CN111838165A - Herbicide composition containing atrazine and application thereof - Google Patents
Herbicide composition containing atrazine and application thereof Download PDFInfo
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- CN111838165A CN111838165A CN202010749999.5A CN202010749999A CN111838165A CN 111838165 A CN111838165 A CN 111838165A CN 202010749999 A CN202010749999 A CN 202010749999A CN 111838165 A CN111838165 A CN 111838165A
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- atrazine
- herbicide composition
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- 230000002363 herbicidal effect Effects 0.000 title claims abstract description 61
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000004009 herbicide Substances 0.000 title claims abstract description 56
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- 239000003921 oil Substances 0.000 description 5
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ARIWANIATODDMH-UHFFFAOYSA-N Lauric acid monoglyceride Natural products CCCCCCCCCCCC(=O)OCC(O)CO ARIWANIATODDMH-UHFFFAOYSA-N 0.000 description 2
- 241000209072 Sorghum Species 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
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- 241000207892 Convolvulus Species 0.000 description 1
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000005592 Penoxsulam Substances 0.000 description 1
- SYJGKVOENHZYMQ-UHFFFAOYSA-N Penoxsulam Chemical compound N1=C2C(OC)=CN=C(OC)N2N=C1NS(=O)(=O)C1=C(OCC(F)F)C=CC=C1C(F)(F)F SYJGKVOENHZYMQ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 241000205407 Polygonum Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000008051 alkyl sulfates Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
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- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
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- 239000000575 pesticide Substances 0.000 description 1
- 239000003090 pesticide formulation Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
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- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
- A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
- A01N43/70—Diamino—1,3,5—triazines with only one oxygen, sulfur or halogen atom or only one cyano, thiocyano (—SCN), cyanato (—OCN) or azido (—N3) group directly attached to a ring carbon atom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, 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
- A01N43/42—Biocides, 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 condensed with carbocyclic rings
Landscapes
- 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
Description
技术领域technical field
本本发明属于农用除草剂领域,涉及一种含有莠去津的除草剂组合物及其应用。The invention belongs to the field of agricultural herbicides, and relates to an atrazine-containing herbicide composition and application thereof.
背景技术Background technique
高粱因其具有抗旱耐涝、耐盐碱、耐瘠薄等特点,一直作为中国旱地农田的先锋作物,具有饲用、酿造用和纤维用等诸多特点,在中国农业经济中占有重要的地位。近年来,随着农业的机械化、规模化和劳动力缩减的趋势日加明显,使得高粱田杂草化学防除技术在高粱生产中必将成为不可缺少的重要措施。而高粱属于“小杂粮”的范畴,专用除草剂或登记的品种很少。Sorghum has been regarded as a pioneer crop in China's dryland farmland because of its characteristics of drought resistance, waterlogging resistance, salinity resistance, and barren resistance. In recent years, with the increasing trend of mechanization, scale and labor force reduction in agriculture, chemical weed control technology in sorghum field will become an indispensable and important measure in sorghum production. Sorghum belongs to the category of "small grains", and there are few special herbicides or registered varieties.
目前高粱田除草剂主要以莠去津和酰胺类复配的土壤封闭剂为主。封闭除草剂的药效受环境尤其是土壤湿度影响很大,在干旱地区和免耕条件下药效下降明显,因而只有依靠增加其使用量才能达到防治杂草的目的。莠去津作为高粱田应用面积最大的除草剂,长期大剂量使用造成对环境的危害和杂草抗性的上升。莠去津在自然环境中180天后才能被部分分解,同时,莠去津淋溶性强,易于在土壤中向下迁移而进入地下水,从而造成地下水污染,对土壤环境的影响很大。而且由于长期使用莠去津,也导致了大量抗性杂草种群的形成和杂草群落演替现象,如近年来研究表明莠去津和乙草胺除草剂及复配剂的应用使香附子、田旋花上升为优势杂草;马唐对莠去津的抗性上升,防除效果降低。综上所述,莠去津存在用量大,土壤中的残留多,对一些莠去津的抗性杂草(主要如马唐)防除效果较差等问题。At present, the herbicides in sorghum fields are mainly soil sealants compounded by atrazine and amides. The efficacy of closed herbicides is greatly affected by the environment, especially soil moisture. The efficacy of closed herbicides declines significantly in arid areas and under no-tillage conditions. Therefore, the purpose of weed control can only be achieved by increasing their use. Atrazine is the most widely used herbicide in sorghum fields, and its long-term high-dose use has caused environmental damage and increased weed resistance. Atrazine can only be partially decomposed after 180 days in the natural environment. At the same time, atrazine has strong leaching properties and is easy to migrate down in the soil and enter the groundwater, thereby causing groundwater pollution and having a great impact on the soil environment. Moreover, due to the long-term use of atrazine, it has also led to the formation of a large number of resistant weed populations and the phenomenon of weed community succession. , Tian Convolvulus rose to dominant weeds; crabgrass resistance to atrazine increased, and the control effect decreased. To sum up, atrazine exists in a large amount, and there are many residues in the soil, and the control effect of some atrazine-resistant weeds (mainly crabgrass) is poor.
中国专利201810139901.7公开一种化合物及其除草活性(结构式如下),该化合物主要用于水稻田,对五氟磺草胺的抗性稗草、一年生和多年生禾本科及阔叶杂草有防除效果,但该专利方案并未提及将其与其他除草剂混配使用的情况。Chinese Patent 201810139901.7 discloses a compound and its herbicidal activity (the structural formula is as follows), the compound is mainly used in paddy fields, and has control effect on penoxsulam-resistant barnyard grass, annual and perennial grasses and broadleaf weeds, However, the patent scheme does not mention its use in combination with other herbicides.
发明内容SUMMARY OF THE INVENTION
本发明要解决的技术问题是提供一种含有莠去津的除草剂组合物,可用于防除高粱田稗草、马唐、藜、苋菜等杂草,但对高粱却非常安全;可降低莠去津的用量,减少土壤中的残留,同时对莠去津产生抗性的马唐也有优异的防除效果,达到很好的优势互补的目的。The technical problem to be solved by the present invention is to provide a herbicide composition containing atrazine, which can be used to control weeds such as sorghum field barnyardgrass, crabgrass, quinoa, amaranth, etc., but is very safe for sorghum; At the same time, it also has an excellent control effect on the crabgrass that is resistant to atrazine, and achieves the purpose of complementing its advantages.
本发明的技术方案为:The technical scheme of the present invention is:
一种含有莠去津的除草剂组合物,其包括活性组分;所述活性组分包括活性成分A和活性成分B,该活性成分A为莠去津;An atrazine-containing herbicidal composition, comprising an active component; the active component includes an active component A and an active component B, and the active component A is atrazine;
该活性成分B为式I结构的化合物及其药学上可接受的盐;The active ingredient B is a compound of formula I and a pharmaceutically acceptable salt thereof;
其中,活性成分A与活性成分B的质量比为10:1~80。Wherein, the mass ratio of active ingredient A and active ingredient B is 10:1-80.
其中,所述药学上可接受的盐,是由式I结构的化合物分别与胺类、碱金属和碱土金属碱类或季铵盐碱类形成的盐。Wherein, the pharmaceutically acceptable salt is the salt formed by the compound of formula I with amines, alkali metal and alkaline earth metal bases or quaternary ammonium salt bases, respectively.
根据本发明较佳实施例,其中:所述活性组分的总施用量为300ga.i./hm2,且其中活性成分A与活性成分B的质量比为1:1~1:4(注:g a.i./hm2,即每公顷活性成分的克数)。该用量和配比下,对稗草、马唐、苘麻等杂草的总体防效高达98%以上。According to a preferred embodiment of the present invention, wherein: the total application amount of the active component is 300 ga.i./hm 2 , and the mass ratio of the active component A to the active component B is 1:1 to 1:4 (Note : g ai/hm 2 , i.e. grams of active ingredient per hectare). Under the dosage and ratio, the overall control effect on weeds such as barnyardgrass, crabgrass and abalone is as high as 98%.
根据本发明较佳实施例,其中:活性成分A与活性成分B的质量比为5:1~1:2;更优选为5:1~1:1。以这个比例混配,当活性组分的总施用量为180-300g a.i./hm2时,实测防效E-理论防效E0的差值最大,两种成分的相互协同增益的效果最显著。According to a preferred embodiment of the present invention, wherein: the mass ratio of the active ingredient A to the active ingredient B is 5:1 to 1:2; more preferably, it is 5:1 to 1:1. Mixed in this ratio, when the total application amount of active components is 180-300g ai/hm 2 , the difference between the measured control effect E and the theoretical control effect E 0 is the largest, and the effect of mutual synergistic gain of the two components is the most significant. .
根据本发明较佳实施例,其中:所述除草剂组合物还包含助剂;所述助剂包括表面活性剂、润湿剂、分散剂、乳化剂、快渗剂、溶剂以及填料等其他有益于所述活性组分在制剂中稳定和药效发挥的已知物质,可以是农药制剂中常用或允许使用的各种成分。例如,可以将所述活性组分制成乳油、水剂、浓乳剂、微乳剂、可湿性粉剂、水悬浮剂、油悬浮剂、水分散颗粒剂、或可溶性粉剂(粒剂)等。所述表面活性剂为十二烷基硫酸钠、仲烷基硫酸钠、十二烷基苯磺酸钠、聚氧乙烯脂肪酸酯、聚氧乙烯脂肪醇醚、聚氧乙烯脂肪氨、乙氧基蓖麻油、脂肪酸聚乙二醇酯、烷基酚聚氧乙烯醚、脂肪醇聚氧乙烯醚等。According to a preferred embodiment of the present invention, wherein: the herbicide composition further comprises adjuvants; the adjuvants include surfactants, wetting agents, dispersing agents, emulsifiers, fast penetration agents, solvents and fillers and other beneficial agents The known substances for the stability of the active ingredient in the formulation and the exertion of the medicinal effect can be various ingredients commonly used or allowed to be used in the pesticide formulation. For example, the active ingredient can be formulated into emulsifiable concentrates, waters, concentrated emulsions, microemulsions, wettable powders, water suspensions, oil suspensions, water dispersible granules, or soluble powders (granules) and the like. The surfactant is sodium lauryl sulfate, sodium secondary alkyl sulfate, sodium dodecylbenzenesulfonate, polyoxyethylene fatty acid ester, polyoxyethylene fatty alcohol ether, polyoxyethylene fatty ammonia, ethoxylate base castor oil, fatty acid polyethylene glycol ester, alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, etc.
根据本发明较佳实施例,其中:所述活性组分在除草剂组合物中的总含量为0.5-95.0wt%。According to a preferred embodiment of the present invention, wherein: the total content of the active components in the herbicide composition is 0.5-95.0 wt %.
根据本发明较佳实施例,其中:所述除草剂组合物为固体分散制剂或液体分散制剂。所述液体分散制剂包括乳油剂、水分散颗粒剂、浓乳剂、微乳剂、可湿性粉剂、水悬浮剂及油悬浮剂中的一种或几种。所述固体分散制剂为可溶性粉剂/可溶性颗粒剂等。According to a preferred embodiment of the present invention, wherein: the herbicide composition is a solid dispersion formulation or a liquid dispersion formulation. The liquid dispersion preparation includes one or more of emulsifiable concentrates, water-dispersible granules, concentrated emulsions, microemulsions, wettable powders, water suspensions and oil suspensions. The solid dispersion preparation is soluble powder/soluble granule and the like.
根据本发明较佳实施例,其中:除草剂组合物为预混制剂或双组分单独包装制剂;所述预混制剂中活性成分A与活性成分B已按质量比例预先混合,使用前兑水/土壤/肥料稀释至预定浓度;所述双组分单独包装制剂按质量比分别包装,在使用前自行混合,使用前兑水/土壤/肥料稀释至预定浓度。According to a preferred embodiment of the present invention, wherein: the herbicidal composition is a premixed formulation or a two-component individually packaged formulation; the active ingredient A and the active ingredient B in the premixed formulation have been pre-mixed in mass proportions, and are mixed with water before use. /soil/fertilizer diluted to a predetermined concentration; the two-component individually packaged preparations are separately packaged according to mass ratio, mixed before use, and diluted with water/soil/fertilizer to a predetermined concentration before use.
本发明还涉及上述含有莠去津的除草剂组合物在高粱田杂草防除中的应用,所述杂草包括高粱田一年生及多年生禾本科及阔叶杂草,尤其是稗草、马唐、藜、苋菜、苘麻、蓼等杂草,而在防治稗草、马唐、苘麻等几种杂草方面优势十分明显。The present invention also relates to the application of the above-mentioned atrazine-containing herbicide composition in the control of weeds in sorghum fields, the weeds include annual and perennial grass and broadleaf weeds in sorghum fields, especially barnyardgrass, crabgrass, Quinoa, amaranth, abalone, polygonum and other weeds, and in the control of barnyardgrass, crabgrass, abalone and other weeds have obvious advantages.
本发明的除草剂组合物可与其它具有除草、杀虫或杀菌性能的化合物特别是土壤处理的除草剂混合使用,也可与杀线虫剂、防护剂、生长调节剂、植物营养素或土壤调节剂混合使用。The herbicidal composition of the present invention can be used in admixture with other compounds with herbicidal, insecticidal or fungicidal properties, especially herbicides for soil treatment, as well as with nematicides, repellants, growth regulators, plant nutrients or soil regulators Mixed use.
本发明含有莠去津的除草剂组合物的技术效果包括:The technical effects of the atrazine-containing herbicidal composition of the present invention include:
(1)研究人员在对式I结构化合物进一步研究发现,虽然式I结构的化合物对水稻田一年生及多年生禾本科及阔叶杂草表现出高效的防除效果,尤其是对稗草、马唐、藜、苋菜等有很好的防除作用,其中稗草属于一年生禾本科杂草,马唐都也属于禾本科,但式I结构的化合物对同属禾本科的高粱却非常安全,这使得式I结构化合物可被用于高粱地中其他禾本科及阔叶杂草的防治。(1) The researchers further studied the compound of formula I and found that although the compound of formula I showed efficient control of annual and perennial grass and broadleaf weeds in paddy fields, especially for barnyard grass, crabgrass, Quinoa, amaranth, etc. have very good control effects, wherein barnyardgrass belongs to the annual Gramineae weed, and crabgrass also belongs to Gramineae, but the compound of formula I structure is very safe to sorghum belonging to the same family of Gramineae, which makes the structure of formula I very safe. The compounds can be used for the control of other grass and broadleaf weeds in sorghum fields.
(2)本发明将莠去津与式1化合物组合应用,取得了很好的增效效果,不仅可降低莠去津的用量,减少土壤中的残留,特别是对莠去津产生抗性的马唐也有优异的防除效果,达到很好的优势互补作用。(2) The present invention combines atrazine with the compound of formula 1, and achieves a good synergistic effect, which can not only reduce the amount of atrazine, but also reduce the residue in the soil, especially the atrazine resistance. Crabgrass also has excellent control effect, achieving a good complementary effect.
(3)对于目前存在的高粱田专用除草剂或登记的品种很少、单用一种药剂难以防除所有杂草等问题,本发明将莠去津与式I结构的化合物联合使用后,对稗草、马唐及阔叶杂草藜、苘麻等都有很好的防除效果,混用具有明显增效作用,各药剂可优势互补,既达扩大杀草谱目的,又可以降低成本,减少施药次数和莠去津的使用量,减缓对莠去津产生抗性杂草的选择速度,节约劳动量。(3) for the problems such as the existing special herbicides for sorghum field or the registered varieties, and it is difficult to control all weeds with a single agent, the present invention combines atrazine with the compound of formula I structure, and is effective against barnyardgrass. Grass, crabgrass, broad-leaved weeds, quinoa, abalone, etc. have good control effects. Mixed use has obvious synergistic effect. Each agent can complement each other's advantages, which not only achieves the purpose of expanding the weed killing spectrum, but also reduces costs and reduces the number of applications. and the amount of atrazine used to slow down the selection of atrazine-resistant weeds and save labor.
与现有技术相比,本发明首次将式I结构的化合物及其药学上可接受的盐与莠去津按照一定比例联合使用,取得了意料之外的技术效果,使两种除草活性成分不仅实现了优势互补,杂草防除能力得到了显著增效。由此说明,式I结构的化合物及其药学上可接受的盐与莠去津两种除草活性成分在联合使用情况下产生协同作用,起到了协同增益的功效。Compared with the prior art, the present invention uses the compound of formula I structure and its pharmaceutically acceptable salt and atrazine in combination according to a certain proportion for the first time, and has achieved unexpected technical effects, making the two herbicidal active ingredients not only Complementary advantages have been achieved, and the weed control ability has been significantly increased. This shows that the compound of formula I and its pharmaceutically acceptable salt and the two herbicidal active ingredients of atrazine have a synergistic effect when used in combination, and have the effect of synergistic gain.
具体实施方式Detailed ways
为了使本发明的技术效果更清楚地被了解,以下结合本发明的具体实施例进行说明。但指出的是,基于本发明思路的除草剂组合物,可以用已知的方法制备成适合农业使用的任意一种剂型,不限于以下具有实施例所列的类型。In order to make the technical effects of the present invention more clearly understood, the following description is made in conjunction with the specific embodiments of the present invention. However, it is pointed out that the herbicidal composition based on the idea of the present invention can be prepared into any formulation suitable for agricultural use by known methods, and is not limited to the types listed in the following examples.
实施例1Example 1
本实施例除草剂组合物为一种可湿性粉剂,其中活性组分总含量为66wt%,其中莠去津60wt%、活性成分B为式I结构的化合物,含量为6wt%。The herbicide composition of this embodiment is a wettable powder, wherein the total content of active components is 66wt%, wherein atrazine is 60wt%, and the active component B is a compound of formula I, and the content is 6wt%.
使用的助剂为:十二烷基苯磺酸钠2.0wt%,白碳黑5wt%,木质素磺酸钠10wt%,最后用硅藻土补足至100wt%。The adjuvants used are: sodium dodecylbenzenesulfonate 2.0wt%, white carbon black 5wt%, sodium lignosulfonate 10wt%, and finally supplemented with diatomaceous earth to 100wt%.
制备方法:按上述配方将有效成分莠去津、式I结构的化合物以及助剂、填料充分混合,经超细粉碎机粉碎后,即可制成相应的可湿性粉剂农药。Preparation method: according to the above formula, the active ingredient atrazine, the compound of formula I structure, auxiliary agents and fillers are fully mixed, and after being pulverized by an ultrafine pulverizer, the corresponding wettable powder pesticide can be prepared.
实施例2Example 2
本实施例除草剂组合物为一种水分散性颗粒剂,其中活性组分总含量为42wt%,其中莠去津35wt%、活性成分B为式I结构的化合物,含量为7wt%。The herbicide composition of this embodiment is a water-dispersible granule, wherein the total content of active components is 42wt%, of which atrazine is 35wt%, and the active component B is a compound of formula I, and the content is 7wt%.
使用的助剂为:亚甲基双萘磺酸钠甲醛缩合物12wt%,柠檬酸5wt%,可溶性淀粉15wt%,最后用石膏补足至100wt%。The auxiliary agents used are: 12wt% of sodium methylenebisnaphthalene sulfonate formaldehyde condensate, 5wt% of citric acid, 15wt% of soluble starch, and finally supplemented to 100wt% with gypsum.
制备方法:按上述配方将活性组分和助剂等进行混合粉碎,经喷雾干燥或沸腾干燥得到水分散性颗粒剂或再加水捏合后,加入装有一定规格筛网的造粒机中进行造粒。然后再经干燥、筛分(按筛网范围)即得颗粒状产品。Preparation method: Mix and pulverize the active components and auxiliary agents according to the above formula, obtain water-dispersible granules through spray drying or boiling drying, or add water and knead them, and then add them to a granulator equipped with a certain size screen for granulation. grain. Then it is dried and sieved (according to the screen range) to obtain granular products.
实施例3Example 3
本实施例除草剂组合物为一种油悬浮剂,其中活性组分总含量为20wt%,其中莠去津10wt%、活性成分B为式I结构的化合物,含量为10wt%。The herbicide composition of the present embodiment is an oil suspension agent, wherein the total content of active components is 20wt%, wherein atrazine is 10wt%, and the active component B is a compound of formula I, and the content is 10wt%.
使用的助剂为:脂肪醇聚氧乙烯醚5wt%,甘油单月桂酸酯聚氧乙烯醚10wt%,快渗剂T10wt%,最后用植物油补至100wt%。The adjuvants used are: fatty alcohol polyoxyethylene ether 5wt%, glycerol monolaurate polyoxyethylene ether 10wt%, fast penetration agent T10wt%, and finally supplemented to 100wt% with vegetable oil.
制备方法:按上述配方将活性组分和助剂混合均匀,加入砂磨釜中,进行研细,即可制成相应油悬浮剂产品。Preparation method: according to the above formula, the active components and auxiliary agents are mixed uniformly, added into a sand grinding kettle, and ground to be fine, and then the corresponding oil suspension agent product can be prepared.
实施例4Example 4
本实施例除草剂组合物为一种乳油剂,其中活性组分总含量为9wt%,其中莠去津3wt%、活性成分B为式I结构的化合物,含量为6wt%。The herbicide composition of the present embodiment is an emulsifiable concentrate, wherein the total content of active components is 9wt%, of which atrazine is 3wt%, and the active component B is a compound of formula I, and the content is 6wt%.
使用的助剂为:N,N-二甲基甲酰胺10wt%,脂肪醇聚氧乙烯醚10wt%,甘油单月桂酸酯聚氧乙烯醚10wt%,快渗剂T10wt%,最后用溶剂油补至100wt%。The additives used are: N,N-dimethylformamide 10wt%, fatty alcohol polyoxyethylene ether 10wt%, glycerol monolaurate polyoxyethylene ether 10wt%, fast penetration agent T10wt%, and finally supplemented with solvent oil. to 100wt%.
制备方法:按上述配方将活性组分和助剂混合,使溶解成均匀油相即可制成相应乳油产品。Preparation method: according to the above formula, the active component and the auxiliary agent are mixed, and the corresponding emulsifiable concentrate product can be prepared by dissolving into a uniform oil phase.
实施例5Example 5
本实施例除草剂组合物为一种水乳剂,其中活性组分总含量为20wt%,其中莠去津4wt%、活性成分B为式I结构的化合物,含量为16wt%。The herbicide composition of this embodiment is an aqueous emulsion, wherein the total content of active components is 20 wt%, of which atrazine is 4 wt%, and the active component B is a compound of formula I, and the content is 16 wt%.
使用的助剂为:N-甲基吡咯烷酮5wt%,聚乙烯醇0.8wt%,失水山梨醇脂肪酸酯聚氧乙烯基醚5wt%,烷基-二乙二醇醚-磺酸钠2.5wt%,农乳2201 2wt%,乙二醇5wt%,最后用水补足至100wt%。The additives used are: N-methylpyrrolidone 5wt%, polyvinyl alcohol 0.8wt%, sorbitan fatty acid ester polyoxyethylene ether 5wt%, alkyl-diethylene glycol ether-sodium sulfonate 2.5wt% %, agricultural milk 2201 2wt%, ethylene glycol 5wt%, and finally make up to 100wt% with water.
制备方法:按上述配方将活性组分和助剂混合,使溶解成均匀油相。将水、抗冻剂等混合,成为均一水相。在高速搅拌下,将水相加入到油相或将油相加入到水相,形成分散性良好的水乳剂。Preparation method: according to the above formula, the active components and auxiliary agents are mixed to dissolve into a uniform oil phase. Mix water, antifreeze, etc. to form a homogeneous aqueous phase. Under high-speed stirring, the water phase is added to the oil phase or the oil phase is added to the water phase to form a water emulsion with good dispersibility.
实施例6Example 6
本实施例除草剂组合物为一种悬浮剂,其中活性组分总含量为18wt%,其中莠去津2wt%、活性成分B为式I结构的化合物,含量为16wt%。The herbicide composition of the present embodiment is a suspending agent, wherein the total content of active components is 18 wt %, wherein atrazine is 2 wt %, and the active component B is a compound of formula I, and the content is 16 wt %.
使用的助剂为:木质素磺酸钠5wt%,白碳黑0.3wt%,农乳2201 5wt%,丙三醇8wt%,硅酮少许,最后加水补足至100wt%。The additives used are: sodium lignosulfonate 5wt%, white carbon black 0.3wt%, agricultural milk 2201 5wt%, glycerol 8wt%, a little silicone, and finally water to make up to 100wt%.
制备方法:按上述配方将活性组分和助剂混合,通过砂磨机砂磨2-4小时,使其平均粒径在5微米以下,即可制成相应的悬浮剂产品。Preparation method: mix the active components and auxiliary agents according to the above formula, and grind them by a sand mill for 2-4 hours to make the average particle size below 5 microns, and then the corresponding suspending agent product can be prepared.
除草效果测定Determination of herbicidal effect
(一)对实施例1-6的联合型除草剂组合物、单独的莠去津除草剂、单独的式I结构的化合物除草剂进行除草防效测定,测定方法如下:(1) the herbicidal control effect is measured to the combined herbicide composition of embodiment 1-6, the independent atrazine herbicide, the independent compound herbicide of formula I structure, and the assay method is as follows:
在温室条件下,采用盆栽的方法测定。具体地,在每个直径为20cm的一次性塑料花盆中装入等量适量的过筛土壤,播种等量的杂草种子,每种每盆播15-20粒(种子为稗草、苘麻合盆栽种),覆土0.5-1cm后压平。将花盆放置于不锈钢方盘中使其从底部自然吸水至土壤饱和。将试材置于温室中培养,待稗草5-6叶期、苘麻4叶期时进行茎叶喷雾处理,每个处理3次重复,并设空白对照。处理6小时后置于温室内按常规管理,并进行观察记录,30天后调查各个处理的杂草地上部分鲜重,计算各处理的鲜重防效(%)。Under greenhouse conditions, the method of potted cultivation was used. Specifically, in each disposable plastic flowerpot with a diameter of 20cm, an equal amount of sifted soil is loaded, and the same amount of weed seeds are sown, and 15-20 seeds are sown in each pot (seeds are barnyardgrass, abalone) Mahe potted plant), cover with soil 0.5-1cm and then flatten. Place the pot in a stainless steel square pan to allow it to naturally absorb water from the bottom until the soil is saturated. The test materials were cultured in a greenhouse, and the stem and leaf spraying treatment was carried out at the 5-6 leaf stage of barnyardgrass and the 4-leaf stage of abalone, and each treatment was repeated 3 times, and a blank control was set. After 6 hours of treatment, they were placed in a greenhouse for routine management, and observed and recorded. After 30 days, the fresh weight of each treated weed was investigated, and the fresh weight control effect (%) of each treatment was calculated.
计算鲜重防效时,需将每个处理(花盆)的杂草地上绿色部分分别剪下来称量其重量,然后按照下述公式来计算每个处理的鲜重防效%。每种杂草单独计算鲜重防效。When calculating the control effect of fresh weight, the green part of the weeds of each treatment (flower pot) should be cut off and weighed, and then the fresh weight control effect % of each treatment should be calculated according to the following formula. The fresh weight control effect was calculated separately for each weed.
按照上述方法,计算实施例1-6的除草剂组合物、单独的莠去津除草剂、单独的式I结构的化合物除草剂分别对稗草、苘麻防治的防效。并以鲜重防效作为实测防效值记录如表1、表2。According to the above method, the control effects of the herbicidal compositions of Examples 1-6, the atrazine herbicide alone, and the compound herbicide with the structure of formula I alone on barnyardgrass and abalone were calculated. And the fresh weight control effect was recorded as the measured control effect value as shown in Table 1 and Table 2.
表1.不同除草剂对稗草的防除功效Table 1. Control efficacy of different herbicides on barnyardgrass
表2.不同除草剂对苘麻的防除功效Table 2. Control efficacy of different herbicides on abalone
表1中、表2中:剂量(ga.i./hm2)表示每公顷除草活性组分的用量。实测防效%E由上述鲜重防效的计算公式计算得到。In Table 1 and Table 2: the dosage (ga.i./hm 2 ) represents the dosage of the herbicidal active ingredient per hectare. The measured control effect %E is calculated by the above calculation formula of fresh weight control effect.
理论防效%E0计算理论和依据为:Theoretical control effect %E 0 calculation theory and basis are:
用Gowing法评价2种除草剂混用后联合作用的理论功效。混配效应计算公式为:E0=X+Y-XY/100,式中:X表示用量为P时除草活性成分A的杂草防效;Y表示用量为Q时除草活性成分B的杂草防效;E0表示除草剂用量为(P+Q)时除草剂(A+B)的理论防效。The theoretical efficacy of the combined effect of two herbicides was evaluated by Gowing method. The formula for calculating the mixing effect is: E 0 =X+Y-XY/100, in which: X represents the weed control effect of the herbicidal active ingredient A when the dosage is P; Y represents the weeds of the herbicidal active ingredient B when the dosage is Q Control effect; E 0 represents the theoretical control effect of herbicide (A+B) when the herbicide dosage is (P+Q).
按Gowing法,当E-E0>0时,说明混配的两种除草剂之间产生增效,即两种除草活性成分混配产生协同作用;当E-E0=0时说明混配除草剂产生相加作用,当E-E0<0时,说明混配除草剂产生拮抗作用。According to the Gowing method, when EE 0 >0, it means that there is a synergy between the two herbicides mixed, that is, the two herbicidal active ingredients are mixed to produce a synergistic effect; when EE 0 =0, it means that the mixed herbicide produces a phase of Additive effect, when EE 0 <0, indicating that the mixed herbicides produce antagonistic effect.
参见表1-表2可明显得知,莠去津以150g a.i./hm2的用量与式1化合物以15-1200g a.i./hm2的用量范围联合使用,使莠去津:式1化合物质量比为10:1~1:8时,对稗草的实测防效E都大于其理论防效E0,且E-E0最小5.1,最大达16.7;对苘麻和稗草的实测防效E都大于其理论防效E0,且E-E0最小5.1,最大达16.6。其中,莠去津:式1化合物质量比在5:1~1:1范围内时,两种成分的相互增效效果尤为显著,能够最大程度减少施用量。而莠去津的用量为150g a.i./hm2,式1化合物用量为300g a.i./hm2时,对稗草的实测防效达到95.4%、对苘麻的实测防效达95.3%,可以说这种配合比例和施用量对稗草和苘麻非常有效。Referring to Table 1-Table 2, it is obvious that atrazine is used in combination with the compound of formula 1 in an amount of 15-1200 g ai/hm in an amount of 150 g ai/hm , so that atrazine: the mass ratio of the compound of formula 1 is used in combination. When the ratio is 10:1 to 1:8, the measured control effect E of barnyardgrass is greater than its theoretical control effect E 0 , and the minimum EE 0 is 5.1, and the maximum is 16.7; the measured control effect E of abalone and barnyardgrass is greater than Its theoretical prevention effect E 0 , and the EE 0 minimum is 5.1, and the maximum is 16.6. Among them, when the mass ratio of atrazine: the compound of formula 1 is in the range of 5:1 to 1:1, the mutual synergistic effect of the two components is particularly significant, and the application amount can be minimized. When the dosage of atrazine is 150g ai/hm 2 and the dosage of the compound of formula 1 is 300g ai/hm 2 , the measured control effect on barnyardgrass reaches 95.4%, and the measured control effect on abalone reaches 95.3%. It can be said that this The proportion and application rate of the species are very effective for barnyardgrass and abalone.
由此可得出结论,本发明实施例1-6将莠去津和式1化合物联合作为除草剂的活性组分进行除草使用时,两种除草剂活性成分之间产生增效,即两种除草活性成分产生协同增益效果。From this, it can be concluded that when atrazine and the compound of formula 1 are used in combination as the active components of herbicides in Examples 1-6 of the present invention, there is a synergy between the active components of the two herbicides, that is, the two active components are synergistic. Herbicidally active ingredients produce synergistic benefits.
(二)对混合杂草的防效测定(2) Determination of control effect on mixed weeds
试验方法:在直径为20cm一次性塑料花盆中装入等量且适量的过筛壤土,播种定量的杂草种子及高粱种子,每种每盆播杂草种子15-20粒,高粱种子10粒(马唐、稗草、苘麻及高粱种子合盆播种),覆土0.5-1cm后压平。将花盆放置于不锈钢方盘中使其从底部自然吸水至土壤饱和。将试材置于温室中培养,待稗草5-6叶期,苘麻4-6叶期,马唐4-6叶期,高粱5-6叶期时进行茎叶喷雾处理,每个处理3次重复,并设空白对照。处理6小时后置于温室内按常规管理,并定期进行观察记录。30天后调查各个处理的杂草地上部分鲜重,计算鲜重防(%),目测高粱的株高、叶色、长势,并与对照比较,评价对高粱的安全性。结果见表3。Test method: Put an equal and appropriate amount of sieved loam in a disposable plastic flower pot with a diameter of 20cm, and sow a quantitative amount of weed seeds and sorghum seeds. Each pot is sown with 15-20 weed seeds and 10 sorghum seeds. Grains (crabgrass, barnyardgrass, abalone and sorghum seeds are sown in combined pots), covered with soil 0.5-1cm and then flattened. Place the pot in a stainless steel square pan to allow it to naturally absorb water from the bottom until the soil is saturated. The test material is placed in the greenhouse for cultivation, and the stem and leaf spraying is carried out when the 5-6 leaf stage of barnyard grass, the 4-6 leaf stage of abalone, the 4-6 leaf stage of crabgrass, and the 5-6 leaf stage of sorghum are carried out. Repeated 3 times, and set blank control. After 6 hours of treatment, they were placed in a greenhouse for routine management, and observation records were made regularly. After 30 days, the fresh weight of each treated weed was investigated, and the fresh weight (%) was calculated. The plant height, leaf color and growth of sorghum were visually observed and compared with the control to evaluate the safety to sorghum. The results are shown in Table 3.
表3.组合物实施例对杂草的防效结果(鲜重防效%)Table 3. The control effect results of the composition examples on weeds (% of fresh weight control effect)
注:表中单一杂草鲜重防效及总体鲜重均为3次重复平均值。Note: The fresh weight control effect and overall fresh weight of a single weed in the table are the average of three replicates.
上表中,总体鲜重防效的计算方法为:把每个处理(花盆)各种杂草的地上部分鲜重加起来,得到总重量,防效计算公式为:In the above table, the calculation method of the overall fresh weight control effect is: add up the fresh weight of the aboveground parts of various weeds in each treatment (flower pot) to obtain the total weight, and the calculation formula of the control effect is:
由表3可明显得知,莠去津单用时,在150g a.i./hm2施加量下对稗草的实测防效只有30.8%、对马唐只有20.6%,对苘麻有60.1%,对三种杂草的总体防效仅为40.5%,总体防效很差;B化合物(式I化合物)单用对稗草和苘麻的实测防效只有70.2%和70.6%,对马唐实测防效略高为80.8%,而对三种杂草的总体防效仅为73.6%。It can be clearly seen from Table 3 that when atrazine is used alone, the measured control effect on barnyardgrass is only 30.8%, only 20.6% on crabgrass, 60.1% on abalone, and 60.1% on three The overall control effect of weeds is only 40.5%, and the overall control effect is very poor; the measured control effect of compound B (the compound of formula I) alone is only 70.2% and 70.6% for barnyardgrass and abalone, and the measured control effect for crabgrass is only 70.2% and 70.6%. was slightly higher at 80.8%, while the overall control efficacy against the three weeds was only 73.6%.
当本实施例1-6中,将莠去津与B化合物复配使用时,对稗草、马唐和苘麻均有较好的防除效果,实测防效在85.4-100%之间,对三种杂草的总体防效也在90%以上。由此说明,莠去津和式I化合物联合用作除草剂活性物质,能够明显提高整体的除草效果,扩大了杀草谱,具有较好的实用价值。处理后对高粱的安全性定期进行调查,无论是施药前期及最终调查结果,各个处理高粱的株高、叶色、长势等方面与对照均无任何差别,说明无论单用和混用对高粱均安全、无药害产生。In Examples 1-6, when atrazine and compound B are used in combination, they have good control effects on barnyardgrass, crabgrass and abalone, and the measured control effect is between 85.4-100%. The overall control effect of the three weeds was also above 90%. This shows that the combination of atrazine and the compound of formula I used as a herbicidal active substance can significantly improve the overall herbicidal effect, expand the herbicidal spectrum, and have good practical value. After the treatment, the safety of sorghum was regularly investigated. Regardless of the pre-application and the final investigation results, the plant height, leaf color, growth and other aspects of each treatment were not different from those of the control. Safe and non-toxic.
由实施例3-5可知,活性组分的总施用量为300g a.i./hm2时,若活性成分A与活性成分B的质量比为1:1~1:4得到的混合型除草剂,对稗草、马唐和苘麻三种杂草的总体防效达到98%以上。可以说,活性成分A与活性成分B的质量比为1:1~1:4时,施用量(折算成活性组分的量)为300g a.i./hm2时,对这类高粱田中的一年生及多年生禾本科及阔叶杂草的防除效果非常理想,同时对高粱非常安全。It can be seen from Examples 3-5 that when the total application amount of active components is 300 g ai/hm 2 , if the mass ratio of active component A and active component B is 1:1 to 1:4, the mixed herbicide obtained will be effective for The overall control effect of barnyardgrass, crabgrass and abalone reached more than 98%. It can be said that when the mass ratio of active ingredient A and active ingredient B is 1:1 to 1: 4 , and the application rate (converted to the amount of active ingredient) is 300g ai/hm2, the annual and It is very effective in controlling perennial grasses and broadleaf weeds and is very safe for sorghum.
此外,基于本发明思路的除草剂组合物,可以用已知的方法制备成适合农业使用的任意一种剂型,不限于以下具有实施例所列的类型。其中,式I的化合物也可替换成药学上可接受的盐,例如可以是由化学式(I)的化合物与胺类、碱金属和碱土金属碱类或季铵盐碱类形成的盐。In addition, the herbicidal composition based on the idea of the present invention can be prepared into any formulation suitable for agricultural use by known methods, and is not limited to the types listed in the following examples. Wherein, the compound of formula I can also be replaced by a pharmaceutically acceptable salt, such as a salt formed by the compound of formula (I) with amines, alkali metal and alkaline earth metal bases or quaternary ammonium salt bases.
以上所述的实施例仅仅是对本发明的优选实施方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案作出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。The above-mentioned embodiments merely describe the preferred embodiments of the present invention, and do not limit the scope of the present invention. Without departing from the design spirit of the present invention, those of ordinary skill in the art can make various modifications to the technical solutions of the present invention. Variations and improvements should fall within the protection scope determined by the claims of the present invention.
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