CN100455567C - Metal salt in iron group of dithiocarbamic acid for fishing medicine - Google Patents
Metal salt in iron group of dithiocarbamic acid for fishing medicine Download PDFInfo
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- CN100455567C CN100455567C CNB200510018516XA CN200510018516A CN100455567C CN 100455567 C CN100455567 C CN 100455567C CN B200510018516X A CNB200510018516X A CN B200510018516XA CN 200510018516 A CN200510018516 A CN 200510018516A CN 100455567 C CN100455567 C CN 100455567C
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- dithiocarbamic acid
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Abstract
The present invention relates to an iron family salt of dithiocarbamic acid, which is used as fishing medicines and belongs to the field of pesticide. The effective constituents of the new-type iron family metal salt of the dithiocarbamic acid accord with the general formula. Firstly, organic amine reacts with a solution of sodium hydroxide or potassium hydroxide, and then, carbon disulfide is slowly dripped in. Temperature is controlled to be lower than 35 DEG C; after the carbon disulfide stops being dripped, reaction continues to be carried out for 2 to 3 hours at the room temperature, and sodium salt or potassium salt intermediates of the dithiocarbamic acid are generated. The present invention is characterized in that in the general formula, M is metal iron or nickel, R is methylamine, dimethylamine, ethylamine, ethylenediamine, propylamine, propane diamine or isopropyl diamine, and n is 1, 1.5, 2 or 3. the sulfate (or chloride) of iron or nickel is added to the sodium salt or potassium salt intermediates of the dithiocarbamic acid, and double decomposition reaction is carried out to generate original drugs of iron or nickel salts of the dithiocarbamic acid. The technological progress of the present invention is very obvious, and the present invention has the advantages that the salt is favorable for ecological balance and environmental protection. The fishing medicines made according to the salt have the advantages of high drug effect and low toxicity, no pollutants are discharged in the preparation processes, and the present invention provides a green technique of environmental protection. In addition, obviously, besides meeting the application of high requirement fishing medicines, the iron family salt of dithiocarbamic acid is also suitable for crops.
Description
Technical field
The present invention belongs to pesticide field as the dithiocar-bamate of fishing medicine.
Background technology
Dithiocar-bamate is a known technology as the pesticide-germicide medicine on the agricultural, and as the N on the market, N-dimethyl dithiocarbamic acid class, ethylene dithiocarbamic acid class commercially available agricultural chemical also have sale.Above-mentioned agricultural chemicals mainly is to be used for farm crop, prevents all kinds of disease and pests but up to now.Shang Weijian is relevant for the report of dithiocar-bamate as the fishing medicine.Particularly dithiocarbamic acid molysite and nickel salt.To the medication of farm crop disinfection and deinsectization, as required, or the effective ingredient that from soil, absorbs the drug of the root yarn by plant, or spraying medicine is directly killed pathogenic insect pest on plant leaf, thus safeguard the stalwartness growth of farm crop.Requiring of fish medication and farm crop medication is different, and the fishing medication is that medicine is splashed in the breed waters of fish, and medicine directly enters in the body of the class of breeding fish.In general, the fish health is little, and intracorporeal organ is petite, and the comparison farm crop require also more harsh.Used medicine not only requires kill bacteria, sick worm, and can not any murder by poisoning be arranged to fish itself, does not also allow indirectly the fishery product eater to be worked the mischief.Therefore, to fishing medicine special requirement: low toxicity, efficient, consumption is few, the medicine dispersing property is good, can form finely dispersed drug level at water field of big area.
There is following problem in several fishing medicines in current market
Chrysanthemum ester class: the safe concentration scope is little, and the safe concentration of permission is low, has deviation to cause crushing blow to breed slightly.
Organic phosphates: the eubiosis in organophosphorus havoc waters is the agricultural chemicals of being about to ban use of.
Copper sulfate: drug effect is low, and consumption is big, and the residual excessive meeting of copper causes liver to be poisoned, and the price height.
Chlorinated product: unstable chemcial property, packing and transportation inconvenience to some extent the strong impulse smell is arranged, and consumption is big, price is high.
Avermectins: though be a kind of broad spectrum pesticide, DeGrain, and consumption is too big, and cost is high too.
Existing dithiocar-bamate can not satisfy the requirement of fishing medication, though zinc salt of dithiocarbamate in water specific activity at the nonirrigated farmland height, but still existing problems.For example, zinc salt of dithiocarbamate is extremely unstable, and pure product all easily decompose, and just say nothing of aqua.Simultaneously existing dithiocar-bamate powder product is to make by organic solvent extraction, not only causes former medicine loss, and causes environmental pollution because of dust and sewage.Even pulvis does not have the problem that exists in the above-mentioned preparation, in use, pulvis is difficult to prepare uniform dispersion liquid, for even medication brings difficulty.As without extraction, directly adopt aqua, then there is the preservation problem, the water liquid of above-mentioned dithiocar-bamate medicine very easily decomposes and lumps, the inevitable adverse consequences that cause because of medication is inhomogeneous during use.
Aminodithioformic acid copper (zinc) salt that Chinese patent CN1368005A " Aminodithioformate-type agricultural chemicals and method for making thereof " relates to also is the farm crop medication.In its effective ingredient general formula, n is 1,2; M is K, Na, Zn, or Cu; Organic amine is methylamine, dimethylamine, Trimethylamine 99 or ethamine.
Summary of the invention
The purpose of this invention is to provide the dithiocarbamic acid iron family metal salt as the fishing medicine, for fishery cultivating provides efficiently, low toxicity, free of contamination novel fishing medicine.
Technical scheme of the present invention is as follows:
This dithiocarbamic acid iron family metal salt comprises N-methyl dithiocarbamic acid iron and N-methyl dithiocarbamic acid nickel.
With above-mentioned aminodithioformic iron family metal salt is that the prescription of the water and milk matter fishing medicine suspension agent of former medicine is:
The former medicine 10-34% of dithiocarbamic acid iron family metal salt
Carrier dispersion agent 8-16%
Multi-functional emulsifier 5-12%
Colloidal dispersion agent 0.2-5%
Antioxidant 1-3%
Sanitas 0.2-3%
Frostproofer 2-3%
Surplus is the sodium salt that water and replacement(metathesis)reaction are produced
PH:6-7 temperature: room temperature
Preparation method by above-mentioned water and milk matter fishing medicine suspending agent formula fishing medicine is:
1), makes the reaction of organic amine and sodium hydroxide or potassium hydroxide solution earlier, slowly drip dithiocarbonic anhydride again, controlled temperature is below 35 ℃, dithiocarbonic anhydride dropwises, the what room temperature continues reaction 2-3 hour, generate nabam salt or sylvite intermediate, wherein organic amine can be methylamine, ethamine or propylamine;
2), in above-mentioned nabam salt or sylvite intermediate, add iron(ic) chloride or ferric sulfate or nickelous chloride or single nickel salt, carry out replacement(metathesis)reaction again, generate the water medium product of dithiocarbamic acid iron or nickel salt;
3), with ball mill grinding former medicine fineness is reached below 300 microns the water medium product that generates, add carrier dispersion agent, multi-functional emulsifier, colloidal dispersion agent, antioxidant, sanitas and frostproofer more in proportion after, brute force stirs and gets final product packing.
By the dithiocarbamic acid iron family metal salt of the present invention as the former medicine of fishing medicine, the organic amine of use comprises methylamine, ethamine and propylamine, and the salify iron family metal of employing comprises iron and nickel.
By the fishing medicine suspension agent of the water and milk matter fishing medicine suspending agent formula preparation that comprises the former medicine of dithiocarbamic acid iron family metal salt of the present invention is the fishery medication of good technology upgrading, and the sick effect of treatment fishing is obvious, also can do general farm crop medication certainly.
Technical progress of the present invention is fairly obvious, and more outstanding advantage is favourable ecology, environmental, by the fishing medicine that the present invention produced is that homodisperse fishing is with disperseing soup water and milk matter suspension agent, drug effect is very high, and toxicity is but very low, the preparation process non-pollutant discharge, atom utilization is 100%, is a kind of environment-friendly technology.In addition, self-evident, except that satisfying the application of high request fishing medicine, also be applicable to farm crop certainly.
Embodiment
By following example illustrated the present invention from raw material to intermediate, from intermediate to the water medium product of former medicine, and the water medium product of getting former medicine is prepared homodisperse fishing with the whole process of disperseing the soup suspension agent; And the effect of water and milk matter fishing medicine suspension agent treatment fishing disease of the present invention
The preparation of example 1.N-methyl dithiocarbamic acid nickel
Aqueous methylamine solution and 400 gram sodium hydroxide with 900 grams 33% dissolve in reaction kettle for reaction earlier, slowly be added dropwise in the reaction solution again 760 gram dithiocarbonic anhydride, control reaction temperature is below 35 ℃ during dropping, dithiocarbonic anhydride dropwises, the what room temperature continues reaction 2-3 hour, add 650 gram nickelous chlorides more in batches, stirred 30 minutes, promptly obtain 40% the 2700 water medium products that restrain N-methyl dithiocarbamic acid nickel.Yield is 91%.
The former medicine of 2700 grams with above-mentioned 40% adds suitable quantity of water and becomes particulate below 300 microns with ball mill grinding, wherein adds
Ultrafine kaolin 600 grams
Tween-80 600 grams
Xanthan gum 250 grams
Tenox PG 500 grams
Sodium Benzoate 150 grams
Glycerine 250 grams
Add water to 5000 grams again, add powerful the stirring, and use the high speed shear mulser, emulsification pretreatment, the homodisperse water and milk matter suspension agent product of the N-methyl dithiocarbamic acid nickel of acquisition 20%.
Example 2, the sick effect example of water and milk matter fishing medicine suspension agent of the present invention treatment fishing
The sick effect of water and milk matter fishing medicine suspension agent treatment fishing that contains N-methyl dithiocarbamic acid iron
| Fishing pool area | Fishing pool incidence | Symptom | Use the medicine name of suspension agent | With concentration (pure product content) | Administrated method | Effect after the medication |
| 10 mu | Explosive hemorrhagic disease | The dead fish of persistence | N-methyl dithiocarbamic acid iron | 120mg/m 3 | Full pool spilling head | Stop dead fish the 3rd day morning |
Claims (3)
1, dithiocarbamic acid iron family metal salt is N-methyl dithiocarbamic acid iron or N-methyl dithiocarbamic acid nickel.
2, the dithiocarbamic acid iron family metal salt with claim 1 is the water and milk matter fishing medicine suspension agent of former medicine, it is characterized in that:
The former medicine 10-34% of dithiocarbamic acid iron family metal salt
Carrier dispersion agent 8-16%
Multi-functional emulsifier 5-12%
Colloidal dispersion agent 0.2-5%
Antioxidant 1-3%
Sanitas 0.2-3%
Frostproofer 2-3%
Surplus is sodium salt or the sylvite that water and replacement(metathesis)reaction are produced
PH:6-7 temperature: room temperature
Above-mentioned multi-functional emulsifier is a tween-80.
3. the preparation method according to the water and milk matter fishing medicine suspension agent of claim 2 is:
1), makes the reaction of organic amine and sodium hydroxide or potassium hydroxide solution earlier, slowly drip dithiocarbonic anhydride again, controlled temperature is below 35 ℃, dithiocarbonic anhydride dropwises, the what room temperature continues reaction 2-3 hour, generate nabam salt or sylvite intermediate, wherein organic amine is a methylamine, ethamine or propylamine;
2), in above-mentioned nabam salt or sylvite intermediate, add iron(ic) chloride or ferric sulfate or nickelous chloride or single nickel salt, carry out replacement(metathesis)reaction again, generate the water medium product of dithiocarbamic acid iron or nickel salt;
3), with ball mill grinding former medicine fineness is reached below 300 microns the water medium product that generates, add carrier dispersion agent, multi-functional emulsifier, colloidal dispersion agent, antioxidant, sanitas and frostproofer more in proportion after, it is packing that brute force stirs.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510018516XA CN100455567C (en) | 2005-04-07 | 2005-04-07 | Metal salt in iron group of dithiocarbamic acid for fishing medicine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510018516XA CN100455567C (en) | 2005-04-07 | 2005-04-07 | Metal salt in iron group of dithiocarbamic acid for fishing medicine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1687028A CN1687028A (en) | 2005-10-26 |
| CN100455567C true CN100455567C (en) | 2009-01-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200510018516XA Expired - Fee Related CN100455567C (en) | 2005-04-07 | 2005-04-07 | Metal salt in iron group of dithiocarbamic acid for fishing medicine |
Country Status (1)
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| CN (1) | CN100455567C (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3523960A (en) * | 1967-08-03 | 1970-08-11 | Progil | Stabilization process of metal ethylene bis-dithiocarbamates |
| CN1049771A (en) * | 1989-09-01 | 1991-03-13 | 帝国化学工业公司 | Composition pesticide |
| CN1368005A (en) * | 2002-03-04 | 2002-09-11 | 贾朝钧 | Aminodithioformate-type agricultural chemicals and preparing process thereof |
-
2005
- 2005-04-07 CN CNB200510018516XA patent/CN100455567C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3523960A (en) * | 1967-08-03 | 1970-08-11 | Progil | Stabilization process of metal ethylene bis-dithiocarbamates |
| CN1049771A (en) * | 1989-09-01 | 1991-03-13 | 帝国化学工业公司 | Composition pesticide |
| CN1368005A (en) * | 2002-03-04 | 2002-09-11 | 贾朝钧 | Aminodithioformate-type agricultural chemicals and preparing process thereof |
Non-Patent Citations (10)
| Title |
|---|
| N N-双-硫代氨基甲酸盐类化合物的合成研究. 朱思成等人.山东师大学报自然科学版，第13卷第1期. 1998 |
| N N-双-硫代氨基甲酸盐类化合物的合成研究. 朱思成等人.山东师大学报自然科学版，第13卷第1期. 1998 * |
| 二硫化碳下游产品的开发及应用进展. 马文展等.现代化工，第10期. 1995 |
| 二硫化碳下游产品的开发及应用进展. 马文展等.现代化工，第10期. 1995 * |
| 巧用代森铵治疗鱼病. 鲍胜华.科学养鱼，第10卷. 2004 |
| 巧用代森铵治疗鱼病. 鲍胜华.科学养鱼，第10卷. 2004 * |
| 过渡金属络合物类降解塑料光敏剂的合成 结构与性能的表征. 陈庆华等.塑料工业，第28卷第1期. 2000 |
| 过渡金属络合物类降解塑料光敏剂的合成 结构与性能的表征. 陈庆华等.塑料工业，第28卷第1期. 2000 * |
| 防老剂的最新发展动向（一）. 张虹等.世界橡胶工业，第31卷第2期. 2004 |
| 防老剂的最新发展动向（一）. 张虹等.世界橡胶工业，第31卷第2期. 2004 * |
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| CN1687028A (en) | 2005-10-26 |
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Granted publication date: 20090128 Termination date: 20120407 |