CN108812667A - A kind of Herbicidal combinations containing Acetochlor - Google Patents

A kind of Herbicidal combinations containing Acetochlor Download PDF

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Publication number
CN108812667A
CN108812667A CN201810970490.6A CN201810970490A CN108812667A CN 108812667 A CN108812667 A CN 108812667A CN 201810970490 A CN201810970490 A CN 201810970490A CN 108812667 A CN108812667 A CN 108812667A
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acetochlor
tam
grams
fluorophenyl
thioacetamide
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杨维清
龙燕
谢瑞阳
杨梓轩
赵正权
冯璨
李进
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
    • A01N37/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/26Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the group; Thio analogues thereof
    • 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)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention discloses a kind of synergistic herbicidal pesticide composites, with 2- (the fluoro- 2- pyridine acyloxy of 6-)-N- (4- fluorophenyl)-N- (1- Methylethyl) thioacetamide(TAM-5)It is that acceptable auxiliary element collectively constitutes in effective component, with pesticide with Acetochlor, wherein TAM-5 and Acetochlor weight ratio are 1:1 to 1:10.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 annual gramineae weed and broadleaf weeds, and can inhibit part perennial weeds, especially suitable for weeding in cotton field, significantly improve herbicidal effect, while to industrial crops cotton safety.

Description

A kind of Herbicidal combinations containing Acetochlor
Technical field
The present invention relates to a kind of weeding class composition pesticides, especially for Cotton Fields, Soybean Field, sugarcane field, corn field, The farmlands such as Rapeseed Field, tea place and bare place weeding.
Background technique
Acetochlor molecular formula C14H20ClNO2, molecular weight 269.77, No. CAS:34256-82-1, structural formula such as 1 institute of formula Show.Its Full Name in English 2-chloro-N- (ethoxymethyl)-N- (2-ethyl-6-methylphenyl) acetamide, English Literary abbreviation acetochlor.Acetochlor Chinese chemical name is known as -6 methyl of 2- ethyl -- and N- ethoxyl methyl-alpha-chloro acetyl replaces Aniline, acetochlor sterling are weak yellow liquid(Relative density is 1.11), because peony is often presented containing impurity raw medicine, boiling point is high It is not soluble in water in 200 DEG C(Solubility 223mg/L in water), it is organic to be soluble in ethyl alcohol, methanol, acetone, chloroform, toluene etc. Solvent.Acetochlor is in 1971 by Monsanto Company(The U.S.)It succeeds in developing, is current several weedings most important in the world One of agent kind, and one of maximum herbicide of China's usage amount at present.Acetochlor is selective bud pre-treatment herbicide, can Effectively to prevent and kill off the broadleaf weeds of annual gramineous weed and part small-sized seed.To herba digitariae, herba setariae viridis, herba eleusines indicae, barnyard grass, The annual gramineous weeds such as semen euphorbiae, amur foxtail, wild avena sativa, annual bluegrass, hard grass, herba eragrostidis pilosae have special efficacy, to Chenopodiaceae, Amaranthaceae, The broadleaf weeds such as polygonaceae, dayflower, ox chickweed, china dodder also have certain preventive effect, but effect comparison gramineae weed is poor, right Perennial weeds is invalid.Acetochlor herbicide effect mechanism:It is main to inhibit cell to grow by hindering protein to synthesize, make weeds Young shoot, young root growth stop, and then dead.Mode is passed in Acetochlor absorption:Mainly pass through monocotyledonous plumule or double The hypocotyl of cotyledon plant absorbs, and conducts upwards after absorption, and the ability that gramineae weed absorbs Acetochlor is stronger than broadleaf weeds, institute To prevent and kill off the effect of gramineae weed better than broadleaf weeds.45 days or so the lasting period of Acetochlor in the soil, mainly by micro- Biodegrade, mobility in the soil is small, is primarily retained in 0-3 cm layer of soil.Acetochlor mainly uses crop:Soybean Field, corn field, Peanut Fields, cotton field, potato fields.Further, since wheat, rice, millet, sorghum, cucumber, watermelon, muskmelon, spinach Dish, leek are sensitive to Acetochlor, should be used with caution or disable.Acetochlor belongs to processing soil treatment agent, and usual dosage is larger, usually because of ground Domain, soil property, water content is different and differs greatly:Soybean Field dosage:110-140g (acetochlor tc)/mu;Corn field dosage: 60-140g (acetochlor tc)/mu;Peanut Fields dosage:50-110g (acetochlor tc)/mu;Cotton Fields dosage:70-150g (acetochlor tc)/mu;Potato fields dosage:90-130g (acetochlor tc)/mu.The main dosage form 990g/L second grass of Acetochlor Amine missible oil, 900g/L acetochlor ec, 50% acetochlor ec, 50% Acetochlor microemulsion, 50% Acetochlor aqueous emulsion.Acetochlor Synthesis technology is relatively easy, synthesis step is shorter, and there are mainly two types of synthesis technologies, the first is to pass through:2,6- first ethyl aniline It is reacted with monoxone and phosphorus trichloride, generates the first and second base of 2,6- -2- chloro acetanilide.Ethyl alcohol and polyformaldehyde and hydrochloric acid exist Lower reaction generates chloromethyl ethyl ether.2,6- first and second base -2- chloro acetanilides and chloromethyl ethyl ether are condensed, and generate second Careless amine;Second is to pass through:2,6- first ethyl aniline are reacted with monoxone and phosphorus trichloride, generate the first and second bases of 2,6--chlorine For acetanil;Ethyl alcohol reacts in presence of hydrochloric acid with polyformaldehyde, and chloromethyl ethyl ether is obtained after etherificate;Last 2- methyl -6- Ethyl chloro acetanilide and chloromethyl ethyl ether carry out condensation reaction, obtain Acetochlor.
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.Cotton field Weeds mainly have 24 sections about more than 60, wherein with the herba digitariae, herba eleusines indicae, semen euphorbiae, non-irrigated barnyard grass, herba setariae viridis, double in gramineae weed It is maximum that density occurs for fringe ditch millet, Bermuda grass etc.;Broadleaf weeds is with Eclipta prostrata, Amaranthus retroflexus, argy wormwood, chenopodium glaucum linn, Acalypha-austratis-L, piemarker etc. It is main;Sedge weed is based on the rhizome of nutgrass flatsedge.In Yellow River basin cotton region, with the rise of temperature after sowing cotton seed, cotton field is a variety of miscellaneous Grass starts rudiment successively, until mid or late May forms first emergence peak in field, at this time with herba setariae viridis, herba digitariae, non-irrigated barnyard grass, Chenopodiaceae Deng based on, with rainfall and pour water later it may also occur that primary small germination peak;To July, with the arrival in rainy season, the rhizome of nutgrass flatsedge Equal weeds are largely unearthed, and second germination peak is formed, and at the same time, the weeds that early period is unearthed enter the growth most flower phase, because And easily cotton is caused seriously to cause harm.China cotton field is widely distributed, and different cotton region weed communities and dominant population are different.It is long River basin cotton region, has a moderate climate with heavy rainfall, is suitable for weed growth, dominant weed is based on herba digitariae, herba eleusines indicae and the rhizome of nutgrass flatsedge.North For Fang Mianqu to like to form various weed communities based on cool resistance to early weeds, common weed mainly has herba digitariae, Bermuda grass, dish etc. 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 Main weeds are increasingly becoming, intractable weed harm is got worse, and increases chemical weed control difficulty.The chemical weed control of China cotton field exists The problem of be that method of administration is improper first.The distribution of China cotton field is wide, primary and secondary after the generation of planted in different ecological areas weeds and spraying herbicide The succession of herbaceous of weeds is wanted still to lack further investigation, it is not formed targetedly to prevent and kill off formula to the Popular Science Education of numerous cotton growers not Foot, the not perfectly flat weighing apparatus of various regions application technology level, because selecting the improper past of medicament and administration time, dosage method etc. in practice It is past to cause phytotoxicity.Late, fundamental research is weaker, and cotton field chemical weed control is of less types for China cotton field chemical weed control starting, 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 Fruit 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 (Save 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)In report the artificial Xihua Univ of patent application(Clear, Ma Menglin of inventor Yang Wei etc.)General formula be TAM 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 3rd)In report patent Shen It asks someone as Xihua Univ(Clear, Zhang Yuanyuan of inventor Yang Wei etc.)Mutual-through type is that the 2- pyridine acyloxy-N- of TAM 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 artificial Xihua Univ of patent application(Clear, Zhang Yuanyuan of inventor Yang Wei etc.)General formula 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 Middle broadleaf weeds and gramineae weed.The TAM-5 in the compound that general formula is TAM(Formula 3)Activity of weeding is best, 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 Soybean Field, corn field, flower Farmlands and the bare place weedings such as raw field, cotton field, potato fields.Although aforementioned Chinese patent(Application number CN2013100201928, January 21 2013 date of application, March 26 2014 Granted publication date)In report general formula be TAM 2- pyridine acyl-oxygen The disubstituted thioacetyl amine compound of base-N- is mainly used for the excellent of broadleaf weeds and gramineae weed in farmland as herbicide Good purposes.But 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, requires the defects of high to certain weeds careless age.These defects are reduced to a certain extent in other words in order to overcome, In initial experimentation We conducted TAM-5 respectively with imazethapyr, metosulam, atrazine, Diflufenican, spy Nearly 30 kinds of fourth benzthiazuron, flufenacet, pyrithiobac-sodium, Acetochlor etc. the herbicides that can prevent and kill off broadleaf weeds and gramineae weed Kind is combined(Combination including three kinds of herbicide components)A large amount of screening experiments.Finally, we by a large amount of indoor and Field experiment and further Economic Evaluation, have found the Synergistic herbicide compositions of TAM-5 and Acetochlor.Astoundingly It was found that the Synergistic herbicide compositions are for the industrial crops fields such as Soybean Field, corn field, Peanut Fields, cotton field, potato fields selectivity Weeding, not only herbicidal effect is good, has notable synergistic effect, and do not have visible phytotoxicity to industrial crops.
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 methyl-6-fluoropyrid- ine-2-carboxylate(Hereinafter referred to as TAM-5 in the present invention), structural formula such as formula 3 It is shown;And with Chinese for -6 methyl-N- ethoxyl methyl of 2- ethyl-alpha-chloro acetanil(It is used in the present invention Its Chinese is referred to as Acetochlor)(English name is 2-chloro-N- (ethoxymethyl)-N- (2-ethyl-6- Methylphenyl) acetamide, English abbreviation acetochlor), structural formula is as shown in Equation 1;The present invention is with the change of TAM-5 It closes object and Acetochlor is that acceptable auxiliary element collectively constitutes in effective component, with pesticide.
The permission weight ratio of TAM-5 and Acetochlor is 10 in Herbicidal combinations of the present invention:1 to 1:100, it is preferably in a proportion of 1:1 to 1:10.
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(In the present invention hereinafter referred to as For TAM-4)And 2- (the fluoro- 2- pyridine acyloxy of 6-)-N- (4- chlorphenyl)-N- (1- Methylethyl) thioacetamide [English name Referred to as (N- (4-chlorophenyl)-N-isopro- pylthiocarbamoyl) methyl-6-fluoropyridine-2- carboxylate(Hereinafter referred to as TAM-9 in the present invention)Substitution is acceptable in effective component, with pesticide with Acetochlor Auxiliary element 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 %.? Wettable powder(WP)Middle Herbicidal combinations concentration is, such as the rest part in 10-90 weight %, 100 weight % is by routinely making Agent auxiliary element composition.In suspending agent(SC)Middle Herbicidal combinations concentration is, such as 1-90 weight %, preferably 5-75 weight %, 100 Rest part in weight % is made of conventional formulation auxiliary element.In suspoemulsion(SE)Middle Herbicidal combinations concentration is, 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)Middle Herbicidal combinations concentration is, 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 Acetochlor 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:Aqueous emulsion, microcapsule formulations, wettable powder, Water dispersant, suspending agent, suspoemulsion, microcapsule formulations etc..Such as several typical common dosage forms and preparation can be with:
Aqueous emulsion (EW), the raw medicine liquid or raw medicine for being insoluble in water are dissolved in the resulting liquid dispersion of organic solvent not soluble in water The liquid preparation that Yu Shuizhong is formed.When preparation can by described active drug ingredient and including solvent, emulsifier, co-emulsifier, Auxiliary element including antifreeze, defoaming agent, antimicrobial, pH adjusting agent, density adjuster, thickener etc., through high shear Emulsification is made.Solvent therein can choose in pesticide in benzene class, ketone or the alcohols equal solvent such as common toluene, dimethylbenzene It is one or more of;Emulsifier can choose such as above-mentioned ethoxylated alkyl ether, ethoxyquin alkyl phenylate, alkylbenzene sulfonate, ring Oxidative ethane-propylene oxide block copolymer, alkyl phenol polyglycol ether, polyoxyethylene fatty acid ester, sorbitan alkyl ester, polyoxy One or more of the poly- alkane alkene polyamine of alkane alkene, amides etc.;Co-emulsifier can choose such as butanol, isobutanol, dodecanol- 1, one or more of alkanes alcohols such as tetradecanol -1, octadecanol -1;Antifreeze can choose such as above-mentioned sodium chloride, Urea, ammonium sulfate, ethylene glycol, one or more of polyalcohols such as 1,2- propylene glycol;Thickener and stabilizer also can choose One or more of such as above-mentioned xanthan gum (XG), polyvinyl alcohol (PVA), aluminum magnesium silicate, and use when necessary Auxiliary agents such as pH adjusting agent and defoaming agent etc..
Microcapsule formulations(CJ)Refer to and forms " core-shell structure copolymer " structure small container using natural or synthesis high molecular material, it will Pesticide coats wherein, and the formulations of pesticide in water that suspend.Micro-capsule suspension appearance is a thick working fluid, with water Emulsion and aqueous suspension agent are similar.With micro- sem observation, its shape of microcapsules is spherical in shape, rugby shape, grain or other shapes.It is micro- Capsule 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 micro- glue Capsule pesticide has the characteristics that the lasting period is long, toxicity is low, safe ready, just becomes a developing direction of pesticides new formulation.Micro- glue The customary preparation methods of capsule have complex coacervation, Simple coacervation, interfacial polymerization, situ aggregation method, orifice-coagulating bath method etc..Most Occur some novel processing steps, such as molecular inclusion, microchannel emulsification method, supercritical fluid quick expansion again in recent years Method, yeast microcapsule method, self-assembled multilayer film method.Microcapsules often have sodium alginate, chitosan, gelatin, porous-starch with wall material Deng.Complex coacervation is most popular method in above-mentioned microcapsule preparation method.Complex coacervation preparation principle is with two kinds with phase The substance of counter charges makees embedded object, and core material disperses wherein, to change change pH values, temperature or solution concentration, due to the effect between charge, Make two kinds of wall material solubility declines and is condensed into microcapsules precipitation.A kind of positively charged colloidal solution and another kind are negatively charged Colloidal solution mutually mix, since the interaction between xenogenesis charge forms compound polyelectrolyte and separate, be deposited on Microcapsules are obtained around capsule-core.Complex coacervation is often capsule material with gelatin, Arabic gum.Gelatin is protein, in aqueous solution, Contain-NH on strand2With-COOH and its accordingly dissociate group-NH3 +With-COO-, but contain-NH3 +With-COO-Ion is how much, It is influenced by PH values.For gelatin solution in pH 4.0 or so, positive charge is most.Arabic gum is polysaccharide, water-soluble In liquid ,-COOH and-COO is contained on strand-, there is negative electrical charge.Therefore in gelatin and Arabic gum mixed aqueous solutions, PH is adjusted when being about 4.0, gelatin and Arabic gum form compound because charged phase neutralizes instead, solubility reduction, from system Middle cohesion encystation is precipitated.Curing agent formaldehyde is added, formaldehyde and gelatin generate the condensation reaction of amine aldehyde, and gelatin molecule crosslinking reticulates Structure keeps the shape of micro-capsule, becomes irreversible micro-capsule;Add 2% NaOH to adjust medium pH 8 ~ 9, it is anti-to be conducive to the condensation of amine aldehyde It should carry out completely.
Suspending agent(SC)That is agricultural chemicals suspension agent(SC), it is water insoluble solids pesticide or not mixed liquid pesticidal in water or oil Dispersion.When preparation, with water or oil for decentralized medium, by TAM-5 of the present invention and acetochlor composition and auxiliary element(Such as Thickener, stabilizer, Ricinate, antifreezing agent, pH adjusting agent, defoaming agent etc.)Through soybean dietary fiber(Grinding)It is made.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)I.e. the hybrid dispersions of the insoluble pesticide of water in water, one such effective component are 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 and Acetochlor of the present invention, 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:
Embodiment 1:50% Acetochlor aqueous emulsion (EW)
500 grams of Acetochlors, 130 grams of trimethylbenzenes, 40 grams of ethylene glycol, 40 grams of epoxy ethane-epoxy propane block copolymerizations are weighed respectively Object, 30 grams of emulsifier op-4s, 260 grams of water, it is spare;Preparation:Raw medicine, emulsifier, solvent, co-emulsifier are mixed and are made into uniform oil Water, antifreeze are mixed and are made into uniform water phase by phase, under high shear agitation, oil are mutually poured into water phase, full and uniform mixing ?.
Embodiment 2:40% TAM-5 aqueous emulsion (EW)
400 grams of TAM-5,150 grams of trimethylbenzenes, 30 grams of ethylene glycol, 30 grams of epoxy ethane-epoxy propane block copolymerizations are weighed respectively Object, 20 grams of emulsifier op-4s, 370 grams of water, it is spare;Preparation:Raw medicine, emulsifier, solvent, co-emulsifier are mixed and are made into uniform oil Water, antifreeze are mixed and are made into uniform water phase by phase, under high shear agitation, oil are mutually poured into water phase, full and uniform mixing ?.
Embodiment 3:30% TAM-5 wettable powder(WP)
300 grams of TAM-5,35 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:It will be each Material sequentially adds in reaction kettle, and stirring mixes them thoroughly, and is crushed to 5~20 μm.
Embodiment 4:40% Herbicidal combinations TAM-5 Acetochlor wettable powder(WP)
100 grams of TAM-5,300 grams of Acetochlors, 35 grams of lignosulfonates calcium, 30 grams of sodium carboxymethylcelluloses, 30 grams are weighed respectively Aluminum magnesium silicate, 40 grams of neopelexes, 20 grams of tetrabutylammonium bromide, 430 grams of kaolin, 15 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.
Embodiment 5:30% Herbicidal combinations TAM-5 Acetochlor suspending agent(SC)
40 grams, 35 grams 100 grams of TAM-5,200 grams of Acetochlors, 40 grams of lignosulfonates calcium, tetrabutylammonium bromide carboxylics are weighed respectively Sodium carboxymethylcellulose pyce, 35 grams of aluminum magnesium silicates, 30 grams of neopelexes, 50 grams of polyethylene glycol, 470 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.
Embodiment 6:8% Herbicidal combinations TAM-5 Acetochlor microcapsule formulations(CJ)
Weigh respectively 20 grams of TAM-5,60 grams of Acetochlors, 45 grams of gelatin, 35 grams of poly-aspartates, 15 grams of Tween-60s, 50 grams I Primary glue, 25 grams of polyethylene glycol, 70 gram of 20% formalin, 10% acetum are appropriate(Titer is i.e. by the titration in preparation process It operates and determines usage amount, similarly hereinafter), 20% NaOH solution(Titer), distilled water complementary to 1000 grams, it is spare;
Preparation step(1)It is prepared by poly-aspartate and gelatin mixed solution:After gelatin is impregnated swelling with distillation appropriate amount of water, heating Dissolution is heated to 50 DEG C, and poly-aspartate is added, and appropriate distilled water is added, and 50 DEG C of heat preservations are spare in stirring.(2)Arabic peptization The preparation of liquid:Appropriate distilled water is added in reaction unit, Arabic gum powder is added, is heated to 80 DEG C or so, being gently mixed makes Dissolution, 80 DEG C of heat preservations are spare.(3)The preparation of TAM-5 and Acetochlor effective component emulsion:By TAM-5, Acetochlor, Tween-60, Polyethylene glycol, above-mentioned preparation gumwater, be placed in tissue mashing machine, emulsify 30 seconds to get emulsion.(4)Mixing: Under the conditions of 50~55 DEG C, above-mentioned poly-aspartate and gelatin mixed solution is added, being gently mixed makes to be uniformly mixed.(5)Micro-capsule Preparation:Under constant stirring, 10% acetum is added dropwise into aforementioned mixed liquor, adjusts pH to 3.8~4.0;(6)Micro-capsule Solidification:Under constant stirring, about 30 DEG C of distilled water is added in micro-capsule liquid, micro-capsule liquid will be contained and taken from 50~55 DEG C of water-baths Under, be stirred continuously, natural cooling, when temperature drops to 32~35 DEG C, be added ice cube, continue stirring to temperature be 10 DEG C hereinafter, 20% formalin is added, continues 15~25min of stirring, then with its pH 8~9 of 20%NaOH solution tune, continue stirring 20~ 30min, observation stand and settle to micro-capsule until being precipitated.(7)The filtering and drying of micro-capsule:Completely to micro-capsule sedimentation, it crosses and filters out Fall supernatant, micro-capsule distillation is washed to formaldehydeless taste, centrifugation, drying.
Embodiment 7:50% Herbicidal combinations TAM-5 Acetochlor water dispersible granules(WDG)
100 grams of TAM-5,400 grams of Acetochlors, 70 grams of lignin, 30 grams of acrylic acid minor matters polymer, 30 grams of dodecanes are weighed respectively Base sodium sulfonate, 70 grams of polyethylene glycol, 40 grams of 600C suspension aids, 260 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.
Embodiment 8:30% Herbicidal combinations TAM-5TAM-4TAM-9 Acetochlor water dispersible granules(WDG)
30 grams of TAM-5,30 grams of TAM-9,30 grams of TAM-4,210 grams of Acetochlors, 70 grams of lignin, 70 grams of acrylic acid branches are weighed respectively Polymer, 50 grams of dodecyl sodium sulfates, 70 grams of polyethylene glycol, 30 grams of 600C suspension aids, 410 grams of bentonites are saved, it is spare;It will Each material sequentially adds in reaction kettle, is uniformly mixed, then grinds in sand mill, and suitable quantity of water is added, and is granulated, is drying to obtain water Dispersible granule.
Embodiment 9:50% TAM-5 Acetochlor aqueous emulsion (EW)
50 grams of TAM-5,450 grams of Acetochlors, 140 grams of trimethylbenzenes, 40 grams of ethylene glycol, 35 grams of ethylene oxide-epoxies third are weighed respectively Alkane block copolymer, 25 grams of emulsifier op-4s, 260 grams of water, it is spare;Preparation:Raw medicine, emulsifier, solvent, co-emulsifier are mixed It is made into uniform oily phase, water, antifreeze are mixed and are made into uniform water phase, under high shear agitation, oil is mutually poured into water phase, is filled Divide uniformly mixing.
By following experiment it can be shown that two effective component TAM-5 and Acetochlor 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 as follows(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 Acetochlor
Application method:It is used as processing soil treatment agent, using sowing the previous day spray pesticide, and to above soil(1-4 centimetres of soil Layer)Carefully mixed.40% TAM-5 aqueous emulsion (EW)(It is prepared according to the embodiment of the present invention 2), 50% Acetochlor aqueous emulsion (EW)(It is prepared according to the embodiment of the present invention 1)And to gramineae weed and broadleaf weeds after compounding(Herba digitariae grass seed send out tooth before, dragon Before certain herbaceous plants with big flowers seed sends out tooth)Indoor virulence experimental result, as shown in Table 1.
The activity of weeding effect of one potted plant experiment of table
1 indoor pot of table the experimental results showed that, reactive compound(TAM-5)After being compounded with two kinds of ingredients of Acetochlor, if having Synergistic effect is ratio between the two, works as TAM-5:Acetochlor ratio is greater than 1:When 1, without synergistic effect;Work as TAM-5: Acetochlor ratio is equal to 1:When 1, also without notable synergistic effect, only adduction.Work as TAM-5:Acetochlor ratio is less than 1:When 2, there is notable synergistic effect, ratio is higher, and synergistic effect is more obvious.It is shown according to experimental result:Work as TAM-5:Acetochlor Weight ratio is 1:2 to 1:10 Herbicidal combinations synergistic effects are significant.
Two, field efficacy is tested
By taking Cotton Fields as an example:In Cotton Fields, following preparations are used as processing soil treatment agent, are applied by spraying using sowing the previous day Medicine, and to above soil(1-4 cm layer of soil)It is mixed.40% TAM-5 aqueous emulsion (EW)(It is made according to the embodiment of the present invention 2 It is standby), 50% Acetochlor aqueous emulsion (EW)(It is prepared according to the embodiment of the present invention 1)And 50% TAM-5 Acetochlor aqueous emulsion (EW)(It is prepared according to the embodiment of the present invention 9)To the effect experiment of cotton field weed.30 days investigation fresh weight preventive effects and 5% aobvious after medicine It writes horizontal as shown in table 2.
Table 2 prevents and kill off the field test results of soybean weeds
The experimental result of table 2 shows, TAM-5 and Acetochlor 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, by two kinds of single dose drugs(1:9)Combined composite weedicide, it is real in 3 kinds of different weeds respectively Preventive effect in testing is above the single dose drug of full dosage, further illustrates, TAM-5 can have significant synergy after compounding with Acetochlor Effect, and without antagonism, to cotton safety.

Claims (7)

1. weeding pesticide composition, thio with 2- (the fluoro- 2- pyridine acyloxy of 6-)-N- (4- fluorophenyl)-N- (1- Methylethyl) Acetamide(TAM-5)It is collectively constituted with Acetochlor for acceptable auxiliary element in effective component, with pesticide, wherein 2- (6- Fluoro- 2- pyridine acyloxy)-N- (4- fluorophenyl)-N- (1- Methylethyl) thioacetamide and Acetochlor weight ratio be 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)It is 1 with Acetochlor weight ratio:2 to 1:10.
3. 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.
4. herbicidal composition as described in claim 1, it is characterized in that being used for Soybean Field, corn field, Peanut Fields, cotton field, Ma Ling The industrial crops farmland weeding such as potato field.
5. herbicidal composition as described in claim 1, it is characterized in that being used for bare place selective herbicidal.
6. as in claim 1 herbicidal composition, 2- (the fluoro- 2- pyridine acyloxy of 6-)-N- (4- fluorophenyl)-N- (1- methyl Ethyl) thioacetamide(TAM-5)It 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.
7. its composition is activating plants agent, agrochemical function using function such as claim 1 weeding agricultural chemical compositions In this patent rights protection scope.
CN201810970490.6A 2018-08-24 2018-08-24 A kind of Herbicidal combinations containing Acetochlor Pending CN108812667A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105638711A (en) * 2016-03-04 2016-06-08 西华大学 Synergism weeding composition
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 (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105638711A (en) * 2016-03-04 2016-06-08 西华大学 Synergism weeding composition
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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Application publication date: 20181116