CN104610120B - Preparation method capable of increasing proportion of 1,3-bit normal compound in bisultap - Google Patents
Preparation method capable of increasing proportion of 1,3-bit normal compound in bisultap Download PDFInfo
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- CN104610120B CN104610120B CN201510041764.XA CN201510041764A CN104610120B CN 104610120 B CN104610120 B CN 104610120B CN 201510041764 A CN201510041764 A CN 201510041764A CN 104610120 B CN104610120 B CN 104610120B
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- dimehypo
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- positive structure
- bisultap
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Abstract
The invention discloses a preparation method capable of increasing a proportion of 1,3-bit normal compound in bisultap. The preparation method comprises the following steps: using chloride, thiosulfate and alkali as raw materials, in the existence of a catalyst and at the temperature of 40-90 DEG C, taking a reaction for 1-8 hours, and preparing bisultap. According to the bisultap produced by the preparation method, the proportion of the 1,3-bit normal compound in a sulfonated liquid bisultap is high; compared with the bisultap prepared by the conventional process, the 1,3-bit normal compound is higher than 3-5%; the sulfonated liquid bisultap can be directly used for producing cartap, so that the production cost of cartap is lowered; the problem that in the method of utilizing the bisultap crystal to produce monosultap, bisultap can be still generated; a novel technology and a novel method of using the sulfonated liquid bisultap to directly produce cartap and preparing high-quality raw materials are provided; the preparation method is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to chemical industry chemical field, specifically a kind of preparation method improving 1,3 positive structure body dimehypo ratios.
Background technology
Dimehypo is sandworm toxin insecticide, be a kind of efficiently, moderate toxicity, have stomach toxicity tag and Uptake and translocation and
The wide spectrum of certain ovicidal efficiency, safe, economic insecticide.It is the pesticide species of China's independent development.It can prevent and treat Oryza sativa L., little
The various pests such as wheat, Caulis Sacchari sinensis, vegetable, Cotton Gossypii, fruit tree.By raw materials such as chloropropene, dimethylamine, sodium hyposulfite through amination, acidifying, take off
The operations such as water, chlorination, sulfonation produce.Sulfonated liquid dimehypo is crude product, has positive structure body in sulfonated liquid dimehypo crude product
And isomer, i.e. 2-N, N dimethylamine base -1,3- double thiosulfonic acid X base propane (positive structure body), 3-N, N dimethylamine base -1,2- is double
Thiosulfonic acid X base propane (isomer).Due to 3-N, the double thiosulfonic acid X base propane of N dimethylamine base -1,2- can not form clam worm
Poison, does not have insecticidal effect, and therefore in sulfonated liquid dimehypo, positive structure body burden accounting is high, shows that in dimehypo, effective ingredient is high, just
Structure body high income, quality is good.
At present all producers be all will be crystallized for sulfonated liquid dimehypo after shachongdan powder and primary crystallization mother solution, a lot
Primary crystallization mother solution reconcentration is crystallized by producer, and the mother solution of secondary crystallization is tuned into dimehypo again and sells.Due to sulfonated liquid dimehypo
Produce Cupric sulfate exactly to crystallize out positive structure body dimehypo, and isomer dimehypo is uncrystallizable out, so improving sulfonation
Liquid dimehypo positive structure body ratio just can improve the yield of positive structure body, just can improve the flour extraction of Cupric sulfate.Producing Cupric sulfate has one
Positive structure body could not crystallize out a bit, and substantial amounts of isomer exists in crystalline mother solution, because dimehypo GB is despite adopting liquid phase
Chromatography, but positive isomer is not made a distinction, positive isomer appearance simultaneously, because a large amount of isomer of dimehypo exists,
At present dimehypo water solution parasite killing needs to increase enough amounts and just has drug effect, and peasant uses the enthusiasm of Dimehypo increasingly
Low, really improve the quality of dimehypo water solution or the generation eliminating dimehypo, be for having that dimehypo water solution pesticide is found a way out
Effect approach.
The sulfonated liquid dimehypo positive structure body accounting that domestic existing process produces at present, in 70-77%, is hovered not high at one
Level.Domestic production cartap is all that the Cupric sulfate being obtained with after the crystallization of sulfonated liquid dimehypo is produced for raw material, main
If because sulfonated liquid dimehypo internal (position) isomer is too many, product quality can not be up to standard.It is directly produced with sulfonated liquid dimehypo and kill snout moth's larva
Red product, improves sulfonated liquid dimehypo positive structure body ratio, reduces content of isomer, it appears particularly important, need not crystallize production and kill
Worm is single, and positive structure body can obtain all of substantially increasing the utilization rate of sulfonated liquid dimehypo positive structure body, eliminate dimehypo
Water preparation produces, and production cost thus can be greatly reduced.
Content of the invention
It is an object of the invention to provide a kind of preparation method improving 1,3 positive structure body dimehypo ratios, on solving
State the problem proposing in background technology.
For achieving the above object, the present invention provides following technical scheme：
A kind of preparation method improving 1,3 positive structure body dimehypo ratios, comprises the following steps that：
(1) weigh the chloride of 240-385g and put in the four-hole bottle equipped with stirring for the 1000mL；
(2) add methanol 200-300mL；
(3) reduce the temperature to -5-30 DEG C, add the alkali of 20-70g toward in four-hole bottle, chloride pH value is transferred to 5-11；
(4) add catalyst 1.4-8g toward in four-hole bottle, catalyst is tetrabutyl ammonium bromide, tetrabutylammonium iodide, four fourths
Base ammonium hydrogen sulfate, Polyethylene Glycol, benzyltrimethylammonium bromide, methyl tricapryl ammonium chloride, Dodecyl trimethyl ammonium chloride, ten
One of tetraalkyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, 15- crown ether-5 and hexaoxacyclooctadecane-6-6；
(5) thiosulfate 380-506g, sulfonating reaction 1-8 hour at a temperature of 40-90 DEG C are added toward in four-hole bottle；
(6) remove and reclaim methanol；
(7) centrifugation is desalted, and obtains sulfonated liquid dimehypo product；
(8) use the positive structure body of liquid chromatogram measuring sulfonated liquid dimehypo, the content of isomer, calculate positive structure body accounting and yield
As the further scheme of the present invention：Alkali described in step (3) is sodium hydroxide, potassium hydroxide, sodium carbonate, carbon
One of sour potassium, sodium bicarbonate, potassium bicarbonate, ammonia.
As the present invention further scheme：Thiosulfate described in step (5) is sodium thiosulfate, thio sulfur
One of sour potassium, Ammonium hyposulfite..
As the present invention further scheme：Dimehypo described in step (7) is 2-N, N dimethylamine base -1, and 3- is double
Thiosulfonic acid X base propane and 3-N, N dimethylamine base -1, the mixture of the double thiosulfonic acid X base propane of 2-, wherein, thiosulfonic acid X
X base in base is sodio, potassio, ammonium.
As the present invention further scheme：Described thiosulfate and muriatic proportioning are (1.9-2.5):1.
As the present invention further scheme：The quality of described catalyst is the 0.3-10% of chloride quality.
Compared with prior art, the invention has the beneficial effects as follows：The present invention is being urged with thiosulfate using chloride
Under agent presence and suitable process conditions, substantially increase the effectiveness of chloride and the indexing of thiosulfuric acid reactant salt, improve
Operation yield, 1,3 positive structure body dimehypo ratio is high, and higher 3-5 percentage point than common process, sulfonated liquid dimehypo can be direct
Produce cartap, reduce the production cost of cartap, eliminate and still have dimehypo using dimehypo crystallization production Cupric sulfate
The problem producing；It is to be directly produced cartap preparation high-quality feedstocks with sulfonated liquid dimehypo to provide a kind of new technique and Xin Fang
Method, suitable large-scale industrial production.
Specific embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of not making creative work, all
Belong to the scope of protection of the invention.
Embodiment 1
In the embodiment of the present invention, a kind of preparation method improving 1,3 positive structure body ratios in sulfonated liquid dimehypo, concrete step
Suddenly as follows：
(1) weigh the chloride of 280g60% and put in the four-hole bottle equipped with stirring for the 1000mL；
(2) add methanol 200mL；
(3) reduce the temperature to 0 DEG C, add the Caustic soda of 32g toward in four-hole bottle, chloride pH value is transferred to 7；
(4) add benzyltrimethylammonium bromide 1g toward in four-hole bottle；
(5) sodium thiosulfate 406g, sulfonating reaction 1.5 hours at a temperature of 80 DEG C are added toward in four-hole bottle；
(6) remove and reclaim methanol；
(7) centrifugation is desalted, and obtains sulfonated liquid dimehypo product；
(8) mass percent of the positive isomer of sulfonated liquid dimehypo, 1,3 positive structure body dimehypo is surveyed with high performance liquid chromatography
Content is 38.9%, and 1,2 position isomer dimehypo content is 8.6%, 1,3 positive structure body accounting 81.9%.
Embodiment 2
In the embodiment of the present invention, a kind of preparation method improving 1,3 positive structure body ratios in sulfonated liquid dimehypo, concrete step
Suddenly as follows：
(1) weigh the chloride of 300g52% and put in the four-hole bottle equipped with stirring for the 1000mL；
(2) add methanol 220mL；
(3) reduce the temperature to 20 DEG C, add the soda of 25g toward in four-hole bottle, chloride pH value is transferred to 6.5；
(4) add cetyl trimethylammonium bromide 6g toward in four-hole bottle；
(5) sodium thiosulfate 390g, sulfonating reaction 2 hours at a temperature of 70 DEG C are added toward in four-hole bottle；
(6) remove and reclaim methanol；
(7) centrifugation is desalted, and obtains sulfonated liquid dimehypo product；
(8) mass percent of the positive isomer of sulfonated liquid dimehypo, 1,3 positive structure body dimehypo is surveyed with high performance liquid chromatography
Content is 36.3%, and 1,2 position isomer dimehypo content is 7.8%, 1,3 positive structure body accounting 82.3%.
Embodiment 3
In the embodiment of the present invention, a kind of preparation method improving 1,3 positive structure body ratios in sulfonated liquid dimehypo, concrete step
Suddenly as follows：
(1) weigh the chloride of 312g50% and put in the four-hole bottle equipped with stirring for the 1000mL；
(2) add methanol 260mL；
(3) reduce the temperature to -3 DEG C, add the ammonia of 67g toward in four-hole bottle, chloride pH value is transferred to 8.0；
(4) add 4-butyl ammonium hydrogen sulfate 10g toward in four-hole bottle；
(5) sodium thiosulfate 447g, sulfonating reaction 4 hours at a temperature of 65 DEG C are added toward in four-hole bottle；
(6) remove and reclaim methanol；
(7) centrifugation is desalted, and obtains sulfonated liquid dimehypo product；
(8) mass percent of the positive isomer of sulfonated liquid dimehypo, 1,3 positive structure body dimehypo is surveyed with high performance liquid chromatography
Content is 35.1%, and 1,2 position isomer dimehypo content is 7.7%, 1,3 positive structure body accounting 82.1%.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of the spirit or essential attributes of the present invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit requires rather than described above limits, it is intended that all in the implication and scope of the equivalency of claim by falling
Change is included in the present invention.
Moreover, it will be appreciated that although this specification is been described by according to embodiment, not each embodiment only wraps
Containing an independent technical scheme, only for clarity, those skilled in the art should for this narrating mode of description
Using description as an entirety, the technical scheme in each embodiment can also form those skilled in the art through appropriately combined
Understandable other embodiment.
Claims (6)
1. a kind of preparation method improving 1,3 positive structure body dimehypo ratios is it is characterised in that comprise the following steps that:
(1) weigh the chloride of 240-385g and put into 1000mL equipped with the four-hole bottle of agitating device；
(2) add methanol 200-300mL；
(3) reduce the temperature to -5-30 DEG C, add the alkali of 20-70g toward in four-hole bottle, chloride pH value is transferred to 5-11；
(4) add catalyst 1.4-8g toward in four-hole bottle, described catalyst is tetrabutyl ammonium bromide, tetrabutylammonium iodide, four
Butyl ammonium hydrogen sulfate, Polyethylene Glycol, benzyltrimethylammonium bromide, methyl tricapryl ammonium chloride, dodecyl front three curtain ammonium chloride,
Tetradecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, one of 15- crown ether-5, hexaoxacyclooctadecane-6-6；
(5) thiosulfate 380-506g, sulfonating reaction 1-8 hour at a temperature of 40-90 DEG C are added toward in four-hole bottle；
(6) remove and reclaim methanol；
(7) centrifugation is desalted, and obtains sulfonated liquid dimehypo product；
(8) use positive structure body, the content of isomer of liquid chromatogram measuring sulfonated liquid dimehypo, calculate positive structure body accounting and yield.
2. the preparation method improving 1,3 positive structure body dimehypo ratios according to claim 1 is it is characterised in that step
(3) alkali described in is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, in ammonia one
Kind.
3. the preparation method improving 1,3 positive structure body dimehypo ratios according to claim 1 is it is characterised in that step
(5) thiosulfate described in is one of sodium thiosulfate, Potassium hyposulfite., Ammonium hyposulfite..
4. the preparation method improving 1,3 positive structure body dimehypo ratios according to claim 1 is it is characterised in that step
(7) dimehypo described in is 2-N, N mono- dimethylamino -1,3 a pair of thiosulfonic acid X base propane and 3-N, N dimethylamine base 1,
The mixture of the double thiosulfonic acid X base propane of 2-, wherein, the X base in thiosulfonic acid x base is sodio, potassio, ammonium.
5. the preparation method improving 1,3 positive structure body dimehypo ratios according to claim 1 is it is characterised in that described
Thiosulfate and muriatic proportioning are (l.9-2.5):l.
6. the preparation method improving 1,3 positive structure body dimehypo ratios according to claim 1 is it is characterised in that described
The quality of catalyst is the 0.3-10% of chloride quality.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510041764.XA CN104610120B (en) | 2015-01-28 | 2015-01-28 | Preparation method capable of increasing proportion of 1,3-bit normal compound in bisultap |
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| CN201510041764.XA CN104610120B (en) | 2015-01-28 | 2015-01-28 | Preparation method capable of increasing proportion of 1,3-bit normal compound in bisultap |
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| CN104610120B true CN104610120B (en) | 2017-02-22 |
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Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1063310C (en) * | 1996-03-02 | 2001-03-21 | 陈节生 | Agricultural chemical having fertilizer function and its prodn. method |
| CN1273240A (en) * | 1999-05-07 | 2000-11-15 | 湖南南天实业股份有限公司 | Sulfonating reaction process in production of bisultap |
| CN1191013C (en) * | 2000-07-21 | 2005-03-02 | 长春市恒大实业有限责任公司 | Novel pesticide of monosultap ammonium and productive technology thereof |
| CN100410239C (en) * | 2005-04-21 | 2008-08-13 | 段儒华 | Simplified production technology of bisultap |
| CN102304076A (en) * | 2011-07-05 | 2012-01-04 | 江苏兄弟维生素有限公司 | Preparation method of sodium n-propyl thiosulfate |
| CN103130697A (en) * | 2013-02-26 | 2013-06-05 | 北京彤程创展科技有限公司 | Preparation method of post-vulcanization stabilizing agent organic thiosulfate |
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Address after: No.1, Yuwang Road, high tech Industrial Development Zone, you County, Zhuzhou City, Hunan Province, 412005 Patentee after: Hunan Haohua Chemical Co., Ltd Address before: 412000 Zhuzhou City, Hunan Province Ding Shifeng District Road No. 18 Patentee before: HUNAN HAOHUA CHEMICAL Co.,Ltd. |
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