CN106220628A - A kind of preparation method of diquat dibromide novel anionic salt - Google Patents
A kind of preparation method of diquat dibromide novel anionic salt Download PDFInfo
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- CN106220628A CN106220628A CN201610602467.2A CN201610602467A CN106220628A CN 106220628 A CN106220628 A CN 106220628A CN 201610602467 A CN201610602467 A CN 201610602467A CN 106220628 A CN106220628 A CN 106220628A
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- Prior art keywords
- diquat dibromide
- acid
- preparation
- salt
- bromine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
- C07D471/14—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/09—Bromine; Hydrogen bromide
- C01B7/096—Bromine
Abstract
The invention discloses the preparation method of a kind of diquat dibromide novel anionic salt, comprise the following steps: with diquat dibromide dibromo salt solution as raw material, add the concentrated nitric acid of excess, or non-acid with strong oxidizing property and oxidant hydrogen peroxide, intensification is fully reacted, the bromine generated reclaims through distillation condensation, after precipitation is steamed in the rotation of reacted solution, through alcohol analysis, separates and be dried and to obtain finished product.This method production cost is low, and reaction is simple, the advantage that product yield is high, is suitable for industrialized production, it is often more important that displacing expensive bromine, bromine, as a kind of widely used industrial chemicals, can sell as product；Can also obtain Bromofume with ethylene reaction, be cycled to used in the preparation of diquat dibromide dibromo salt, the price height fundamentally solving bromine itself is brought the problem that existing diquat dibromide production cost is high, has obvious economic benefit.
Description
Technical field
The invention belongs to chemical industry and pesticide field, be specifically related to the system of a kind of diquat dibromide novel anionic salt
Preparation Method.
Background technology
Diquat dibromide is the steriland herbicide of a kind of function admirable, and the stem and leaf simultaneously applying also for Rhizoma Solani tuber osi and Radix Pachyrhizi Erosi is urged
Withered, diquat dibromide described on ordinary meaning i.e. refers to diquat dibromide dibromo salt, and by 2,2 '-bipyridyl and Bromofume ring-closure reaction obtain
Arrive.Be only second to the third-largest steriland herbicide of glyphosate and diquat dibromide as the whole world, in recent years, diquat dibromide market demand increases
Add very fast.While it is true, due to the price height of high bromine content and bromine itself in diquat dibromide dibromo salt, cause diquat dibromide to produce
High cost, limits the extensive application of diquat dibromide to a certain extent.
It is its cationic moiety because of what diquat dibromide dibromo salt played herbicide effect, unrelated with anion bromine, thus need to seek
The preparation method of diquat dibromide novel novel anionic salt, to replace diquat dibromide dibromo salt, thus solves existing diquat dibromide production cost
Too high problem.
Summary of the invention
Present invention aims to the problems referred to above and the preparation method of a kind of diquat dibromide novel anionic salt, the party are provided
Method production cost is low, and reaction is simple, and product yield is high, is suitable for industrialized production.
In order to solve the problems referred to above, the technical solution adopted in the present invention is such, a kind of diquat dibromide novel anionic
The preparation method of salt, comprises the following steps: with diquat dibromide dibromo salt solution as raw material, adds the acid of non-acid with strong oxidizing property and oxidant
Hydrogen peroxide, heats up after fully reacting, and the bromine of generation reclaims through distillation condensation, after dehydration is steamed in the rotation of reacted solution, and warp
Alcohol analysis, separate and be dried to obtain the finished product of the diquat dibromide anion salt corresponding with the anion of added non-acid with strong oxidizing property.
The non-acid with strong oxidizing property added is sulphuric acid, acetic acid or p-methyl benzenesulfonic acid, when the non-acid with strong oxidizing property added is
During sulphuric acid, the addition of sulphuric acid is more than 1 times of the amount of diquat dibromide dibromo salt material, preferably 1-2 times；When the non-strong oxygen added
When the property changed acid acid is acetic acid or p-methyl benzenesulfonic acid, the addition of acetic acid or p-methyl benzenesulfonic acid is the amount of diquat dibromide dibromo salt material
More than 2 times, preferably 2-3 times.
The concentration of the hydrogen peroxide added is 30% or 50%., the addition of hydrogen peroxide is the amount of diquat dibromide dibromo salt material
1.2-1.8 again, preferably 1.3-1.7 times.
The invention provides the preparation method of another kind of diquat dibromide novel anionic salt, comprise the following steps: with diquat dibromide
Dibromo salt solution is raw material, adds the concentrated nitric acid of excess, heats up and fully reacts, and the bromine of generation reclaims through distillation condensation,
After dehydration is steamed in the rotation of reacted solution, through alcohol analysis, separate and be dried and to obtain diquat dibromide nitrate finished product.
In this preparation method, the concentration of concentrated nitric acid is preferably 50-98%, and the addition of concentrated nitric acid is diquat dibromide dibromo salt
4-8 times of the amount of material, preferably 5-7 times.
The mechanism of this preparation method is identical with the mechanism of aforementioned preparation process, and a concentrated nitric acid part for excess serves as oxidation
Agent, another part provides participates in the hydrion reacted and the supply as anion nitrate anion.
In above-mentioned 2 kinds of preparation methoies, in alcohol analysis, alcohol used is methanol, ethanol, ethylene glycol or isopropanol, the use of alcohol
Amount steams 2-5 times of the solution quality after being dehydrated for reacted solution through rotation.
Reaction temperature is 100～130 DEG C, preferably 100-120 DEG C.
The distillation condensation of bromine is reclaimed, and can carry out, it is possible to carry out after the completion of reaction in course of reaction.
In described diquat dibromide dibromo salt aqueous solution, diquat dibromide dibromo salt can be bought, it is possible to is to condense back through distillation
Bromine after receipts, carries out additive reaction with ethylene and obtains Bromofume, then the Bromofume and 2 that will generate, and 2 '-bipyridyl is carried out
Cyclization obtains.
Beneficial effect: this method production cost is low, reaction is simple, the advantage that product yield is high, is suitable for industrialized production, more
It is important that displace expensive bromine, bromine, can be direct as product as a kind of widely used industrial chemicals
Sell；Bromofume can also be obtained with ethylene reaction, be cycled to used in the preparation of diquat dibromide dibromo salt, fundamentally solve bromine
The price height of element itself is brought the problem that existing diquat dibromide production cost is high, has obvious economic benefit.
Detailed description of the invention
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, this embodiment
It is only used for explaining the present invention, is not intended that limiting the scope of the present invention.
Embodiment 1
By diquat dibromide dibromo salt 34.4g wiring solution-forming (40wt%), it is slowly added dropwise the sulphuric acid 30.2g that concentration is 50%, then heats up
To 100 DEG C, be slowly added dropwise 30% hydrogen peroxide 17g, fully react, and distill condensation reclaim bromine, without obvious bromine vapor out after,
Stopping the recovery of bromine, obtain bromine 12g, precipitation 13g is steamed in the solution rotation after reaction terminates, and after cooling down, adds in concentrated solution
Entering dehydrated alcohol 300g, be sufficiently stirred for crystallization, filter, with alcohol flushing, be dried to obtain diquat dibromide sulfate 22.4g, yield is
80%。
Embodiment 2
By diquat dibromide dibromo salt 34.4g wiring solution-forming (40wt%), add acetic acid 14.4g, then heat to 100 DEG C, be slowly added dropwise
30% hydrogen peroxide 17.2g, fully reacts, and distills condensation recovery bromine.Without obvious bromine vapor out after, stop bromine recovery,
Obtain bromine 13.5g.Precipitation 13.1g is steamed in solution rotation after reaction terminates, after cooling down, adds absolute methanol alcohol in concentrated solution
300g, is sufficiently stirred for crystallization, filters, and with alcohol flushing, is dried to obtain diquat dibromide acetate 25.8g, yield 85.0%.
Embodiment 3
By diquat dibromide dibromo salt 34.4g wiring solution-forming (40wt%), add p-methyl benzenesulfonic acid 34.5g, then heat to 100 DEG C, slow
Slow dropping 30% hydrogen peroxide 17.2g, fully reacts, and distills condensation and reclaim bromine, without obvious bromine vapor out after, stop bromine
Recovery, obtain bromine 13.2g.Precipitation 13.1g is steamed in solution rotation after reaction terminates, after cooling down, adds nothing in concentrated solution
Water methanol 300g, is sufficiently stirred for crystallization, filters, and with alcohol flushing, is dried to obtain diquat dibromide tosilate 56.7g, yield
82.4%。
Embodiment 4
By diquat dibromide dibromo salt 34.4g wiring solution-forming (40wt%), it is added slowly to concentrated nitric acid (69%) 56.6g, then heats to 100
DEG C, fully react, and distill condensation recovery bromine.Without obvious bromine vapor out after, stop bromine recovery, obtain bromine 13.3g.
Reaction terminates the rotation of rear solution and steams precipitation 18.3g, after cooling down, adds dehydrated alcohol 300g, be sufficiently stirred for knot in concentrated solution
Crystalline substance, filters, and with alcohol flushing, is dried to obtain diquat dibromide nitrate 25.1g, yield 81.5%.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Within god and principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (10)
1. the preparation method of a diquat dibromide novel anionic salt, it is characterised in that comprise the following steps: with diquat dibromide dibromo salt
Solution is raw material, adds non-acid with strong oxidizing property and oxidant hydrogen peroxide, heats up and fully reacts, and the bromine of generation is cold through distillation
Solidifying reclaim, after dehydration is steamed in the rotation of reacted solution, through alcohol analysis, separate and be dried with the anion of added non-acid with strong oxidizing property
The finished product of corresponding diquat dibromide anion salt.
The preparation method of a kind of diquat dibromide novel anionic salt the most according to claim 1, it is characterised in that added
Non-acid with strong oxidizing property acid is sulphuric acid, acetic acid or p-methyl benzenesulfonic acid.
The preparation method of a kind of diquat dibromide novel anionic salt the most according to claim 2, it is characterised in that when being added
Non-acid with strong oxidizing property when being sulphuric acid, the addition of sulphuric acid is 1-2 times of the amount of diquat dibromide dibromo salt material.
The preparation method of a kind of diquat dibromide novel anionic salt the most according to claim 2, it is characterised in that when being added
Non-acid with strong oxidizing property when being acetic acid or p-methyl benzenesulfonic acid, the addition of acetic acid or p-methyl benzenesulfonic acid is diquat dibromide dibromo salt material
2-3 times of amount.
The preparation method of a kind of diquat dibromide novel anionic salt the most according to claim 1, it is characterised in that added
The concentration of hydrogen peroxide is 30% or 50%.
The preparation method of a kind of diquat dibromide novel anionic salt the most according to claim 1, it is characterised in that hydrogen peroxide
Addition is 1.2-1.8 times of the amount of diquat dibromide dibromo salt material.
The preparation method of a kind of diquat dibromide novel anionic salt the most according to claim 1, it is characterised in that institute in alcohol analysis
Alcohol be methanol, ethanol, ethylene glycol or isopropanol, the solution quality that the consumption of alcohol is reacted solution after dehydration is steamed in rotation
2-5 times.
The preparation method of a kind of diquat dibromide novel anionic salt the most according to claim 1, it is characterised in that the steaming of bromine
Evaporate condensation to reclaim, can carry out in course of reaction, it is possible to carry out after the completion of reaction.
9. the preparation method of a diquat dibromide novel anionic salt, it is characterised in that comprise the following steps: with diquat dibromide dibromo salt
Solution is raw material, adds the concentrated nitric acid of excess, heats up and fully reacts, and the bromine of generation reclaims, after reaction through distillation condensation
Solution rotation steam dehydration after, through alcohol analysis, separate and be dried and to obtain diquat dibromide nitrate finished product.
10. the preparation method of a diquat dibromide novel anionic salt, it is characterised in that the concentration of concentrated nitric acid is 50%-98%, dense nitre
4-8 times of the amount that addition is diquat dibromide dibromo salt material of acid.
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| CN201610602467.2A CN106220628A (en) | 2016-07-28 | 2016-07-28 | A kind of preparation method of diquat dibromide novel anionic salt |
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| CN201610602467.2A CN106220628A (en) | 2016-07-28 | 2016-07-28 | A kind of preparation method of diquat dibromide novel anionic salt |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2823987A (en) * | 1955-06-15 | 1958-02-18 | Ici Ltd | New quaternary salts |
| US3651060A (en) * | 1968-10-04 | 1972-03-21 | Ici Ltd | 1 1'-ethylene-2 2'-bipyridlium salts |
| JPS62135474A (en) * | 1985-12-09 | 1987-06-18 | Tokuyama Soda Co Ltd | Viologen compound |
-
2016
- 2016-07-28 CN CN201610602467.2A patent/CN106220628A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2823987A (en) * | 1955-06-15 | 1958-02-18 | Ici Ltd | New quaternary salts |
| US3651060A (en) * | 1968-10-04 | 1972-03-21 | Ici Ltd | 1 1'-ethylene-2 2'-bipyridlium salts |
| JPS62135474A (en) * | 1985-12-09 | 1987-06-18 | Tokuyama Soda Co Ltd | Viologen compound |
Non-Patent Citations (1)
| Title |
|---|
| 成新云等: "关于溴化氢回收利用的探讨", 《盐业与化工》 * |
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