CN106831649B - A kind of dazomet preparation process - Google Patents
A kind of dazomet preparation process Download PDFInfo
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- CN106831649B CN106831649B CN201611224369.6A CN201611224369A CN106831649B CN 106831649 B CN106831649 B CN 106831649B CN 201611224369 A CN201611224369 A CN 201611224369A CN 106831649 B CN106831649 B CN 106831649B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/15—Six-membered rings
- C07D285/16—Thiadiazines; Hydrogenated thiadiazines
- C07D285/34—1,3,5-Thiadiazines; Hydrogenated 1,3,5-thiadiazines
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Abstract
Dazomet preparation process disclosed by the invention, comprising: first step reaction, methylamine add appropriate extractant after reacting with carbon disulfide, separation obtains intermediate N methyl aminodithioformic acid；Second step reaction, intermediate N methyl aminodithioformic acid reacts in the reaction system for being added to suitable sulfate and surfactant with formaldehyde obtains dazomet.The present invention program avoids influence of the carbon disulfide remnants to product crystal structure, bulk density and production security by further eliminating product carbon disulfide in the first step extractant that row adds again after reaction.
Description
Technical field
The present invention relates to a kind of preparation method of pesticide, especially a kind of dazomet preparation process.
Background technique
Dazomet produces the history for having had many years, since bromomethane has destructiveness, international grain to atmospheric ozone layer
It is forbidden to use bromomethane after agriculture organization prescribed 2005, while dazomet is recommended as the substitute species of bromomethane in the whole world by FAO
It promotes the use of.The dosage form of dazomet is usually pulvis, wettable powder, and in use process, dust drifts about these preparations frequent occurrence,
It causes damages to people and crop.Also there are dust pollution and inconvenience in production, packaging, transportational process simultaneously, in order to reach
Non-dusting purpose, people take various physics, the method for chemistry prepares dazomet granule.Company provides according to pertinent literature
Material overcomes in the prior art insufficient and defect, successfully develops one using carbon disulfide, monomethyl amine, formaldehyde as main material, sulphur
The preparation process of hydrochlorate, the stable no dust dazomet granule that surfactant is auxiliary material solves the drift of dazomet dust
Shifting problem.
Home and abroad is mainly using the technique of German BASF (patent in the U.S.: US5495017) at present.The technique
Using carbon disulfide, monomethyl amine, formaldehyde as primary raw material, by adding the reagents such as alkyl diamine, alkylamine in the first step, cotton is obtained
Grand granule.The technique can obtain the granule of stable no dust drift, but the process requirement puts into special installation, and the energy disappears
When consuming greatly, and generating a large amount of stink damp, it be easy to cause the pollution of raw medicine loss and environment.
Summary of the invention
To solve the above problems, in the first step, row adds again after reaction the invention discloses a kind of dazomet preparation process
The extractant added further eliminates product carbon disulfide, and avoids carbon disulfide remnants close to product crystal structure, accumulation
The influence of degree and production security.
Dazomet preparation process disclosed by the invention, comprising: first step reaction, methylamine adds suitable after reacting with carbon disulfide
Extractant is measured, separation obtains intermediate N methyl aminodithioformic acid；Second step reaction, intermediate N methyl dithiocarbamates
Formic acid reacts in the reaction system for being added to suitable sulfate and surfactant with formaldehyde obtains dazomet.
This programme passes through solvent (such as methylene chloride, dichloroethanes, the chlorobenzene for adding density ratio water big in the first step is reacted
Deng) extra carbon disulfide in extraction reaction solution, prevent carbon disulfide take in next step (because carbon disulfide has volatility,
Such as enter second step to react, it is fluffy to will cause dazomet crystal, and heap density reduces, and eventually affects the particle matter of dazomet product
Amount), improve the quality of product.Flash-point additionally, due to carbon disulfide is -30 DEG C；Upper explosion limit (volume fraction): 60.0；Explosion
Lower limit (volume fraction): 1.0；Ignition temperature: 90 DEG C, it can be seen that when containing carbon disulfide steam in product dazomet particle,
The dangerous situations such as burning, detonation easily occur in it in production, packaging, transportational process, and influence to produce movable safety, this
Scheme avoids carbon disulfide and enters second step reaction and follow-up process, to highly improve the movable safety of production
Property, and the recovery utilization rate of carbon disulfide is promoted, discharge is reduced, harm of the production activity to environment is reduced.
A kind of improvement of dazomet preparation process disclosed by the invention, first step reaction are that first is sequentially added in consersion unit
Amine aqueous solution, water stir, and control reaction temperature, and carbon disulfide is added dropwise into stirring system, are added dropwise and maintain to react to anti-after terminating
Answering terminating point, reaction was completed, and suitable extractant is added into the water layer of acquisition through the isolated intermediate N methyl of reextraction
Aminodithioformic acid.
A kind of improvement of dazomet preparation process disclosed by the invention, second step reaction reaction system in also be added with strong pole
Property solvent.
This programme in second step reacts by being added appropriate intensive polar solvent (such as methanol, ethyl alcohol), thus suitably
The polarity of reaction system environment is adjusted, and the dissolubility of dazomet improves crystallization effect to prevent product to be quickly precipitated in enhancing system
Fruit, so that impurity residual rate can also be reduced by improving crystal habit, improves product to improve Product bulk density
The total quality of granular mass and product.
A kind of improvement of dazomet preparation process disclosed by the invention, second step reaction are that first is sequentially added in consersion unit
Intermediate N methyl dithiocarbamates are added in aldehyde aqueous solution, sulfate, surfactant, intensive polar solvent, stirring into system
Formic acid maintains to react to reaction terminating point, then dazomet particle can be obtained through separation.
A kind of improvement of dazomet preparation process disclosed by the invention, the first step reaction in extractant be methylene chloride, dichloro
It is any in ethane, chlorobenzene.
A kind of improvement of dazomet preparation process disclosed by the invention, the intensive polar solvent in reaction system that second step reacts
It is any in methanol, ethyl alcohol.
A kind of improvement of dazomet preparation process disclosed by the invention, second step reaction in sulfate be zinc sulfate, barium sulfate,
One or several kinds of mixture in calcium sulfate.
A kind of improvement of dazomet preparation process disclosed by the invention, second step reaction in surfactant be dodecyl sulphur
Sour sodium, nonylphenol polyoxyethylene ether sulfate, sodium alkyl sulfonate, mixture one or several kinds of in sodium lignin sulfonate.
A kind of improvement of dazomet preparation process disclosed by the invention, the first step reaction in, carbon disulfide is excessively added, with
The molar ratio of methylamine is greater than 0.5:1.Sufficiently to consume methylamine, and reduce a possibility that it causes damages.
A kind of improvement of dazomet preparation process disclosed by the invention, additive amount of the sulfate in second step reaction system are
Account for the 0.1%-1% of formaldehyde mole.
A kind of improvement of dazomet preparation process disclosed by the invention, addition of the surfactant in second step reaction system
Amount is the 0.1%-1% for accounting for formaldehyde mole.
A kind of improvement of dazomet preparation process disclosed by the invention, the first step reaction in methylamine reacted with second step in formaldehyde
Molar ratio be 1:(1-1.1).To promote intermediate sufficiently to react.
In the present invention program, in the addition of first step extractant and the addition of second step intensive polar solvent, dosage is simultaneously
Not stringent restriction, and make the actual conditions of actual process and add in right amount, in the specific range for meeting process requirement
It can slightly take the circumstances into consideration to use more or less slightlyly, the implementation without influencing the present invention program.
Dazomet preparation process disclosed by the invention, by using the first step after reaction again row addition extractant,
Product carbon disulfide is further eliminated, and avoids carbon disulfide remnants to product crystal structure, bulk density and production
The influence of safety；When passing through addition intensive polar solvent in second step simultaneously to the polar adjustment of system, and being crystallized to product
The control of machine avoids product in early stage too fast precipitation, to realize the improvement to product crystal habit, reduces impurity residual, leads to
The cooperation for crossing the two schemes finally promotes product particle quality and product total quality.
Specific embodiment
With reference to embodiment, the present invention is furture elucidated, it should be understood that following specific embodiments are only used for
It is bright the present invention rather than limit the scope of the invention.
Embodiment 1
In the present embodiment, dazomet preparation process, comprising: first step reaction, methylamine adds suitable after reacting with carbon disulfide
Extractant is measured, separation obtains intermediate N methyl aminodithioformic acid；Second step reaction, intermediate N methyl dithiocarbamates
Formic acid reacts in the reaction system for being added to suitable sulfate and surfactant with formaldehyde obtains dazomet.
Embodiment 2
In the present embodiment, dazomet preparation process, comprising: it is water-soluble to sequentially add methylamine in consersion unit for first step reaction
Liquid, water, stirring control reaction temperature, and carbon disulfide is added dropwise into stirring system, are added dropwise after terminating and maintain reaction to reaction terminating
Reaction was completed for point, and it is thio through the isolated intermediate N methyl two of reextraction that suitable extractant is added into the water layer of acquisition
Carbamic acid；Second step reaction, intermediate N methyl aminodithioformic acid and formaldehyde be added to suitable sulfate and
Reaction obtains dazomet in the reaction system of surfactant.
It is distinguished with above-described embodiment, is also added with intensive polar solvent in the reaction system of second step reaction.
It is distinguished with above-described embodiment, second step reaction is that formalin, sulfuric acid are sequentially added in consersion unit
Intermediate N methyl aminodithioformic acid is added in salt, surfactant, intensive polar solvent, stirring into system, maintains reaction
Dazomet particle can be obtained to reaction terminating point, then through separation.
It is distinguished with above-described embodiment, extractant is that (extractant can also be dichloro to methylene chloride in first step reaction
Ethane or chlorobenzene).
It is distinguished with above-described embodiment, the intensive polar solvent in the reaction system of second step reaction is that methanol is (highly polar
Solvent can also be ethyl alcohol).
Distinguished with above-described embodiment, second step reaction in sulfate be zinc sulfate (barium sulfate can also be include and
It is not limited to following any situation: barium sulfate；Calcium sulfate；Zinc sulfate, barium sulfate；Calcium sulfate, zinc sulfate；Barium sulfate, calcium sulfate；
Zinc sulfate, barium sulfate, calcium sulfate.When sulfate is mixture situation, mass ratio is arbitrary value).
It is distinguished with above-described embodiment, surfactant is dodecyl sodium sulfate (surface-active in second step reaction
Agent can also be include but not limited to following any situation: nonylphenol polyoxyethylene ether sulfate；Sodium alkyl sulfonate；Lignin
Sodium sulfonate；Dodecyl sodium sulfate, nonylphenol polyoxyethylene ether sulfate；Sodium alkyl sulfonate, sodium lignin sulfonate；Nonyl phenol is poly-
Ethylene oxide ether sodium sulfate, sodium alkyl sulfonate；Dodecyl sodium sulfate, sodium lignin sulfonate；Dodecyl sodium sulfate, alkyl sulfonic acid
Sodium；Nonylphenol polyoxyethylene ether sulfate, sodium lignin sulfonate；Dodecyl sodium sulfate, nonylphenol polyoxyethylene ether sulfate,
Sodium alkyl sulfonate；Sodium lignin sulfonate, dodecyl sodium sulfate, nonylphenol polyoxyethylene ether sulfate；It is sodium alkyl sulfonate, wooden
Plain sodium sulfonate, dodecyl sodium sulfate；Nonylphenol polyoxyethylene ether sulfate, sodium alkyl sulfonate, sodium lignin sulfonate；Dodecane
Base sodium sulfonate, nonylphenol polyoxyethylene ether sulfate, sodium alkyl sulfonate, sodium lignin sulfonate.Surfactant is mixing principle
When shape, mass ratio is arbitrary value).
It is distinguished with above-described embodiment, in first step reaction, carbon disulfide is excessively added, big with the molar ratio of methylamine
In 0.5:1 (in first step reaction, the molar ratio of carbon disulfide and methylamine can be include but not limited to following any situation:
0.55:1,0.6:1,0.65:1,0.7:1,0.75:1,0.8:1,0.85:1,0.9:1,0.95:1,1:1,1.05:1 and it is greater than
Other arbitrary values within the scope of 0.5:1).
It is distinguished with above-described embodiment, additive amount of the sulfate in second step reaction system is to account for formaldehyde mole
0.1% (additive amount of the sulfate in second step reaction system can also include without for (percentage for accounting for formaldehyde mole)
Be limited to following any situation: 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1% and
Other arbitrary values within the scope of 0.1%-1%).
It is distinguished with above-described embodiment, additive amount of the surfactant in second step reaction system is to account for formaldehyde mole
(additive amount of the surfactant in second step reaction system can also be (percentage for accounting for formaldehyde mole) to the 0.1% of amount
Include but not limited to following any situation: 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%,
Other arbitrary values within the scope of 1% and 0.1%-1%).
Distinguished with above-described embodiment, the first step reaction in methylamine reacted with second step in formaldehyde molar ratio be 1:1
(in the first step reaction methylamine reacted with second step in formaldehyde molar ratio can also be include but not limited to any feelings as follows
Shape: 1:1.01,1:1.02,1:1.03,1:1.04,1:1.05,1:1.06,1:1.07,1:1.08,1:1.09,1:1.1 and 1:
Other arbitrary values in (1-1.1) range).
Illustrate the excellent place of the present invention program with the specific embodiment in the present invention program claimed range below, it is right
The technical solution of the limited range of the present invention is representative.
Specific embodiment one
The first step reaction: under atmospheric pressure at room, with stirring, thermometer, dropping funel 250ml four-hole bottle in be added
The monomethylamine aqueous solution (about 0.395M) of 72g17% starts stirring, while there-necked flask is cooling with ice-water bath, and bis- sulphur of 18.2g is added dropwise
Change carbon (about 0.239M), maintaining reaction temperature is no more than 30 DEG C, and reaction was completed by 2h, and standing separates oil reservoir and applies, and water layer is added suitable
The about 20ml dichloroethanes of amount stirs 0.5h, and standing separates oil reservoir, and the intermediate water solution through dichloroethanes abstraction purification is direct
For the next step.
Second step reaction: under atmospheric pressure at room, with stirring, thermometer, dropping funel 250ml four-hole bottle in successively add
Enter 132g9% formalin (about 0.396M), 0.2g zinc sulfate (about 0.00124M), 0.2g ferric tri-dodecanesulfonate
(0.000694M), about 5g methanol, stirs evenly in right amount, and the resulting intermediate water solution of previous step is added dropwise.Control temperature is no more than
30℃.Stop reaction after being kept stirring after being added dropwise to complete 30 minutes.Material after the reaction was completed is filtered, clear water washs filter cake,
40 DEG C of filter cake or less drying, obtain bulk density 0.8g/cm3More than, content (purity, similarly hereinafter) 98.5%, partial size is less than 150 μm
Dazomet particle 32g.Yield is 97.6%.
Specific embodiment two
In addition to the extractant being added in first step reaction becomes 20ml chlorobenzene, remaining is the same as specific embodiment one, reaction knot
Shu Hou obtains bulk density 0.8g/cm3More than, content 98.1%, dazomet particle 31g of the partial size less than 150 μm.Yield is
96%.
Specific embodiment three
In addition to the solvent being added in second step reaction becomes 5g ethyl alcohol from 5g methanol, remaining is the same as specific embodiment one, reaction
After, obtain bulk density 0.7g/cm3More than, content 98.3%, dazomet particle 32g of the partial size less than 150 μm.Yield is
97.5%.
Specific embodiment four
In addition to being added without extractant in first step reaction, remaining is with specific embodiment one, after reaction, is accumulated
Density 0.5g/cm3, content 89%, 200~400 μm of partial size of dazomet particle 33g.Yield is 90%.
Specific embodiment five
In addition to being added without intensive polar solvent in second step reaction, remaining is with specific embodiment one, after reaction, obtains heap
Product density 0.4g/cm3, content 86%, 200~400 μm of partial size of dazomet particle 33g.Yield is 88%.
Comparative example
It is added without outside intensive polar solvent in addition to being added without extractant in first step reaction, in second step reaction, remaining is same
Specific embodiment one obtains bulk density 0.2g/cm after reaction3, content 78%, the dazomet that 200~400 μm of partial size
Grain 33g.Yield is 81%.
Can intuitively it illustrate with the comparison of comparative example through the foregoing embodiment, when extractant is added in part, part
When adding intensive polar solvent or add extractant and when intensive polar solvent, compared with the comparative example that do not add, the present invention
Scheme the bulk density of dazomet grain products, crystallinity, product purity and in terms of have a great improvement, and
Effect is best when adding extractant and intensive polar solvent in two-step reaction respectively.
This place embodiment is not exhaustive claimed midpoint of technical range and in embodiment technology
In scheme to single or multiple technical characteristics it is same replacement be formed by new technical solution, equally all the present invention claims
In the range of protection；Simultaneously the present invention program it is all enumerate or unlisted embodiment in, in the same embodiment each
Parameter is merely representative of an example (i.e. a kind of feasible scheme) for its technical solution, and between parameters and is not present stringent
Cooperation and qualified relation, wherein each parameter can be replaced mutually when stating and asking without prejudice to axiom and the present invention, special declaration
Except.
The technical means disclosed in the embodiments of the present invention is not limited to the technical means disclosed in the above technical means, and further includes
Technical solution consisting of any combination of the above technical features.The foregoing is a specific embodiment of the present invention, should refer to
Out, for those skilled in the art, without departing from the principle of the present invention, can also make several
Improvements and modifications, these modifications and embellishments are also considered to be within the scope of the present invention.
Claims (1)
1. a kind of dazomet preparation process, comprising:
First step reaction, sequentially adds methylamine water solution, water in consersion unit, stirs, and controls reaction temperature, to stirring system
Middle dropwise addition carbon disulfide, maintenance reaction after terminating is added dropwise, and to reaction terminating point, reaction was completed, adds into the water layer of acquisition appropriate
Extractant through the isolated intermediate N methyl aminodithioformic acid of reextraction；
The carbon disulfide is excessively added, and is greater than 0.5:1 with the molar ratio of methylamine；The extractant is methylene chloride, dichloro
It is any in ethane；
Second step reaction, formalin, sulfate, surfactant, intensive polar solvent are sequentially added in consersion unit, is stirred
It mixes, intermediate N methyl aminodithioformic acid is added into system, maintain to react to reaction terminating point, then can obtain through separation
To dazomet particle；
The sulfate is zinc sulfate, barium sulfate, mixture one or several kinds of in calcium sulfate；The surfactant is ten
It is dialkyl sulfonates, nonylphenol polyoxyethylene ether sulfate, sodium alkyl sulfonate, one or several kinds of mixed in sodium lignin sulfonate
Close object, the intensive polar solvent is methanol, any in ethyl alcohol.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5495017A (en) * | 1991-12-21 | 1996-02-27 | Basf Aktiengesellschaft | Preparation of substantially dust-free tetrahydro-3,5-dimethyl-1,3,5-thiadiazine-2-thione granules |
| CN1447802A (en) * | 2000-08-17 | 2003-10-08 | 巴斯福股份公司 | Method for production of particle-contg. prepn. of tetrahydro-3, 5-dimethyl-1,3,5-thiadiazin-2-thione |
| CN1543787A (en) * | 2003-11-20 | 2004-11-10 | 上海交通大学 | Process for preparing dazomet dustless stable fine granule |
-
2016
- 2016-12-27 CN CN201611224369.6A patent/CN106831649B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5495017A (en) * | 1991-12-21 | 1996-02-27 | Basf Aktiengesellschaft | Preparation of substantially dust-free tetrahydro-3,5-dimethyl-1,3,5-thiadiazine-2-thione granules |
| CN1447802A (en) * | 2000-08-17 | 2003-10-08 | 巴斯福股份公司 | Method for production of particle-contg. prepn. of tetrahydro-3, 5-dimethyl-1,3,5-thiadiazin-2-thione |
| CN1543787A (en) * | 2003-11-20 | 2004-11-10 | 上海交通大学 | Process for preparing dazomet dustless stable fine granule |
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Address after: Jiaojiang District of Taizhou City, Zhejiang province 318000 road outside No. 97 Patentee after: Shunyi Co., Ltd Address before: 318000 No.97 Waisha Road, Jiaojiang District, Taizhou City, Zhejiang Province Patentee before: Zhejiang Haizheng Chemical Co., Ltd. |