CN102007917B - Composite bactericide and application thereof - Google Patents

Composite bactericide and application thereof Download PDF

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CN102007917B
CN102007917B CN 201010537038 CN201010537038A CN102007917B CN 102007917 B CN102007917 B CN 102007917B CN 201010537038 CN201010537038 CN 201010537038 CN 201010537038 A CN201010537038 A CN 201010537038A CN 102007917 B CN102007917 B CN 102007917B
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procymidone
bactericide
composite bactericide
composite
rotten
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CN102007917A (en
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张传清
刘亚慧
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Linyi Guoli Chemical Co ltd
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Zhejiang A&F University ZAFU
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Abstract

The invention discloses a composite bactericide. The composite bactericide comprises the following components in percentage by weight: 5 to 90 percent of procymidone and 10 to 95 percent of component B, wherein the component B is difenoconazole, tebuconazole, triazolone, propiconazol or myclobutanil. The invention also discloses an emulsion-type bactericide which is prepared from the composite bactericide. Each L of the emulsion-type bactericide comprises 50 to 900 g of the composite bactericide. The invention also discloses a powder/grain-type bactericide which is prepared from the composite bactericide. The powder/grain-type bactericide comprises 10 to 90 weight percent of the composite bactericide. The composite bactericide can be used for preventing fungal diseases of vegetables, fruit trees or rape.

Description

Composite bactericide and uses thereof
Technical field
The present invention relates to a kind of bactericide, particularly a kind of composite bactericide for control vegetables, fruit tree and rape disease.
Background technology
The plant disease that procymidone [procymidone, N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-di carbonyl imide] causes Various Diseases fungal pathogenses such as Botrytis, Monilia, Sclerotinia and Alternarias has good control efficiency.There are some researches show that this medicament is the Antifungi growth by the bi-component histidine kinase signal pathway that activates fungi.Increase sharply through the germ of chemicals treatment such as the OS-2 phosphorylation level in the fungus bodies such as ash arrhizus bacteria (Botrytis cinerea) and cucumber anthrax (Colletotrichumlagenarium), the TCHK signal pathway of fungi is in the sustained activation state so that the glycerine in the fungus body accumulates in a large number, finally causes thalline dead.
Procymidone is the modern protective fungicide of broad spectrum activity contact killing type of releasing early 1970s, is the another class special efficacy bactericide of preventing and treating the diseases such as gray mold after benzimidazole germicide.The dicarboximide fungicides such as procymidone at present on producing Main Problems be drug-fast generation.Beever etc. just detect the existence of ash arrhizus bacteria field drug-fastness bacterial strain in nineteen eighty-three.Pomegranate spot alternaric bacteria (Alternaria alternate) namely develops immunity to drugs less than 5 years in the medication control.The important plant pathogenic fungi such as domestic vegetables, Botrytis cinerea germ, chain sclerotinia sclerotiorum (Moniliniaf ructicola), sclerotinite (Sclerotinia homoeocarpa) and white rot pyrenomycetes (Sclerotium cepivorum) all produces field resistance to dicarboximide fungicides such as procymidones.And the dual drug-fast strain of not only benzimidazoles-resisting bactericide but also anti-procymidone has appearred in field, is having a strong impact on effective use of procymidone.In addition, lack the application that enough therapeutic actions are also limiting procymidone.At present, delay with the main policies of administering the fungicide resistance development have the use that reduces medicament, with the composite reagent of different mechanism of action or by turns use.
Summary of the invention
The technical problem to be solved in the present invention provides the composite bactericide that a kind of energy is used for control vegetables, rape and fruit diseases, and this composite bactericide can be used for preventing and treating the pesticide resistance gray mold especially.
In order to solve the problems of the technologies described above, the invention provides a kind of composite bactericide, its component and weight content are: 5%~90% procymidone (component A) and 10%~95% (B component), B component is Difenoconazole or Tebuconazole (tebuconazole), triazolone (triadimefon), propiconazole (propiconazole) or nitrile bacterium azoles (Myclobutanil).
The present invention also provides the emulsion-type bactericide that utilizes above-mentioned composite bactericide to make simultaneously, contains the composite bactericide of 50~900g in the emulsion-type bactericide of every L.
The present invention also provides the powder that utilizes above-mentioned composite bactericide to make/grain type bactericide simultaneously, and the weight content of composite bactericide is 10%~90% in this powder/grain type bactericide.
The present invention also provides the purposes of above-mentioned composite bactericide simultaneously: be used for control vegetables, fruit tree and rape fungal disease.
Improvement as the purposes of composite bactericide of the present invention: fungal disease is eliminating vegetable botrytis, vegetable leaf mildew, vegetables stalk break, vegetables early blight, strawberry and grape grey mould, fruit tree dry rot or sclerotinia rot of colza.
Composite bactericide of the present invention according to the difference of controlling object, can be processed into the various pesticidal preparations of different content and formulation in actual use, for example emulsion-type bactericide and powder/grain type bactericide.The composite bactericide that contains 50~900g in every L emulsion-type bactericide, 1%~45% solvent (containing emulsifier), 1%~20% auxiliary agent, all the other are water; Above-mentioned percentage is the volume content of this composition in the emulsion-type bactericide.Component and the weight content of powder/grain type bactericide are: the auxiliary agent of 10%~90% composite bactericide, 9%~75% adsorbent or filler and 1%~20%.
Because the difference of constituent content, the emulsion-type bactericide can be divided into suspending agent (SC), aqueous emulsion (EW) and micro-emulsion type (ME), and powder/grain type bactericide can be divided into wetting powder (WP) and water dispersible granules (WG).The various formulations of above-mentioned composite bactericide all are to adopt conventional production process to be formed by the composite bactericide configuration, the conventional variety of the usefulness of producing when related emulsifier, solvent, auxiliary agent, adsorbent/filler is the configuration agricultural chemicals in the component.Such as: emulsifier can be selected agricultural newborn 33#, Nongru-700 # or agricultural newborn 602# etc., and solvent can be selected dimethylbenzene, DMF or ethanol etc., and adsorbent/filler can be selected diatomite, white carbon or perlite etc., and auxiliary agent can be selected organosilicon, polyethylene glycol etc.
The present invention is directed to use in existing the production the key medicament of preventing and treating gray mold, stalk break---procymidone has efficient, cheap but result for the treatment of is poor and drug-fast situation occurred; Utilize compatibility medicament such as Difenoconazole etc. to have with procymidone without mutual pesticide resistance, low toxicity, safety, Environmental compatibility is good, result for the treatment of is good characteristics, the composite bactericide of a group of control vegetables, fruit tree and rape disease (particularly pesticide resistance gray mold) is provided.By the bactericide with above-mentioned different mechanism of action---procymidone (component A) and B component (B component be in Difenoconazole, Tebuconazole, triazolone, propiconazole or the nitrile bacterium azoles a kind of) are carried out composite, bring out one's strengths to make up for one's weaknesses, reach and strengthen therapeutic action, raising effect, delay and administer drug-fast purpose.Composite bactericide of the present invention, can be used for control eliminating vegetable botrytis, vegetable leaf mildew, vegetables stalk break, vegetables early blight, strawberry and grape grey mould or the fungal diseases such as fruit tree mycotic ulcer disease, fruit tree dry rot and sclerotinia rot of colza, belong to novel, efficient, low toxicity bactericide.
The inventor by to the antibacterial mechanisms of the drug-fast generations such as gray mold, evolution and improvement technology, procymidone and drug-fast research for the invention provides technology and theoretical foundation.The present invention is by with a kind of compound screening that carries out in procymidone (component A) and the B component (B component is Difenoconazole or Tebuconazole or triazolone or propiconazole or nitrile bacterium azoles), its target is the improvement pesticide resistance, reduces production costs, and improves result for the treatment of.The present invention mainly prevents and treats gray mold, early blight and the stalk break of anti-procymidone.The present invention meets the needs that current green non-pollution agricultural product are produced.
Procymidone in the complex preparation has higher activity, cost very low but lack therapeutic action, develop immunity to drugs to gray mold etc.; Difenoconazole, Tebuconazole, triazolone, propiconazole and eyeball bacterium azoles all belong to efficient medicament (for gray mold, early blight and stalk break etc.), especially with procymidone without mutual pesticide resistance, have higher therapeutic action.After procymidone and Difenoconazole or Tebuconazole or triazolone or propiconazole or nitrile bacterium azoles two medicines are composite, drug effect significantly increases, production cost of the present invention is than using separately Difenoconazole, Tebuconazole, triazolone, propiconazole, eyeball bacterium azoles or procymidone will reduce by 15%~30%, can be stabilized in more than 70% the control efficiency of gray mold etc.
The present invention is through indoor bioassay and field control effectiveness test, and its result shows, 2 kinds of affine mutual appearances of composition, use safety, effect significantly, can effectively prevent and treat the disease such as gray mold.The present invention compares with other agricultural chemicals, has the following advantages:
1, formulation product of the present invention belongs to the agricultural chemicals of high-efficiency low-toxicity, low-residual, environmentally compatible, has protection and therapeutic action concurrently, meets the requirement of green agriculture production and environmental protection.
2, the present invention can also solve the undesirable problem of procymidone result for the treatment of effectively except solving the pesticide resistance problems to procymidone such as gray mold.
3, product using method of the present invention is simple, cost is low, and peasant household all can accept.
4, the present invention prevents and treats the effective of gray mold etc. to crop safety, and effect can be stabilized in more than 70%, is not easy to develop immunity to drugs.
When used in the actual field of composite bactericide of the present invention, every mu was used active ingredient 5~50 grams (these data are the amount of composite bactericide, i.e. the effective dose of emulsion-type bactericide or powder/grain type bactericide).During use the preparation of this composite bactericide being diluted with water to valid density is 0.01~5 gram/L, and using method is foliar spray.
In order to obtain composite bactericide of the present invention, the inventor had once carried out following experiment:
Experiment 1, formula indoor screening:
It is that procymidone is dissolved in respectively acetone with difenoconazole technical material by different part by weight that virulence is measured with coefficient of synergism, adopts mycelial growth method mensuration to the inhibitory action of Botrytis cinerea (table 1), then calculates EC 50Value and coefficient of synergism.According to main controlling object, can select the proportioning of coefficient of synergism (SR) 〉=1.5, and carry out appropriate dosage forms processing.
Table 1, prevent and treat the prescription screening of gray mold
Figure BSA00000339311400031
Figure BSA00000339311400041
Annotate: the weight ratio that refers to 2 kinds of components in the above bracket.
Experiment 2, formula indoor screening:
It is that procymidone is dissolved in respectively acetone with Original Tebuconazole by different part by weight that virulence is measured with coefficient of synergism, adopts mycelial growth method mensuration to the inhibitory action of Fulvia fulva (table 2), then calculates EC 50Value and coefficient of synergism.
Table 2, prevent and treat the prescription screening of cladosporium leaf and fruit mould of tomato
Figure BSA00000339311400042
Figure BSA00000339311400051
Annotate: the weight ratio that refers to 2 kinds of components in the above bracket.
Experiment 3, formula indoor screening:
It is that the former medicine of procymidone and triazolone is dissolved in respectively acetone by different part by weight that virulence is measured with coefficient of synergism, adopts mycelial growth method mensuration to the inhibitory action of eggplant sclerotium germ (table 3), then calculates EC 50Value and coefficient of synergism.
The prescription screening of table 3, control eggplant stalk break
Figure BSA00000339311400052
Figure BSA00000339311400061
Annotate: the weight ratio that refers to 2 kinds of components in the above bracket.
Experiment 4, formula indoor screening:
It is that procymidone is dissolved in respectively acetone with propiconazole by different part by weight that virulence is measured with coefficient of synergism, adopts mycelial growth method mensuration to the inhibitory action of Sclerotinia sclerotiorum (table 4), then calculates EC 50Value and coefficient of synergism.
The prescription screening of table 4, control sclerotinia rot of colza
Figure BSA00000339311400062
Annotate: the weight ratio that refers to 2 kinds of components in the above bracket.
Experiment 5, formula indoor screening:
It is that procymidone is dissolved in respectively acetone with the former medicine of eyeball bacterium azoles by different part by weight that virulence is measured with coefficient of synergism, adopts mycelial growth method mensuration to the inhibitory action of cucumber anthracnose (table 5), then calculates EC 50Value and coefficient of synergism.
The prescription screening of table 5, control cucumber anthracnose
Figure BSA00000339311400071
Annotate: the weight ratio that refers to 2 kinds of components in the above bracket.
Embodiment
Embodiment 1, a kind of composite bactericide, the procymidone by 75% and 25% Difenoconazole form; Above-mentioned % is % by weight.
It is 80% suspending agent (SC) that above-mentioned composite bactericide is made effective weight content, it is the composite bactericide that contains 800g in every L suspending agent, the auxiliary agent of the solvent of 45mL (glycerine), 70mL (alkylnaphthalene sulfonate, methyl naphthalene sulfonate formaldehyde condensate and silicone defoaming agent), all the other are deionized water.By the prescription requirement, will above-mentioned former medicine, auxiliary agent, solvent, deionized water etc. fully mix, put into the shearing of high shear emulsifying agent high speed, pump sand milling to the sand mill namely gets suspending agent after the filtration again.This suspending agent is hereinafter to be referred as 80% rotten benzene SC.
Field control effectiveness test:
Prevent and treat the test of grey mould fruit rot of strawberry with above-mentioned suspending agent (80% rotten benzene SC).This test is located at Suburban District of Hangzhou, every test area 0.50hm 2, subjects is the identical strawberry of upgrowth situation.Spray March 10 in 2008 is medicine for the first time, and spray in March 20 is medicine for the second time, sprays altogether 2 times.Formulation rate is respectively 80% rotten benzene SC per hectare 170 and 350mL.Contrast medicament I is 50% procymidone WP per hectare 600g; Contrast medicament II is 25% Difenoconazole EC per hectare 500mL.
Control efficiency sees Table 6.80% rotten benzene SC per hectare 170 and 350mL are respectively 72.95% and 82.37% to the control efficiency of gray mold.Therefore, under the prerequisite of identical effective dose, the present invention is better than contrasting medicament, significant difference.
Table 6,80% rotten benzene SC control grey mould fruit rot of strawberry effect
Figure BSA00000339311400081
*: the different lowercase in same columns value back represents that the P=0.05 level difference is remarkable.
Embodiment 2, a kind of composite bactericide, the procymidone by 10% and 90% Tebuconazole form; Above-mentioned % is % by weight.It is 50% wetting powder (WP) that above-mentioned composite bactericide is made effective weight content, it is the composite bactericide that contains 500g in every kg pulvis, the auxiliary agent of 50g (lauryl sodium sulfate and sodium lignin sulfonate), the precipitated calcium carbonate of 35g, all the other are kaolin.Former medicine, various auxiliary agent and filler etc. are fully mixed in the ratio of prescription, behind ultra-fine pulverizer disintegrating, can obtain.This wetting powder (WP) is hereinafter to be referred as 50% rotten penta WP.
Field control effectiveness test:
Prevent and treat the test of eggplant leaf mold with above-mentioned wetting powder (50% rotten penta WP).This test is located at the Zhuji City suburb, every test area 0.40hm 2, subjects is the identical eggplant of upgrowth situation.Spray Mays 15 in 2008 is medicine for the first time, and spray in Mays 22 is medicine for the second time, sprays altogether 2 times.Formulation rate is 50% rotten penta WP per hectare 350g and 500g.Contrast medicament I is 50% procymidone WP per hectare 500g.Contrast medicament II is 80% Tebuconazole WP per hectare 315g.
Control efficiency sees Table 7.50% rotten penta WP per hectare 350g and 500g are respectively 68.14% and 83.09% to the control efficiency of leaf mold.Under the prerequisite of identical effective dose, the present invention is better than contrasting medicament, significant difference.
The rotten penta WP control of table 750% eggplant leaf mold effect
Medicament Repeat 1 Repeat 2 Repeat 3 Repeat 4 On average Average preventive effect (%)
50% rotten penta WP 350g/hm 2 0.24 0.38 0.32 0.36 0.325 68.14b *
50% rotten penta WP 500g/hm 2 0.21 0.15 0.19 0.14 0.1725 83.09a
50% procymidone WP 500g/hm 2 0.48 0.42 0.46 0.47 0.4575 55.15c
80% Tebuconazole WP 315g/hm 2 0.51 0.47 0.49 0.50 0.4925 51.7c
CK (clear water contrast) 0.95 0.85 1.04 1.24 1.02 /
*: the different lowercase in same columns value back represents that the P=0.05 level difference is remarkable.
Embodiment 3, a kind of composite bactericide, the procymidone by 75% and 25% propiconazole form; Above-mentioned % is % by weight.
It is 40% suspending agent (SC) that above-mentioned composite bactericide is made effective weight content, it is the composite bactericide that contains 400g in every L suspending agent, the solvent of 50mL (ethylene glycol), the auxiliary agent of 65mL (fatty alcohol-polyoxyethylene ether, polyether antifoam agent and starch phosphate sodium), all the other are deionized water.By the prescription requirement, former medicine, auxiliary agent, solvent, deionized water etc. are fully mixed, put into high shear emulsifying agent high speed and shear, pump sand milling to the sand mill namely gets suspending agent after the filtration again.This suspending agent is hereinafter to be referred as 40% rotten the third SC.
Field control effectiveness test
(40% rotten the third SC) carries out the test of early blight of tomato with above-mentioned suspending agent.This test is located at Suburban District of Hangzhou, every test area 0.40hm 2, subjects is the identical tomato of upgrowth situation.Spray April 25 in 2009 is medicine for the first time, and spray in Mays 2 is medicine for the second time, sprays altogether 2 times.Formulation rate is 40% rotten the third SC per hectare 400 and 650mL.Contrast medicament I is 50% procymidone WP per hectare 650g.Contrast medicament II is 62% propiconazole EC per hectare 250mL.
Control efficiency sees Table 8.40% rotten the third SC per hectare 400 and 650mL are respectively 62.43b% and 74.60% to the control efficiency of early blight.Under the prerequisite of identical effective dose, the present invention is better than contrasting medicament, significant difference.
Table 8,40% rotten the third ME prevent and treat the early blight of tomato effect
Medicament Repeat 1 Repeat 2 Repeat 3 Repeat 4 On average Average preventive effect (%)
40% rotten the third SC 400mL/hm 2 0.35 0.38 0.42 0.47 0.355 62.43b *
40% rotten the third SC 650mL/hm 2 0.32 0.25 0.27 0.34 0.24 74.60a
50% procymidone WP 650g/hm 2 0.54 0.41 0.49 0.62 0.4525 52.12c
62% propiconazole EC 250mL/hm 2 0.38 0.49 0.44 0.37 0.42 55.97c
CK (clear water contrast) 0.86 0.95 0.81 0.94 0.954 /
*: the different lowercase in same columns value back represents that the P=0.05 level difference is remarkable.
Embodiment 4, a kind of composite bactericide, the procymidone by 75% and 25% triazolone form; Above-mentioned % is % by weight.
It is 50% wetting powder (WP) that above-mentioned composite bactericide is made effective weight content, namely contains the composite bactericide of 500g in every kg pulvis, the auxiliary agent of 50g (polyacrylamide and precipitated calcium carbonate), and the talcum powder of 12g, all the other are kaolin.Former medicine, various auxiliary agent and filler etc. are fully mixed in the ratio of prescription, behind ultra-fine pulverizer disintegrating, can obtain.This wetting powder (WP) is hereinafter to be referred as 50% rotten three WP.
Protection and result for the treatment of are measured:
Cucumber is cultivated in the greenhouse, the artificial infection anthrax bacteria.Carrying out the medicament foliar spray respectively at 24 hours (therapeutic action) behind inoculation anthrax bacteria front 24 hours (protective effect) and the inoculation anthrax bacteria processes.Chemicals treatment is that 50% rotten three WP are diluted with water to 50mg/L (being the composite bactericide that contains 50mg among every L), be treated to CK (contrast) with clear water, contrast medicament I is 50% procymidone WP 50mg/L (being the procymidone that contains 50mg among every L), and contrast medicament II is 25% triazolone WP 50mg/L (being the triazolone that contains 50mg among every L).Effective dose is identical, in 7 days " Invest, Then Investigate " incidences of inoculation anthrax bacteria.Effect sees Table 9.50% rotten three WP 50mg/L are respectively 73.1% and 71.2% to protection and the result for the treatment of of cucumber anthracnose, are better than 2 kinds of contrast medicaments, significant difference.
Table 9,50% rotten three WP are to protection and the result for the treatment of of cucumber anthracnose
Medicament Protection effect (%) Result for the treatment of (%)
50% rotten three WP 50mg/L 73.1 71.2
50% procymidone WP 50mg/L 54.5 30.3
25% triazolone WP 50mg/L 60.1 62.3
Embodiment 5, a kind of composite bactericide, the procymidone by 50% and 50% nitrile bacterium azoles form; Above-mentioned % is % by weight.
It is 50% wetting powder (WP) that above-mentioned composite bactericide is made effective weight content, namely contains the composite bactericide of 500g in every kg pulvis, the auxiliary agent of 75g (polyacrylamide and precipitated calcium carbonate), and the talcum powder of 50g, all the other are kaolin.Former medicine, various auxiliary agent and filler etc. are fully mixed in the ratio of prescription, behind ultra-fine pulverizer disintegrating, can obtain.This wetting powder (WP) is hereinafter to be referred as 50% rotten nitrile WP.
The resistance management effect measuring:
(50% rotten nitrile WP) administers grey mould fruit rot of strawberry to the drug-fast test of procymidone with above-mentioned wetting powder.This test is carried out simultaneously at Zhuji City and Suburban District of Hangzhou, every test area 0.60hm 2, subjects is the identical strawberry of upgrowth situation.Examination spray on March 10th, 2008 is medicine for the first time, at the grey mould fruit rot of strawberry epidemic period every spray in 10 days once, continues on May 1st, 2010.Formulation rate is 50% rotten nitrile WP per hectare 500g.Contrast medicament I is 50% procymidone WP per hectare 500g, and contrast medicament II is 40% nitrile bacterium azoles WP per hectare 625g.
Respectively at the sampling of on March 10th, 2008 and on May 8th, 2010, analyze administer before and administer after experimental field gray mold to the development of drug resistance situation of procymidone.Regulation effect sees Table 10.50% rotten nitrile WP per hectare 500g is 48% to the resistance management effect of grey mould fruit rot of strawberry.And alone 50% procymidone WP per hectare 500g is-53.25% to the resistance management effect of grey mould fruit rot of strawberry.This proof the present invention better solved disease especially gray mold to the pesticide resistance problem of procymidone.
Table 10,50% rotten nitrile WP are to the drug-fast regulation effect of gray mold
Figure BSA00000339311400111
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.

Claims (1)

1. composite bactericide, it is characterized in that this composite bactericide be following any one:
Formed procymidone by procymidone and Difenoconazole: the weight ratio of Difenoconazole=3: 1, described composite bactericide is used for preventing and treating gray mold;
Formed procymidone by procymidone and Tebuconazole: the weight ratio of Tebuconazole=1: 9, described composite bactericide is used for preventing and treating cladosporium leaf and fruit mould of tomato;
Form procymidone by procymidone and eyeball bacterium azoles: the weight ratio of nitrile bacterium azoles=1: 9, described composite bactericide are used for the control cucumber anthracnose.
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CN103210926A (en) * 2013-04-26 2013-07-24 华中农业大学 Bactericide for preventing and treating sclerotinia rot of colza and preparation method thereof
CN103734195A (en) * 2014-01-03 2014-04-23 灵川县金田农资经营部 Biogas liquid compounded fungicide for preventing and treating anthrax
CN103739394A (en) * 2014-01-03 2014-04-23 灵川县金田农资经营部 Biogas liquid compounded fungicide for preventing and treating gray mold
CN103755471A (en) * 2014-01-03 2014-04-30 灵川县金田农资经营部 Biogas slurry compound bactericide for preventing and treating leaf mold
CN104621133A (en) * 2015-01-19 2015-05-20 沈阳农业大学 Sterilizing composition containing procymidone and difenoconazole and preparation method and application of sterilizing composition
CN108208005A (en) * 2016-12-13 2018-06-29 丹阳市中药材科技发展协会 One planting fruit-trees fungicide
CN110183453B (en) * 2019-05-24 2021-08-24 浙江农林大学暨阳学院 Method for preparing 3-phenyl- [1,2,4] triazolo [4,3-a ] pyridine compound under catalysis of no metal

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