CN1307807A - Preparation of synergistic diniconazole composite - Google Patents
Preparation of synergistic diniconazole composite Download PDFInfo
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- CN1307807A CN1307807A CN 01101771 CN01101771A CN1307807A CN 1307807 A CN1307807 A CN 1307807A CN 01101771 CN01101771 CN 01101771 CN 01101771 A CN01101771 A CN 01101771A CN 1307807 A CN1307807 A CN 1307807A
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- synergist
- alkene azoles
- diniconazole
- inorganic acid
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Abstract
The mixed composite of synergistic diniconazole is made of triazolone and synergist which are mixed according to arbitrary proportion. The synergist of the metallic inorganic acid salt with the following general formula: MXn.kH2O, in which M is metal ion of subgroups IIA, IIIA, IVA, IB, IIB, IVB-VIIB and VIII, x is inorganic acid radical, n is integral number of 1-4, k is number of crystal water contaied is said salt, k is 0-18. In said mixture the sulfur with arbitrary proportion also can be mixed. In said invention, the diniconazole is mixed with synergist so that its antimicrobial microstatic spectrum is identical to that of diniconazole and complex compound consist of diniconazole and inorganic salt, and its antimicrobial effect if good, toxicity is low, preparation process is simple and production cost is low. Besides, it has a certain microfertilizer action.
Description
The present invention relates to a kind of preparation method of agricultural chemicals mixed component.
Alkene azoles alcohol is widely known by the people as disinfectant use in agriculture, and its drug effect excellence is one of improved seeds that can be counted on one's fingers in the triazole germicide series.Weak point is the synthetic route more complicated, the raw material costliness, again in addition when E formula ketone is reduced into E formula alcohol, even use the extraordinary hydroboration metal of selectivity also still to exist small part C=C to be reduced into C-C, with the problem that E formula ketone is reduced into E formula alcohol, so production cost and control cost all are higher than other triazole germicide series.
Numerous researchers attempt to utilize the chemical property of alkene azoles alcohol on the basis that keeps alkene azoles alcohol active structure, convert it into derivative, improve purpose active, that reduce cost to reach.The method of report alkene azoles alcohol and inorganic acid salify is arranged in patent documentation, and behind the salify, its drug effect improves really, owing to there is side reaction, yield is not very good during salify, so though the control cost decreases but fall and not quite.Reported also that in patent documentation alkene azoles alcohol becomes the method for complex compound with the inorganic acid salt of alkali metal, alkaline earth metal, the sterilization of its complex compound, bacteriostatic activity all are higher than former parent compound---alkene azoles alcohol, but owing to still have side reaction in the complexing process, the complexing yield is not very good, so though the control cost all decreases than the above two, but still still higher, and complexing technology more complicated, very long.
So searching can reduce the disinfectant use in agriculture of the diniconazole composite of control cost significantly, remain the vital task of pendulum in face of numerous scientific and technical personnel.
The preparation method who the purpose of this invention is to provide a kind of Synergistic diniconazole composite, technology is simple, can reduce the control cost significantly, and the diniconazole composite drug effect height, the toxicity that obtain are low.
The preparation method of Synergistic diniconazole composite of the present invention is characterized in that it being that raw material by containing the pure and mild synergist of alkene azoles mixes with arbitrary proportion, and synergist is the metal inorganic hydrochlorate with following general formula: MXnkH
2O, M are meant the metal ion in IIA, IIIA, IVA, IB, IIB, IVB～VIIB and the VIII family, and X is meant inorganic acid radical, and n is 1～4 integer, and k is the number of the contained water of crystallization of this salt, and k is 0～18.
M preferably is meant Mg, Zn, Cu, Co, Mn, Ni, Sn, Fe, Mo, Al, Pb ion in the general formula, and the best is Mg, Zn, Cu ion.
The inorganic acid radical of X representative can be halogen acids root, sulfate radical, nitrate anion, phosphate radical, hydrogen phosphate, bisulfate ion in the general formula.Halogen acids root the best is chlorion, bromide ion.
The number of contained water of crystallization when k is metal ion and inorganic acid radical salify in the general formula, it can be 0, also can be 1～24 natural number.
Below enumerate formula M XnkH
2The concrete material of O, but be not limited to this:
HgSO
4.H
2O、CaSO
4.2H
2O、Ti(SO
4)
3、BaSO
4、CoSO
4.7H
2O、Fe
2(SO
4)
3.9H
2O、PbSO
4、Ce
2(SO
4).8H
2O、Tl
2SO
4、BeSO
4.4H
2O、Al
2(SO
4)
3.18H
2O、CuSO
4.5H
2O、Cr
2(SO
4)
3.18H
2O、Ag
2SO
4、Zr(SO
4)
2.4H
2O、ZnSO
4.7H
2O、MnSO
4.4H
2O、SrSO
4、MgSO
4.7H
2O、3CdSO
4.8H
2O、NiSO
4.6H
2O、NiSO
4.7H
2O、FeSO
4.7H
2O、SnSO
4。
HgCl
2、CaCl
2.6H
2O、BaCl
2.H
2O、PdCl
2.2H
2O、CoCl
2.6H
2O、AlCl
3.6H
2O、BeCl
2.2H
2O、PbCl
2、FeCl
3.H
2O、AgCl、CrCl
3、CuCl
2.2H
2O、ZnCl
2.2H
2O、SnCl
4.5H
2O、MnCl
2.4H
2O、SrCl
2.6H
2O、MgCl
2.6H
2O、NiCl
2.6H
2O、2CdCl
2.H
2O
Ca
3(PO
4)
2、Ag
3PO
4、Zn
3(PO
4)
2.4H
2O、CaHPO
4.2H
2O、Ca(H
2PO
4)
2.H
2O
HgBr
2、AlBr
3.6H
2O、AgBr
2Hg(NO
3)
2.H
2O、Th(NO
3)
4.4H
2O、Ca(NO
3)
2.4H
2O、Ba(NO
3)
2、Co(NO
3)
2.6H
2O、Fe(NO
3)
3.9H
2O、Pb(NO
3)
2、Bi(NO
3)
3.5H
2O、Al(NO
3)
3.9H
2O、Cu(NO
3)2.6H
2O、AgNO
3、Zr(NO
3)
2.6H
2O、Sr(NO
3)
2、Mn(NO
3)
2.6H
2O、Mg(NO
3)
2.6H
2O、Cd(NO
3)
2.4H
2O、Ni(NO
3)
2.6H
2O、La(NO
3)
2.6H
2O
Alkene azoles of the present invention alcohol is mixed by arbitrary proportion with the metal inorganic hydrochlorate, and alkene azoles alcohol can mix with in the inorganic acid salt one or more.
Although alkene azoles alcohol mixes with arbitrary proportion with inorganic acid salt, but optimum proportioning is: alkene azoles alcohol and inorganic acid salt are with its co-toxicity co-toxicity coefficient when maximum, the amount ratio of alkene azoles alcohol and inorganic acid salt, better is: determined the amount of inorganic acid salt in order to last method after, slightly higher again, the accumulative total consumption of this salt is done within little fertile reasonable safety using amount of time spent for this salt after the increase.
The metal inorganic hydrochlorate mainly is to use as synergist in the present invention, through experiment, also has certain little fertile effect.The metal inorganic hydrochlorate is selected concrete material such as MgCl
2.6H
2O in the not area use of magnesium deficiency fertilizer, only can demonstrate excellent bactericidal effect, and have little fertile acting in the use of magnesium deficiency area.Therefore can select the different metal inorganic acid salt to mix according to the soil fertility situation uses.
As the inorganic acid salt that uses two or more, can arbitrary proportion except the amount of synergist, the better consumption of synergist is: at first determine alkene azoles alcohol and the ratio of each inorganic acid salt with its co-toxicity co-toxicity coefficient maximum, after dividing equally according to the species number of used inorganic acid salt then, merge and use.Be exemplified below:
If A is that one of metal inorganic hydrochlorate is (as ZnCl
2) and alkene azoles alcohol co-toxicity coefficient when maximum, the consumption of inorganic acid salt (mole)
B be the metal inorganic hydrochlorate two (as MgCl
2.6H
2O) and alkene azoles alcohol co-toxicity coefficient when maximum, the consumption of inorganic acid salt (mole)
X is the species number of synergistic blend agent, so
Consisting of of mixed component of the present invention: alkene azoles alcohol: one of metal inorganic hydrochlorate is (as ZnCl
2): the metal inorganic hydrochlorate two (as MgCl
2.6H
2O)=1:A/X: B/X
During three kinds of synergist immixtures, be 1:A/3: B/3: C/3 just, when C is three and the alkene azoles alcohol co-toxicity coefficient maximum of metal inorganic hydrochlorate, the consumption of inorganic acid salt (mole)
The co-toxicity coefficient of alkene azoles alcohol and inorganic acid salt can be determined with calculating by experiment, and determine maximum co-toxicity coefficient.
In said mixture, also the be mixed sulphur of arbitrary proportion of the present invention.Sulphur has the effect of the mixture synergy that alkene azoles alcohol and inorganic acid salt are formed.The optimum amount of sulphur is determined by following: the weight sum of the pure and mild inorganic acid salt of alkene azoles and the part by weight of sulphur are 1: 0.05～5, and the best is 1: 0.05～3.
The mixed component that the inventive method obtains is still made the various preparations of pesticide field acceptable with prior art and is used, as:
1, with the mixed component is active component, in addition suitably, an amount of emulsifier, solvent or cosolvent, stirs and be processed into missible oil.
2, with the mixed component be active component, in addition suitably appropriate amount of addition agent (comprising thickener, tackifier, wetting agent, emulsifier, defoamer, anti-winter agent) is processed into aqueous suspension through ultramicro grinding.
3, with the mixed component be active component, in addition suitably an amount of filler becomes pulvis through grinding and processing.
4, with the mixed component be active component, in addition suitably an amount of wetting agent, filler become wetting powder through grinding and processing.
5, be active component with the mixed component, be processed into various formulations such as granule, fine granule, seed coating medicine, seed dressing.
The present invention can think that the complicated complexing process as described in the prior art of carrying out between alkene azoles alcohol and inorganic acid salt has been given crop or thalline self goes to finish, therefore the present invention only needs simple the mixing to get final product, in the preparation that is processed into this mixed component, can detect the complex compound component of small part, illustrate and in the preparation processing process, can finish a fraction of complexing process.
Advantage of the present invention:
The present invention simply mixes with synergist with alkene azoles alcohol, the constituent that obtains has alkene azoles alcohol and the alkene azoles alcohol bactericidal spectrum same with the complex compound of mineral salt formation, good drug efficacy, toxicity is low, alkene azoles alcohol and mineral salt complexing complex process, cycle is long, the complexing yield is 6.8～89%, and the effective rate of utilization of alkene azoles alcohol of the present invention is 100%, technology is quite simple, thus production cost and the control cost reduce significantly, in addition, also have certain little fertile effect, have bigger economy, society, environmental benefit.
Below be relevant experiment to the constituent that obtains with method of the present invention:
| Numbering | The builder salts hydrochlorate | Numbering | Synergist sulphate | Numbering | Synergist nitrate |
| 1 | ????Mg 2+ | 9 | ????Mg 2+ | 17 | ????Mg 2+ |
| 2 | ????Zn 2+ | 10 | ????Zn 2+ | 18 | ????Zn 2+ |
| 3 | ????Cu 2+ | 11 | ????Cu 2+ | 19 | ????Cu 2+ |
| 4 | ????Fe 2+ | 12 | ????Fe 2+ | 20 | ????Fe 2+ |
| 5 | ????Ni 2+ | 13 | ????Ni 2+ | 21 | ????Ni 2+ |
| 6 | ????Co 2+ | 14 | ????Co 2+ | 22 | ????Co 2+ |
| 7 | ????Al 3+ | 15 | ????Al 3+ | 23 | ????Al 3+ |
| 8 | ????Pb 2+ | 16 | ????Pb 2+ | 24 | ????Pb 2+ |
Synergist in the last table mixes with alkene azoles alcohol and obtains mixed component 1～24.
Experiment one:
With the culture dish of 9 centimetres of diameters, put into filter paper, watering makes filter paper keep moistening, then sprinkles rice paddy seed, treat rice seed germination after, standby when seedling grows to five leaves.The various medicament dilutions made above-mentioned effective mixture are the soup of 25ppm, get 20 milliliters of soups and evenly spray cloth at Miao Zhushang, be placed on diel taking-up in 20～25 insulating boxs of spending, gather back the diseased plant leaf that infects the concurrent unboiled water rice sheath blight from the field, be inoculated in the incubator that is placed on temperature 30 ± 2 degree, humidity 100% on each strain seedling, one week the back check the seedling situation of catching an illness, record, calculate with following formula, the result is as follows:
Formula: preventive effect (%)=(1-treatment region disease refer to/non-processor district disease refer to) * 100
| Numbering | The result | Numbering | The result | Numbering | The result |
| 1 | ?100 | ?9 | ?100 | ?17 | ?100 |
| 2 | ?100 | ?10 | ?100 | ?18 | ?100 |
| 3 | ?99 | ?11 | ?94 | ?19 | ?89 |
| 4 | ?100 | ?12 | ?98 | ?20 | ?100 |
| 5 | ?100 | ?13 | ?100 | ?21 | ?100 |
| 6 | ?100 | ?14 | ?100 | ?22 | ?100 |
| 7 | ?100 | ?15 | ?100 | ?23 | ?100 |
| 8 | ?100 | ?16 | ?100 | ?24 | ?100 |
Disease refers to be divided into Pyatyi:
One-level: lesion area accounts for below 1% of whole area;
Secondary: lesion area accounts for 2～5% of whole area;
Three grades: lesion area accounts for 6～20% of whole area;
Level Four: lesion area accounts for 21～40% of whole area;
Pyatyi: lesion area accounts for more than 40% of whole area.
Experiment two:
With the culture dish of 9 centimetres of diameters, put into filter paper, watering makes filter paper keep moistening, then puts into cucumber seeds, standby when treating behind the seed sprouting two leaf stage.The medicament dilution made above-mentioned effective mixture is the soup of 25ppm, get 20 milliliters of soups and evenly spray cloth on seedling, be placed on diel taking-up in 20～25 insulating boxs of spending, again with the suspension inoculation that has the anthrax bacteria spore, be placed in the incubator of temperature 30 ± 2 degree, humidity 100%, the plant situation of catching an illness is checked in one week back, and record calculates (with experiment one) prevention result, and the result is as follows:
| Numbering | The result | Numbering | The result | Numbering | The result |
| 1 | ?100 | ?9 | ?100 | ?17 | ?100 |
| 2 | ?100 | ?10 | ?97 | ?18 | ?100 |
| 3 | ?100 | ?11 | ?100 | ?19 | ?100 |
| 4 | ?100 | ?12 | ?100 | ?20 | ?88 |
| 5 | ?94 | ?13 | ?100 | ?21 | ?100 |
| 6 | ?100 | ?14 | ?100 | ?22 | ?100 |
| 7 | ?98 | ?15 | ?88 | ?23 | ?100 |
| 8 | ?100 | ?16 | ?100 | ?24 | ?100 |
Experiment three:
With the culture dish of 12 centimetres of diameters, put into filter paper, watering makes filter paper keep moistening, and then putting into kind is the little wheat seeds of Shandong wheat 13, standby when treating to grow to four leaves behind the seed sprouting.The various medicament dilutions made above-mentioned effective mixture are the soup of 25ppm, get 20 milliliters of soups and evenly spray cloth at Miao Zhushang, be placed on diel taking-up in 23～27 insulating boxs of spending, use the plant disease leaf that the powdery mildew germ is arranged that dyes that collects from the field again, be inoculated on every strain seedling, be placed in the incubator of temperature 30 ± 2 degree, humidity 100%, one week the back check the plant situation of catching an illness, record calculates (with experiment one) prevention result, and the result is as follows:
| Numbering | The result | Numbering | The result | Numbering | The result |
| 1 | ?100 | ?9 | ?100 | ?17 | ?100 |
| 2 | ?100 | ?10 | ?100 | ?18 | ?100 |
| 3 | ?100 | ?11 | ?100 | ?19 | ?100 |
| 4 | ?100 | ?12 | ?100 | ?20 | ?100 |
| 5 | ?100 | ?13 | ?100 | ?21 | ?100 |
| 6 | ?100 | ?14 | ?100 | ?22 | ?100 |
| 7 | ?100 | ?15 | ?100 | ?23 | ?100 |
| 8 | ?100 | ?16 | ?100 | ?24 | ?100 |
Experiment four:
With the culture dish of 12 centimetres of diameters, put into filter paper, watering makes filter paper keep moistening, then puts into cucumber seeds, standby when treating to grow to four leaves behind the seed sprouting.The various medicament dilutions made above-mentioned effective mixture are the soup of 25ppm, get 20 milliliters of soups and evenly spray cloth on seedling, be placed on diel taking-up in 20～25 insulating boxs of spending, use the plant disease leaf that Pseudoperonospora cubensis is arranged that dyes that collects from the field again, be inoculated on every strain seedling, be placed in the incubator of temperature 30 ± 2 degree, humidity 100%, one week the back check the plant situation of catching an illness, record calculates (with experiment one) prevention result, and the result is as follows:
| Numbering | The result | Numbering | The result | Numbering | The result |
| 1 | ?87 | ?9 | ?98 | ?17 | ?100 |
| 2 | ?90 | ?10 | ?67 | ?18 | ?99 |
| 3 | ?100 | ?11 | ?79 | ?19 | ?100 |
| 4 | ?88 | ?12 | ?85 | ?20 | ?100 |
| 5 | ?89 | ?13 | ?100 | ?21 | ?100 |
| 6 | ?100 | ?14 | ?100 | ?22 | ?100 |
| 7 | ?98 | ?15 | ?100 | ?23 | ?100 |
| 8 | ?73 | ?16 | ?89 | ?24 | ?78 |
Experiment five:
The mensuration of maximum co-toxicity coefficient:
With the flowerpot of 20 centimetres of diameters plantation wheat seeding, kind is Shandong wheat No. 13, and it is standby wholeheartedly the time to wait to grow to four leaves.CuCl
2.2H
2O, ZnCl
2.2H
2O, MgSO
4.7H
2O, CuSO
4.5H
2O, MgCl
2.6H
2O, ZnSO
4.7H
2The made medicament of the mixture of these six kinds of salt of O and alkene azoles alcohol is diluted to the soup of 6ppm, respectively get 20 milliliters and evenly spray cloth on seedling, dip in dried writing brush and to get an amount of powdery mildew conidium, be inoculated on the seedling, be placed in the greenhouse of temperature 25 ± 2 degree, humidity 100% and cultivate, 20 days " Invest, Then Investigate " blade incidences, result of calculation, the result is as follows:
Corresponding salt co-toxicity coefficient
ZnCl
2.2H
2O?????????184
MgCl
2.6H
2O?????????192
CuCl
2.2H
2O?????????203
ZnSO
4.7H
2O?????????175
MgSO
4.7H
2O?????????188
CuSO
4.5H
2O?????????193
The co-toxicity coefficient of the mixture of other salt and alkene azoles alcohol is measured and is calculated by same procedure.
Experiment six:
Undertaken by the Huo Shi method, select 960 of healthy white rats, female, hero respectively is divided into 192 groups, and five every group, the animal fasting is a gastric infusion after 12 hours, and poisoning dosage is 464,1000,2150,4640 milligrams/kilogram.Observed 14 days continuously behind the animal contaminated, during observe and record animal poisoning symptom and death toll, obtain half according to animal dead quantity and extremely measure, the result is as follows:
| Numbering | ??LD 50 | Numbering | ??LD 50 | Numbering | ??LD 50 |
| ?1 | ＞4640 | ?9 | ＞4640 | ?17 | ＞4640 |
| ?2 | ＞4640 | ?10 | ＞4640 | ?18 | ＞4640 |
| ?3 | ＞4640 | ?11 | ＞4640 | ?19 | ＞4640 |
| ?4 | ＞4640 | ?12 | ＞4640 | ?20 | ＞4640 |
| ?5 | ＞4640 | ?13 | ＞4640 | ?21 | ＞4640 |
| ?6 | ＞4640 | ?14 | ＞4640 | ?22 | ＞4640 |
| ?7 | ＞4640 | ?15 | ＞4640 | ?23 | ＞4640 |
| ?8 | ＞4640 | ?16 | ＞4640 | ?24 | ＞4640 |
Be embodiment below, but the present invention is not limited to this.Each embodiment is by preparation method of the present invention, and alkene azoles alcohol mixes with inorganic acid salt, and mixed component obtains relevant preparation by the preparation method of common pesticide field preparation.
Embodiment one:
Alkene azoles alcohol is made 3.5% missible oil with magnesium chloride hexahydrate, by every mu of active ingredient 4 grams, 25 grams, 1 gram dilution, compare with every mu of active ingredient of 12.5% alkene azoles alcohol wetting powder 1.5 grams, repeat four times, prevent and treat powdery mildew of cucumber with the sprayer even spraying, check result is as follows after 14 days:
Consumption preventive effect %3.5% alkene azoles alcohol and magnesium chloride hexahydrate missible oil 4 90.1
2.5????????86.4
1??????????82.5
12.5% alkene azoles alcohol wetting powder 4 83.1
Embodiment two:
5% Myristicin azoles alcohol missible oil
Alkene azoles alcohol 3.5%
Magnesium chloride hexahydrate 1.5%
Ethanol 30%
Emulsifier (0202-C) 10%
The dimethylbenzene surplus
Embodiment three:
5% Myristicin azoles alcohol missible oil
Alkene azoles alcohol 3.5%
Two water zinc chloride 1.5%
Ethanol 30%
Emulsifier (670) 10%
The dimethylbenzene surplus
Embodiment four:
3.5% diniconazole suspending agent
Alkene azoles alcohol (90%) 4.0%
Copper chloride dihydrate 3.2%
Sulphur 10.2%
Dispersant (lignosulfonates) 3%
Wetting agent (34#, 6202-C etc.) 4%
Bentonite 5%
Emulsifier (34#) 2.0%
Xanthan gum 0.05%
Ethylene glycol 4.0%
Water surplus
Embodiment five:
3.5% synergy diniconazole suspending agent
Alkene azoles alcohol (90%) 3.9%
Green-vitriol 3%
Dispersant (lignosulfonates) 3.0%
Wetting agent (6202-C) 3.0%
Bentonite 6.0%
Ethylene glycol 4.0%
Odium stearate 1.0%
Octanol 1.0%
Water surplus
Embodiment six:
3.5% Myristicin azoles alcohol missible oil
Alkene azoles alcohol (90%) 3.9%
Six water nickel nitrates 3.2%
Ethanol 30%
Emulsifier (33#) 10.0%
The toluene surplus
Alkene azoles alcohol is mixed and made into acceptable forms on the agricultural chemicals with other metal inorganic hydrochlorate, enumerates no longer in an embodiment, by the description of this specification.
Claims (9)
1, a kind of preparation method of Synergistic diniconazole composite is characterized in that it being that raw material by comprising the pure and mild synergist of alkene azoles mixes with arbitrary proportion, and synergist is the metal inorganic hydrochlorate with following general formula: MXnkH
2O, M are meant the metal ion in IIA, IIIA, IVA, IB, IIB, IVB～VIIB and the VIII family, and X is meant inorganic acid radical, and n is 1～4 integer, and k is the number of the contained water of crystallization of this salt, and k is 0～18.
2, preparation method according to claim 1, the sulphur of the arbitrary proportion that it is characterized in that also being mixed.
3, preparation method according to claim 1 is characterized in that X represents halogen acids root, sulfate radical, nitrate anion, phosphate radical, bisulfate ion, hydrogen phosphate.
4, preparation method according to claim 3 is characterized in that described halogen acids root is chlorion, bromide ion.
5, preparation method according to claim 1 is characterized in that M is meant Mg, Zn, Cu, Co, Mn, Ni, Sn, Fe, Mo, Al, Pb ion, is preferably Mg, Zn, Cu ion.
6, preparation method according to claim 1 is characterized in that alkene azoles one or more metal inorganic hydrochlorates pure and in the synergist mix.
7, preparation method according to claim 1, it is characterized in that alkene azoles alcohol and synergist with the ratio of its co-toxicity co-toxicity coefficient maximum or synergist a little more than its co-toxicity coefficient the ratio when maximum mix, the amount of increase is the reasonable volume that synergist is done little fertilizer time spent to the maximum.
8, mixing preparation method according to claim 6, when it is characterized in that alkene azoles alcohol mixes with more than one metal inorganic hydrochlorates, the consumption of each inorganic acid salt is: at first determine alkene azoles alcohol and the ratio of each inorganic acid salt with its co-toxicity co-toxicity coefficient maximum, divide equally according to the species number of used salt then.
9, mixing preparation method according to claim 2 is characterized in that the weight sum of the pure and mild metal inorganic hydrochlorate of alkene azoles and the part by weight of sulphur are 1: 0.05～5, and the best is 1: 0.05～3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011017716A CN1182784C (en) | 2000-01-28 | 2001-01-02 | Preparation of synergistic diniconazole composite |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00110872 | 2000-01-28 | ||
| CN00110872.7 | 2000-01-28 | ||
| CNB011017716A CN1182784C (en) | 2000-01-28 | 2001-01-02 | Preparation of synergistic diniconazole composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1307807A true CN1307807A (en) | 2001-08-15 |
| CN1182784C CN1182784C (en) | 2005-01-05 |
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ID=25739349
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|---|---|---|---|
| CNB011017716A Expired - Fee Related CN1182784C (en) | 2000-01-28 | 2001-01-02 | Preparation of synergistic diniconazole composite |
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| Country | Link |
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| CN (1) | CN1182784C (en) |
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2001
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