is affected, and is not suitable for when soil excessively glues weight, the content of organic matter is excessively high or pH value does not meet certain medicament using soil Earth processing;Second is that some herbicides such as metribuzin, 2,4-D butyl ester etc. are also easy to produce in sand soil, low-lying land due to the leaching of medicament Phytotoxicity;Third is that be affected by meteorological condition, especially spring arid, wind is big and abnormal low temperature or high temperature can all influence weeding effect Fruit.The advantages of stem and leaf treatment after seedling be influenced by soil types, the content of organic matter, soil moisture it is smaller, can be according to being unearthed The suitable herbicide with strong points of weeds type selection.Disadvantage: first is that in drought, air humidity is small and weed growth is slow Herbicidal effect is bad in the case where slow;Second is that some medicaments are also easy to produce phytotoxicity under the conditions of too high or too low for temperature;Third is that after seedling Cauline leaf process must just can be carried out when most of weeds are unearthed and have the leaf area of certain adhering liquid medicine, at this time soybean early period Growth is influenced by crop smothering, causes the underproduction.Therefore, Soybean Field chemical weed control is generally based on soil treatment, after seedling at cauline leaf Supplemented by reason., radix biggish plot more to weeds type needs to carry out secondary chemical weed control.Therefore Soybean Field chemical weed control, It flexibly to be grasped in implementation process, particular problem concrete analysis.Due to, soil property difference in all parts of the country is larger, and climate difference is significant, Increase the difficulty of soybean field weeding.
Soybean Field common weed is just like three-coloured amaranth, knotweed, Chenopodiaceae, black nightshade, Siberian cocklebur, barnyard grass, herba setariae viridis, herba digitariae, broomcorn millet etc..Sugarcane field is normal See that weeds there are the annual grassy weeds such as the rhizome of nutgrass flatsedge, herba digitariae, herba eleusines indicae, bald barnyard, bidens pilosa, Bermuda grass.Corn field is common miscellaneous Not only there are also perennial weeds for raw weeds one year in grass, but also these weeds have multiple out of grass, and difficulty of prevention and cure is big.Agriculture at present Phytotoxicity easily occurs for most-often used glyphosate, glufosinate-ammonium, Acetochlor, Bi Kecao etc. in industry production.It is most of simultaneously aforementioned common Height is required to the careless age of weeds when herbicide is administered, beyond a certain range of careless age, herbicidal effect is substantially reduced.Glyphosate, grass Ammonium phosphine herbicide is more only applicable to bare place weeding.Meanwhile weeds will generate different degrees of resistance to chemical herbicide. These factors, all making herbicide need constantly to release, effect is more preferable, the wider array of new varieties of degrass spectrum.
Chinese patent (application number CN2013100125604, January 15 2013 date of application, Granted publication date 2014 On November 19) in report the general formula of the artificial Xihua Univ of patent application (clear, Ma Menglin of inventor Yang Wei etc.) be TAM's The disubstituted thioacetyl amine compound of 2- pyridine acyloxy-N- and its synthetic method (formula 2).Chinese patent (application number CN2013100201913, January 21 2013 date of application, 2014 Granted publication dates September 3 days) in report patent Shen Ask someone be TAM for Xihua Univ (inventor Yang Wei clear, Zhang Yuanyuan etc.) mutual-through type 2- pyridine acyloxy-N- it is disubstituted thio The novel synthesis of acetamides is reported that the new method uses ester-interchange method to the synthesis of target product, is obtained Very good effect.Chinese patent (application number CN2013100201928, January 21 2013 date of application, Granted publication date On March 26th, 2014) in report the general formula of the artificial Xihua Univ of patent application (inventor Yang Wei clear, Zhang Yuanyuan etc.) and be Purposes of the disubstituted thioacetyl amine compound of 2- pyridine acyloxy-N- of TAM as herbicide, is mainly used for preventing and kill off farmland In.The TAM-5(formula 3 in the compound that general formula is TAM) activity of weeding is best, and broadleaf weeds and gramineae weed can effectively prevent Except annual gramineae weed and broadleaf weeds, but limited inhibitory effect can only be played to part perennial weeds, killed Grass spectrum is not extensive enough.Meanwhile TAM-5(formula 3) production cost for most of herbicide kinds currently on the market, It wants slightly higher, economically considers, also it is necessary to carry out interworking use with other effective herbicides.
Summary of the invention
For above situation, the present invention will report that one kind can effectively prevent and kill off annual gramineae weed and broad-leaved is miscellaneous Grass, and efficient, the safe weeding pesticide composition of part perennial weeds can be inhibited, it can be used for wheatland, Cotton Fields, soybean The farmlands such as field, sugarcane field, corn field and bare place weeding are more mainly used for preventing and kill off rat-tail amur foxtail in wheatland, tall oat grass, black Wheat straw, rough stalked blue grass herba setariae viridis.Although aforementioned Chinese patent (application number CN2013100201928, the date of application 2013 1 Months 21 days, March 26 2014 Granted publication date) in report the 2- pyridine acyloxy-N- that general formula is TAM disubstituted thio Acetamides are mainly used for the excellent purposes of broadleaf weeds and gramineae weed in farmland as herbicide.But it is this kind of Thioacetyl amine compound is prepared into preparation exclusive use and still has that degrass spectrum is not wide enough, unit dispenser cost is higher, right Certain weeds careless age requires the defects of high.These defects are reduced to a certain extent in other words in order to overcome, in initial experiment In journey We conducted TAM-5 respectively with imazethapyr, metosulam, atrazine, Diflufenican, terbufos benzthiazuron, fluorine thiophene Nearly 30 kinds of careless amine, clodinafop-propargyl etc. the herbicide kinds that can prevent and kill off broadleaf weeds and gramineae weed are combined (including three kinds The combination of herbicide component) a large amount of screening experiments.Finally, we pass through a large amount of indoor and field experiments and further warp The evaluation of Ji property, has found the Synergistic herbicide compositions of TAM-5 and clodinafop-propargyl.It has surprisingly been found that the Synergistic herbicide compositions For wheatland selective herbicidal, not only herbicidal effect is good, has notable synergistic effect, and not any to industrial crops cotton Phytotoxicity has outstanding preventive effect to rat-tail amur foxtail, tall oat grass, rye grass, rough stalked blue grass herba setariae viridis in wheatland.
Herbicidal combinations of the present invention are 2- (the fluoro- 2- pyridine acyloxy of 6-)-N- (4- fluorophenyl)-N- (1- with Chinese Methylethyl) [English name is (N- (4-fluorophenyl)-N-isopropylthiocarbamoyl) to thioacetamide Hereinafter referred to as TAM-5 in the methyl-6-fluoropyrid- ine- 2-carboxylate(present invention), structural formula such as formula 3 It is shown;And it is (English for (R) -2- [4- (the fluoro- 2- pyridine oxygroup of the chloro- 3- of 5-) phenoxy group] propionic acid propargyl ester with Chinese Entitled Propynyl (R) -2- [4- [(5-ch- loro-3-fluoro-2-pyridinyl) oxy] phenoxy] Propanoate, English abbreviation Clodinafop-propargyl, the present invention in using its Chinese be referred to as clodinafop-propargyl), structure Formula is as shown in Equation 1;The present invention using the compound of TAM-5 and clodinafop-propargyl as acceptable auxiliary in effective component, with pesticide at Divide and collectively constitutes.
TAM-5 and the permission weight ratio of clodinafop-propargyl are 100:1 to 1:100, preferred proportion in Herbicidal combinations of the present invention For 20:1 to 1:20, more preferable range of results is 5:1 to 1.25:1.
TAM-5 can also be compound 2- (the 6- Chloro-2-Pyridyle similar with TAM-5 structure in Herbicidal combinations of the present invention Acyloxy) [English name is (N- (4-fluorophenyl)-N- to-N- (4- fluorophenyl)-N- (1- propyl) thioacetamide Propylthiocarba- moyl) methyl-6-chloropyridine-2-carboxylate(the present invention in referred to as ) and 2- (the fluoro- 2- pyridine acyloxy of 6-)-N- (4- chlorphenyl)-N- (1- Methylethyl) thioacetamide [English name TAM-4 For (N- (4-chlorophenyl)-N-isopro- pylthiocarbamoyl) methyl-6-fluoropyridine-2- Carboxylate(the present invention in referred to as TAM-9) substitution with clodinafop-propargyl be effective component, with pesticide in acceptable assist Ingredient collectively constitutes.
Acceptable auxiliary element in described pesticide, including used in pesticide at present, unfavorable shadow will not be generated Loud all kinds of common solvents and/or inert filler and/or surfactant and/or preservative and/or antifreezing agent and/or agglomeration resistance Agent and/or defoaming agent and/or cosolvent and/or the corresponding adding ingredient such as stabilizer and/or thickener, and can be according to being produced Dosage form do corresponding selection or adjustment.
Agrochemical formulations generally comprise the Herbicidal combinations of the present invention of 0.1-99 weight %, especially 2-90 weight %.? Herbicidal combinations concentration is in wettable powder (WP), such as the rest part in 10-90 weight %, 100 weight % is by routinely making Agent auxiliary element composition.Herbicidal combinations concentration is in suspending agent (SC), such as 1-90 weight %, preferably 5-75 weight %, 100 Rest part in weight % is made of conventional formulation auxiliary element.Herbicidal combinations concentration is in suspoemulsion (SE), such as 1- 90 weight %, preferably 5-75 weight %, the rest part in 100 weight % are made of conventional formulation auxiliary element.In water dispersant (WDG) Herbicidal combinations concentration is in, such as 1-95 weight %, preferably 10-70 weight %, and the rest part in 100 weight % is by normal Regulation agent auxiliary element composition.The preparation of other powder types includes 1-40 weight % reactive compound, and preferably 5-20 weight % is living Property compound, the rest part in 100 weight % are made of conventional formulation auxiliary element.
Herbicidal combinations of the present invention are needed according to different uses or application Huan Jing ∕ condition, raw by current conventional pesticide TAM-5 in the Herbicidal combinations and clodinafop-propargyl effective component and corresponding auxiliary element are sufficiently mixed by production mode for raw material, system It is standby to become various forms of available corresponding dosage forms.Possible dosage form includes: microcapsule formulations, wettable powder, water dispersion Agent, suspending agent, aqueous emulsion, suspoemulsion, microcapsule formulations etc..Such as several typical common dosage forms and preparation can be with:
Microcapsule formulations (CJ), which refer to, forms " core-shell structure copolymer " structure small container using natural or synthesis high molecular material, by pesticide It coats wherein, and the formulations of pesticide in water that suspend.Micro-capsule suspension appearance is a thick working fluid, with aqueous emulsion And aqueous suspension agent is similar.With micro- sem observation, its shape of microcapsules is spherical in shape, rugby shape, grain or other shapes.Microcapsules Diameter is generally at 3-30 microns.Small rice grain and mung bean grain size are about as much as with the observation of 400 power microscopes.Due to microcapsules agriculture Medical instrument has the features such as lasting period is long, toxicity is low, safe ready, just becomes a developing direction of pesticides new formulation.Microcapsules Customary preparation methods have complex coacervation, Simple coacervation, interfacial polymerization, situ aggregation method, orifice-coagulating bath method etc..It is several recently There is some novel processing steps, such as molecular inclusion, microchannel emulsification method, supercritical fluid quick expansion method, ferment again in year Female microcapsule method, self-assembled multilayer film method.Microcapsules often have sodium alginate, chitosan, gelatin, porous-starch etc. with wall material.? Complex coacervation is most popular method in above-mentioned microcapsule preparation method.Complex coacervation preparation principle is with two kinds with opposite charges Substance make embedded object, core material disperses wherein, to change change pH values, temperature or solution concentration, due to the effect between charge, make two kinds Wall material solubility declines and is condensed into microcapsules precipitation.A kind of positively charged colloidal solution and another negatively charged colloid Solution mutually mixes, and since the interaction between xenogenesis charge forms compound polyelectrolyte and separates, and is deposited on capsule-core week It encloses and obtains microcapsules.Complex coacervation is often capsule material with gelatin, Arabic gum.Gelatin is protein, in aqueous solution, strand It is upper to contain-NH2With-COOH and its accordingly dissociate group-NH3 +With-COO-, but contain-NH3 +With-COO-How much is ion, by medium The influence of pH value.For gelatin solution in pH 4.0 or so, positive charge is most.Arabic gum is polysaccharide, in aqueous solution, point Contain-COOH and-COO in subchain-, there is negative electrical charge.Therefore in gelatin and Arabic gum mixed aqueous solutions, pH is adjusted about When being 4.0, gelatin and Arabic gum form compound because charged phase neutralizes instead, and solubility reduces, and are condensed into from system Capsule is precipitated.Curing agent formaldehyde is added, formaldehyde and gelatin generate the condensation reaction of amine aldehyde, and gelatin molecule is cross-linked into reticular structure, protects The shape for holding micro-capsule becomes irreversible micro-capsule;Add 2% NaOH to adjust medium pH 8 ~ 9, is conducive to amine aldehyde condensation reaction progress Completely.
Suspending agent (SC) i.e. agricultural chemicals suspension agent (SC) is water insoluble solids pesticide or not mixed liquid pesticidal in water or oil Dispersion.When preparation, with water or oil for decentralized medium, (such as by TAM-5 of the present invention and clodinafop-propargyl composition and auxiliary element Thickener, stabilizer, Ricinate, antifreezing agent, pH adjusting agent, defoaming agent etc.) it is made through soybean dietary fiber (grinding).Its Middle Ricinate be phosphate polyethers, alkylnaphthalene sulfonate, alkylbenzene sulfonate, aliphatic alcohol sulfate, alkyl bromination ammonium, Alkyl ammomium chloride, crown ether, quaternary alkylphosphonium salt, alkyl polyoxyethylene base ether sulfate, lignosulfonates, lignin, carboxymethyl cellulose One of element, sodium carboxymethylcellulose, azone, thiophene ketone are several;Thickener and stabilizer are polyvinyl alcohol, condensed phosphoric acid One of salt, xanthan gum, aluminum magnesium silicate etc. are several;Antifreezing agent is sodium chloride, urea, ammonium sulfate, ethylene glycol, glycerol Deng one of or it is several;PH adjusting agent is in potassium dihydrogen phosphate, dipotassium hydrogen phosphate, citric acid, sodium carbonate, potassium carbonate etc. It is one or several kinds of.Organosilicon is commonly used as defoaming agent and foam inhibitor.
Suspoemulsion (SE) the i.e. hybrid dispersions of the insoluble pesticide of water in water, one such effective component is in suspension State, other effective components are in emulsion state.It can be by the present composition and corresponding emulsion, wet point when being prepared when preparation The auxiliary elements such as powder, thickener, stabilizer, antifreezing agent, pH adjusting agent, defoaming agent, conventionally, through wet process Ultramicro-powder It is broken to be mixed to prepare.Wherein emulsifier is alkyl phenol polyoxyethylene ether class (agriculture breast 100#), alkylbenzene sulfonate (agriculture breast 500#), benzene Ethyl phenol polyethenoxy ether class (agriculture breast 600#), alkyl phenol or aralkyl phenol polyethenoxy ether formaldehyde condensation species (Nongru-700 #) Deng one of or it is several.Wherein Ricinate is lignosulfonates, lignin, phosphate polyethers, carboxymethyl fibre Tie up element, sodium carboxymethylcellulose, crown ether, alkylnaphthalene sulfonate, alkylbenzene sulfonate, aliphatic alcohol sulfate, alkyl ammonium halide, season One of phosphonium salt, alkyl polyoxyethylene base ether sulfate, azone, thiophene ketone are several;Thickener and stabilizer are polyethylene One of alcohol, condensed phosphate, xanthan gum, aluminum magnesium silicate etc. are several;Antifreezing agent be sodium chloride, urea, ammonium sulfate, One of ethylene glycol, glycerol etc. are several;PH adjusting agent be potassium dihydrogen phosphate, dipotassium hydrogen phosphate, citric acid, sodium carbonate, One of potassium carbonate etc. is several.Organosilicon is commonly used as defoaming agent and foam inhibitor.
Water dispersible granules (WDG) can fater disintegration in water, and can be uniformly dispersed in formation higher suspension dispersion in water A kind of granular preparation of system.The present composition and auxiliary element one can be reinstated to air-flow smashing or ultra-fine grinding when preparation, Wettable powder is made, this is dry method;The present composition, auxiliary agent, adjuvant etc. are ground in sand mill using water as medium Mill, is made suspending agent, and then re-dry is granulated, this is wet process.
Wettable powder (WP), i.e., solid powder preparation that in water can be evenly dispersed.It, can be according to conventional side when preparation Formula is firstly added the composition of TAM-5 of the present invention and clodinafop-propargyl, and diatomite, clay, precipitated calcium carbonate, white carbon black is then added Etc. common diluent or inert substance, other common auxiliary elements are added, such as alkylnaphthalene sulfonate, alkylbenzene sulfonate, rouge Fat alcohol sulfate, alkyl bromination ammonium, alkyl ammomium chloride, quaternary alkylphosphonium salt, alkyl polyoxyethylene base ether sulfate, lignosulfonates, One of lignin, carboxymethyl cellulose, sodium carboxymethylcellulose, azone, thiophene ketone or several and common stabilizer, The complementary auxiliary component such as foam inhibitor, anticaking agent.
It should be noted that specific dosage form mentioned above is the representative dosage form that the present composition can be prepared, enumerate not It is limited to these above-mentioned dosage forms.
Concrete mode by the following examples is again described in further detail above content of the invention.But it does not answer This range for being interpreted as the above-mentioned theme of the present invention is only limitted to example below by this.The above-mentioned technical idea feelings of the present invention are not being departed from Under condition, the various replacements or change made according to ordinary skill knowledge and customary means, should all include of the invention In range.Each material composition ratio is weight % in embodiment.
Specific embodiment:
The reactive compound TAM-5 aqueous suspension agent (SC) of embodiment 1:20%
200 grams of TAM-5,35 grams of defoaming agent tributyl phosphates, 30 grams of lignosulfonates calcium, 40 grams of carboxymethyl celluloses are weighed respectively Plain sodium, 35 grams of aluminum magnesium silicates, 40 grams of neopelexes, 60 grams of polyethylene glycol, 560 grams of water, it is spare;Successively by each material It is added in reaction kettle, just dispersion is carried out using high-speed shearing machine, effective component partial size is then ground in sand mill in 2~5 μ m。
The clodinafop-propargyl wettable powder (WP) of embodiment 2:15%
150 grams of clodinafop-propargyls, 35 grams of lignosulfonates calcium, 35 grams of sodium carboxymethylcelluloses, 40 grams of aluminum magnesium silicates, 30 are weighed respectively Gram neopelex, 20 grams of tetrabutylammonium bromide, 560 grams of kaolin, 20 grams of pull powder Bx, it is spare;Preparation: will be each Material sequentially adds in reaction kettle, and stirring mixes them thoroughly, and is crushed to 5~20 μm.
The Herbicidal combinations TAM-5 clodinafop-propargyl wettable powder (WP) of embodiment 3:30%
250 grams of TAM-5,50 grams of clodinafop-propargyls, 40 grams of lignosulfonates calcium, 40 grams of sodium carboxymethylcelluloses, 45 grams are weighed respectively Aluminum magnesium silicate, 35 grams of neopelexes, 25 grams of tetrabutylammonium bromide, 485 grams of kaolin, 30 grams of pull powder Bx, it is standby With;Preparation: each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
The Herbicidal combinations TAM-5 clodinafop-propargyl wettable powder (WP) of embodiment 4:40%
200 grams of TAM-5,200 grams of clodinafop-propargyls, 35 grams of lignosulfonates calcium, 35 grams of sodium carboxymethylcelluloses, 25 grams are weighed respectively Aluminum magnesium silicate, 18 grams of neopelexes, 22 grams of tetrabutylammonium bromide, 440 grams of kaolin, 25 grams of pull powder Bx, it is standby With;Preparation: each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
The Herbicidal combinations TAM-5 clodinafop-propargyl suspending agent (SC) of embodiment 5:30%
40 grams, 50 grams 200 grams of TAM-5,100 grams of clodinafop-propargyls, 60 grams of lignosulfonates calcium, tetrabutylammonium bromide carboxylics are weighed respectively Sodium carboxymethylcellulose pyce, 40 grams of aluminum magnesium silicates, 30 grams of neopelexes, 50 grams of polyethylene glycol, 430 grams of water, it is spare.It will be each Material sequentially adds in reaction kettle, carries out just dispersion using high-speed shearing machine, effective component grain is then ground in sand mill Diameter is at 2~5 μm.
The Herbicidal combinations TAM-5 clodinafop-propargylwater water dispersible granule (WDG) of embodiment 6:50%
400 grams of TAM-5,100 grams of clodinafop-propargyls, 50 grams of lignin, 40 grams of acrylic acid minor matters polymer, 40 grams of dodecanes are weighed respectively Base sodium sulfonate, 40 grams of polyethylene glycol, 20 grams of 600C suspension aids, 310 grams of bentonites, it is spare;Each material is sequentially added into reaction It in kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, be granulated, be drying to obtain water dispersible granules.
By following experiment it can be shown that two effective component TAM-5 and clodinafop-propargyl in above-mentioned Herbicidal combinations of the invention Compounding can have apparent synergistic effect.
In the research of herbicide, activity of weeding after active compound is more than that each reactive compound is administered alone Activity when, then show that there are synergistic effects.
The budget activity of the given combination of two kinds of herbicides can calculate it is following (bibliography: author Colby, S.R. etc., Periodical title " Weed ", 1 phase in 1967, P20-22)
When X=% amount of application be p kg/ha in the case where, herbicide A (reactive compound A) loss ratio,
And Y=% amount of application be q kg/ha in the case where, herbicide B (reactive compound B) loss ratio,
And E=% amount of application be p and q kg/ha in the case where, the speculative damage rate of herbicide A and B, then:
E=X+Y-X*Y/100
If actual damage value is more than calculated value, the activity of composition is super adduction, that is, shows synergy.
One, potted plant experiment
Herbicidal combinations TAM-5 clodinafop-propargyl
20% reactive compound TAM-5 aqueous suspension agent (SC) (being prepared according to the embodiment of the present invention 1), 15% clodinafop-propargyl wettable After pulvis (WP) (being prepared according to the embodiment of the present invention 2) and compounding to gramineae weed and broadleaf weeds (the amur foxtail 1-3 leaf phase, The tall oat grass 1-3 leaf phase) indoor virulence experimental result, as shown in table 1.
The activity of weeding effect of 1 potted plant experiment of table
1 indoor pot of table the experimental results showed that, after reactive compound (TAM-5) is compounded with two kinds of ingredients of clodinafop-propargyl, centainly comparing There is notable synergistic effect (data in table one, label has (+) after observing Value Data " symbol, for synergistic effect) in example range, Concrete condition is as follows: reactive compound (TAM-5) and clodinafop-propargyl weight ratio are made between 1.25:1 with notable synergistic for 5:1 With.
Two, field efficacy is tested
By taking wheat paddock as an example: in wheat paddock, 1~2 leaf phase of wheat seedling tender shoots, 1~3 leaf phase of weeds, 20% reactive compound TAM-5 aqueous suspension agent (SC) (preparing according to the embodiment of the present invention 1), 15% clodinafop-propargyl wettable powder (WP) are (according to the present invention Embodiment 2 prepare) and 30% Herbicidal combinations TAM-5 clodinafop-propargyl wettable powder (WP) (according to the embodiment of the present invention 3 make It is standby) to the effect experiment of weeds of wheat.4 weeks investigation fresh weight preventive effects and 5% level of signifiance are as shown in table 2 after medicine.
The field test results of 2 eliminating weed in wheat field of table
The experimental result of table 2 shows, TAM-5 and clodinafop-propargyl compound in the present composition, is capable of forming synergistic effect, and Degrass spectrum can be expanded, while without antagonism, crop safety is improved, herbicidal effect is significantly improved, reduces costs.By table 1, table 2 the experimental results showed that, the composite weedicide combined by two kinds of single dose drugs (5:1) is real in 3 kinds of different weeds respectively Preventive effect in testing is above single dose drug, further illustrates, TAM-5 can have significant synergistic effect after compounding with clodinafop-propargyl, and Without antagonism, to wheat safety.

Claims (8)

1. weeding pesticide composition, thio with 2- (the fluoro- 2- pyridine acyloxy of 6-)-N- (4- fluorophenyl)-N- (1- Methylethyl) Acetamide (abbreviation TAM-5) and clodinafop-propargyl are that acceptable auxiliary element collectively constitutes in effective component, with pesticide, wherein 2- (the fluoro- 2- pyridine acyloxy of 6-)-N- (4- fluorophenyl)-N- (1- Methylethyl) thioacetamide and clodinafop-propargyl weight ratio are 100:1 to 1:100.
2. herbicidal composition as described in claim 1, it is characterized in that the effective component 2- (the fluoro- 2- pyridine acyloxy of 6-)- N- (4- fluorophenyl)-N- (1- Methylethyl) thioacetamide (TAM-5) and clodinafop-propargyl weight ratio are 20:1 to 1:20.
3. herbicidal composition as described in claim 1, it is characterized in that the effective component 2- (the fluoro- 2- pyridine acyloxy of 6-)- N- (4- fluorophenyl)-N- (1- Methylethyl) thioacetamide (TAM-5) and clodinafop-propargyl weight ratio are 5:1 to 1.25:1.
4. herbicidal composition as described in claim 1, it is characterized in that being prepared into not by current conventional pesticide production method With preparations agent such as the available wettable powder of form, water dispersible granules, suspending agent, aqueous emulsion, suspoemulsion, microcapsule formulations Any dosage form in type.
5. herbicidal composition as described in claim 1, it is characterized in that being applied to industrial crops wheat.
6. herbicidal composition as described in claim 1, it is characterized in that being used for Soybean Field, sugarcane field, corn field, Rapeseed Field, tea The farmlands such as garden and bare place weeding.
7. as in claim 1 herbicidal composition, 2- (the fluoro- 2- pyridine acyloxy of 6-)-N- (4- fluorophenyl)-N- (1- methyl Ethyl) thioacetamide (TAM-5) can be by compound 2- (6- fluoro- 2- pyridine acyloxy)-N- similar with TAM-5 structure (4- fluorophenyl)-N- n-propyl thioacetamide, 2- (6- bromo-2-pyridyl acyloxy)-N- (4- fluorophenyl)-N- (1- methyl second Base) generations such as thioacetamide, 2- (6- Chloro-2-Pyridyle acyloxy)-N- (4- fluorophenyl)-N- (1- Methylethyl) thioacetamide It replaces.
8. its composition is activating plants agent, agrochemical function using function such as claim 1 weeding agricultural chemical compositions In this patent rights protection scope.
CN201811053858.9A 2018-09-11 2018-09-11 A kind of wheat paddock Synergistic herbicide compositions containing clodinafop-propargyl Pending CN109258652A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105918328A (en) * 2016-05-03 2016-09-07 西华大学 Weeding farm chemical composition
CN106359429A (en) * 2016-08-23 2017-02-01 西华大学 Tebuthiuron-containing synergistic weeding composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105918328A (en) * 2016-05-03 2016-09-07 西华大学 Weeding farm chemical composition
CN106359429A (en) * 2016-08-23 2017-02-01 西华大学 Tebuthiuron-containing synergistic weeding composition

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