CN102161630A - Industrial preparation method of 2,2-dibromo-2-nitrilo-propionamide - Google Patents
Industrial preparation method of 2,2-dibromo-2-nitrilo-propionamide Download PDFInfo
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- CN102161630A CN102161630A CN2011100539225A CN201110053922A CN102161630A CN 102161630 A CN102161630 A CN 102161630A CN 2011100539225 A CN2011100539225 A CN 2011100539225A CN 201110053922 A CN201110053922 A CN 201110053922A CN 102161630 A CN102161630 A CN 102161630A
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Abstract
The invention provides an industrial preparation method of 2,2-dibromo-2-nitrilo-propionamide. The preparation method comprises the following steps: adding cyanoacetamide and solvent in a reaction container, dropping bromine and hydrogen peroxide under stirring; and continuously reacting for a certain time after dropping, and filtering to obtain 2,2-dibromo-2-nitrilopropionamide, wherein the molar ratio of cyanoacetamide to bromine to hydrogen peroxide is 1:(1.01-1.08):(1.0-1.2). By adopting the industrial preparation method of 2,2-dibromo-2-nitrilopropionamide, the consumption of a bromine raw material can be reduced and the production cost can be reduced.
Description
Technical field
The present invention relates to chemical production technical field, particularly relate to a kind of 2, the industrial production process of 2-two bromo-2-nitrilo propionic acid amides.
Background technology
2,2-two bromo-2-nitrilo propionic acid amides (DBNPA), be a kind of industrial bactericide efficiently, algicide and water conditioner, has wide spectrum, efficiently, characteristics such as easily degraded, noresidue, environmentally safe, can be used to prevent bacterium and the growth and breeding of algae in papermaking, industrial cycle water cooling, metal processing lubricating oil, paper pulp, timber, coating and glued board, can make the mud control agent simultaneously and be widely used in paper mill mud and recirculating cooling water system.But this product kill bacteria, fungi, yeast, cyano bacteria (blue-green algae) and true algae are a kind of sterilant fast, and be rapid decomposable in aqueous environment, and very safe to environment, has broad application prospects and huge commercial value.
Prior art discloses the synthetic technology scheme of some DBNPA.Early 2, the synthetic method of 2-two bromo-2-nitrilo propionic acid amides (DBNPA), with bromate or oxymuriate as oxygenant, as USP3751444, disclosed technology such as Israeli Patent 4611258.But produce a large amount of by product sodium salts in this method production process, be not easy to product and separate, filtrate can't be reused, and product purity is low, and the discharging of waste liquid amount is big.It is a kind of 2 that EP0308184 discloses, and the synthetic method of 2-two bromo-2-nitrilo propionic acid amides is an oxygenant with the hydrogen peroxide, and heating continuously in 10-30min rapid reaction in the reaction times, makes DBNPA under 80-100 ℃ of temperature.With water is solvent, and yield can reach 79.7%-89.7%, and reaction yield can reach 92.7%-100.8% when being solvent with filtrate, but this method temperature of reaction height, product easily decomposes, the product instability, the reaction yield instability of different batches the highlyest differs 10%.
At the problems referred to above, publication number be CN101781233A patent disclosure a kind of 2,2-two bromo-2-malonamide nitriles (claim 2 again, 2-two bromo-2-nitrilo propionic acid amides) synthetic method, it is raw material that this method adopts malonamide nitrile, and Malonamide nitrile and solvent (water or solution) are added in the reactor, drips bromine and carry out bromination reaction under temperature of reaction 15-45 ℃ stirring, adopt 30% hydrogen peroxide as oxygenant, reaction times 0.5h-6h.Adopt the feed molar proportioning to be: Malonamide nitrile: bromine: hydrogen peroxide=1: 1.1-1.3: 0.7-0.90.Though this method is by prolonging the reaction times, reduce temperature of reaction, obtained the stability of DBNPA yield and different batches yield preferably, but the dioxygen water yield that is adopted in this technology is obviously not enough, cause bromine consumption also to increase greatly, because the cost of bromine raw material is comparatively expensive, if realize industrialized widespread use, this method is irrational economically.And this method still belongs to the synthetic method under a kind of lab scale condition.
In a word, need the urgent technical problem that solves of those skilled in the art to be exactly: how can provide a kind of 2, the industrial production process of 2-two bromo-2-nitrilo propionic acid amides reduces the bromine consumption of raw materials, reduces production costs.
Summary of the invention
It is a kind of 2 that technical problem to be solved by this invention provides, and the industrial production process of 2-two bromo-2-nitrilo propionic acid amides reduces the bromine consumption of raw materials, reduces production costs.
In order to address the above problem, the invention discloses a kind ofly 2, the industrial production process of 2-two bromo-2-nitrilo propionic acid amides is characterized in that, comprising:
Malonamide nitrile and solvent are added in the reaction vessel, stir on one side, drip bromine and hydrogen peroxide on one side simultaneously;
After bromine and hydrogen peroxide drip, continue reaction for some time, filter and obtain 2,2-two bromo-2-nitrilo propionic acid amides;
Wherein, the mol ratio of malonamide nitrile, bromine and hydrogen peroxide is 1: 1.01-1.08: 1.0-1.2.
Preferably, be under 5-60 ℃ the condition, to drip bromine and hydrogen peroxide simultaneously in temperature of reaction.
Preferably, the concentration of the hydrogen peroxide of dropping is 40-50%.
Preferably, described solvent is selected from: the mother liquor that water or reaction generate.
Preferably, malonamide nitrile and solvent with magnitude relation is: the solvent of the malonamide nitrile of 1Kg: 3-6L.
Preferably, after bromine and hydrogen peroxide drip, continue reaction 0.2-8 hour.
Compared with prior art, the present invention has the following advantages:
After the present invention is added to reaction vessel with malonamide nitrile and solvent, the mode that adopts bromine and hydrogen peroxide to drip simultaneously prepares DBNPA, and the mol ratio of the used reaction raw materials of this method---malonamide nitrile, bromine and hydrogen peroxide is 1: 1.01-1.08: 1.0-1.2.By increasing the consumption of hydrogen peroxide, the bromide that makes by-product in the reaction process almost quantitative conversion is a bromine, thereby the most effective bromine that utilized, reduced consumption as the bromine of reaction raw materials, reduced production cost, the bromine consumption is saved more than 10% than prior art, and economic benefit is very remarkable.Use method disclosed by the invention and improved reaction yield, yield can reach 99.1-105.2%; Simultaneously, can keep operation to operate steadily and stable yield.
Further, the concentration that the present invention preferably drips hydrogen peroxide is 50%, by dripping the hydrogen peroxide of higher concentration, can reduce the total amount of water in the reaction vessel, because reaction product 2,2-two bromo-2-nitrilo propionic acid amides (DBNPA) are water-soluble substanceses, have then reduced the purification loss that product brings because of being dissolved in mother liquor, have improved the yield of product.
In addition, the mother liquor that the present invention can generate reaction is as solvent, with the whole recycles of the mother liquor that production process produced, and without sewage discharge in the production process then, externally the water source does not pollute, and has realized the environmental protection of production line; Simultaneously,, do the solvent phase ratio, can reduce the bromine consumption, improve the yield of DBNPA with water owing to be dissolved with the part bromine in the mother liquor.
Description of drawings
Fig. 1 is that the present invention is a kind of 2, the schema of the industrial production process embodiment of 2-two bromo-2-nitrilo propionic acid amides.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, the present invention is further detailed explanation below in conjunction with the drawings and specific embodiments.
With reference to Fig. 1, it is a kind of 2 to show the present invention, and the schema of the industrial production process embodiment of 2-two bromo-2-nitrilo propionic acid amides comprises:
In a preferred embodiment of the invention, be under 5-60 ℃ the condition, to drip bromine (liquid bromine) and hydrogen peroxide in temperature of reaction.Further, the concentration of the hydrogen peroxide that drips is 40-50%, by dripping the hydrogen peroxide of higher concentration, can reduce the total amount of water in the reaction vessel, because reaction product 2,2-two bromo-2-nitrilo propionic acid amides are water-soluble substanceses, have then reduced the purification loss that product brings because of being dissolved in mother liquor, have improved the yield of product.Because the concentration of commercially available hydrogen peroxide is generally 27.5% and 50%, so in a preferred embodiment of the invention, the hydrogen peroxide of direct Dropwise 5 0%.In other embodiments, the mode that can blend obtains the hydrogen peroxide of other concentration.
Preferably, malonamide nitrile and solvent with magnitude relation is: the solvent of the malonamide nitrile of 1Kg: 3-6L.Described solvent is selected from: the mother liquor that water or reaction generate.Product filters the mother liquor that the back produces in the production, and it during as the whole recycled of solvent, is reduced discharge of wastewater, and externally the water source does not pollute, and has realized the environmental protection of production line; Simultaneously,, do the solvent phase ratio, can reduce the bromine consumption, improve the yield of DBNPA with water owing to be dissolved with portioned product in the mother liquor.
In a preferred embodiment of the invention, after bromine and hydrogen peroxide drip, continue reaction 0.2-8 hour, filter then.
A kind of 2 of the present invention's proposition, the industrial production process of 2-two bromo-2-nitrilo propionic acid amides, the mode that adopts bromine and hydrogen peroxide to drip simultaneously, and raw materials used---malonamide nitrile, the mol ratio of bromine and hydrogen peroxide is 1: 1.01-1.08: 1.0-1.2, by increasing the consumption of hydrogen peroxide, the bromide that makes by-product in the reaction process almost quantitative conversion is a bromine, thereby the most effective bromine that utilized, reduced consumption as the bromine of reaction raw materials, reduced production cost, the bromine consumption is saved more than 10% than prior art, and economic benefit is very remarkable.Be understandable that though the consumption of hydrogen peroxide increases among the present invention, the price of the relative bromine of hydrogen peroxide price is lower, and is very little to cost impact.In addition, use method disclosed by the invention, improved reaction yield, produce yield and can reach 99.1-105.2%, can keep operation to operate steadily and stable yield.
Need to prove that temperature of reaction of the present invention has considerable influence to reaction yield, 10-50 ℃ of scope, can obtain satisfied production yield by control reaction temperature.Also there is certain influence in reaction times of the present invention to reaction yield, in preferred 0.2-7 hour scope, can obtain satisfied production yield.
Following, provide several specific embodiments the present invention is done further explanation.In the following embodiment of the present invention, the equal round numbers part of the molecular weight of each reactant/resultant, omission mantissa; Wherein,
Malonamide nitrile (NCCH
2CONH
2) molecular weight be 84;
Bromine (Br
2) molecular weight be 160;
Hydrogen peroxide (H
2O
2) molecular weight be 34.
Embodiment 1
In the reactor of 2000L, add entry 1260L and malonamide nitrile 420KG, malonamide nitrile: solvent=1: 3 (weight W t/ volume V), the temperature of control in the reactor is 10-50 ℃, and stirring and dripping bromine 808KG and concentration down simultaneously is 50% hydrogen peroxide 408KG.After two kinds of materials drip off, continue reaction 0.2～7 hour, filter mother liquid obtained applying mechanically, filter the back and obtain product 2,2-cyano group propionic acid amides of 2-two bromo-(DBNPA), its yield are 99.2%.Malonamide nitrile in the present embodiment 1: bromine: the mol ratio of hydrogen peroxide is:
420/84∶808/160∶(1/2×408/34)＝1∶1.01∶1.2
Embodiment 2
Add water 1680L and malonamide nitrile 420KG in the reactor of 2000L, malonamide nitrile: solvent is 1: 4 (Wt/V), and the temperature of control in the still is 5～60 ℃, and stirring and dripping bromine 864KG and concentration down simultaneously is 50% hydrogen peroxide 408Kg.After two kinds of materials splash into, continue reaction after 0.2-7 hour, filter mother liquid obtained applying mechanically, filter back products obtained therefrom 2, the yield of 2-two bromo-2-cyano group propionic acid amides is 103.6%.Malonamide nitrile in the present embodiment 2: bromine: the mol ratio of hydrogen peroxide is:
420/84∶864/160∶(1/2×408/34)＝1∶1.08∶1.2
Embodiment 3
The mother liquor 1260L and the malonamide nitrile 420KG that in the reactor of 2000L, add preparation DBNPA, malonamide nitrile: solvent is 1: 3 (Wt/V), the temperature of control in the reactor is 10-50 ℃, and to drip 808KG bromine and concentration simultaneously be 50% hydrogen peroxide 374KG while stir.After two kinds of materials splash into, continue reaction 0.2-7 hour, filtrated stock is applied mechanically once more, and the filtration products obtained therefrom is DBNPA, and yield is 104.8%.Malonamide nitrile in the present embodiment 3: bromine: the mol ratio of hydrogen peroxide is:
420/84∶808/160∶(1/2×374/34)＝1∶1.01∶1.1
Embodiment 4
The mother liquor 1680L and the malonamide nitrile 420KG that in the reactor of 2000L, add preparation DBNPA, malonamide nitrile: solvent is 1: 4 (Wt/V), the temperature of control in the reactor is 5-60 ℃, and to add 864KG bromine and concentration simultaneously be 50% hydrogen peroxide 374KG while stir.After two kinds of materials splash into, continue reaction 0.2-7 hour, filtrated stock is applied mechanically once more, and the filtration products obtained therefrom is DBNPA, and yield is 105.2%.Malonamide nitrile in the present embodiment 4: bromine: the mol ratio of hydrogen peroxide is:
420/84∶864/160∶(1/2×374/34)＝1∶1.08∶1.1
Embodiment 5
The mother liquor 1680L and the malonamide nitrile 420KG that in the reactor of 2000L, add preparation DBNPA, malonamide nitrile: solvent is 1: 4 (Wt/V), the temperature of control in the reactor is 5-60 ℃, and to add 824KG bromine and concentration simultaneously be 50% hydrogen peroxide 340KG while stir.After two kinds of materials splash into, continue reaction 0.2-7 hour, filtrated stock is applied mechanically once more, and the filtration products obtained therefrom is DBNPA, and yield is 105.2%.Malonamide nitrile in the present embodiment 4: bromine: the mol ratio of hydrogen peroxide is:
420/84∶824/160∶(1/2×340/34)＝1∶1.03∶1.0
Embodiment 6
The mother liquor 1680L and the malonamide nitrile 420KG that in the reactor of 2000L, add preparation DBNPA, malonamide nitrile: solvent is 1: 4 (Wt/V), the temperature of control in the reactor is 5-60 ℃, and to add 840KG bromine and concentration simultaneously be 50% hydrogen peroxide 408KG while stir.After two kinds of materials splash into, continue reaction 0.2-7 hour, filtrated stock is applied mechanically once more, and the filtration products obtained therefrom is DBNPA, and yield is 105.2%.Malonamide nitrile in the present embodiment 4: bromine: the mol ratio of hydrogen peroxide is:
420/84∶840/160∶(1/2×408/34)＝1∶1.05∶1.2
Embodiment 7
The mother liquor 1680L and the malonamide nitrile 420KG that in the reactor of 2000L, add preparation DBNPA, malonamide nitrile: solvent is 1: 4 (Wt/V), the temperature of control in the reactor is 5-60 ℃, and to add 824KG bromine and concentration simultaneously be 50% hydrogen peroxide 374KG while stir.After two kinds of materials splash into, continue reaction 0.2-7 hour, filtrated stock is applied mechanically once more, and the filtration products obtained therefrom is DBNPA, and yield is 105.2%.Malonamide nitrile in the present embodiment 4: bromine: the mol ratio of hydrogen peroxide is:
420/84∶824/160∶(1/2×374/34)＝1∶1.03∶1.1
Need to prove that the described mother liquid recycle of the embodiment of the invention is meant: will react the mother liquor that generates and directly add in the reaction vessel as solvent.Owing to inevitably can produce moisture loss in Industrial processes, the product that extracts also may be taken away a spot of moisture, make up water in reaction vessel that then can be regular.Usually, a liquid level reference line is set in the reaction vessel, adds water and get final product up to reaction soln arrival liquid level reference line.
More than to provided by the present invention a kind of 2, the industrial production process of 2-two bromo-2-nitrilo propionic acid amides, be described in detail, used specific case herein principle of the present invention and embodiment are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Simultaneously, for one of ordinary skill in the art, according to thought of the present invention, the part that all can change in specific embodiments and applications, in sum, this description should not be construed as limitation of the present invention.
Claims (6)
1. one kind 2, the industrial production process of 2-two bromo-2-nitrilo propionic acid amides is characterized in that, comprising:
Malonamide nitrile and solvent are added in the reaction vessel, stir on one side, drip bromine and hydrogen peroxide on one side simultaneously;
After bromine and hydrogen peroxide drip, continue reaction for some time, filter and obtain 2,2-two bromo-2-nitrilo propionic acid amides;
Wherein, the mol ratio of malonamide nitrile, bromine and hydrogen peroxide is 1: 1.01-1.08: 1.0-1.2.
2. the method for claim 1 is characterized in that,
Be under 5-60 ℃ the condition, to drip bromine and hydrogen peroxide simultaneously in temperature of reaction.
3. method as claimed in claim 1 or 2 is characterized in that,
The concentration of the hydrogen peroxide that drips is 40-50%.
4. the method for claim 1 is characterized in that,
Described solvent is selected from: the mother liquor that water or reaction generate.
5. as claim 1 or 4 described methods, it is characterized in that,
Malonamide nitrile and solvent with magnitude relation be: the solvent of the malonamide nitrile of 1Kg: 3-6L.
6. the method for claim 1 is characterized in that,
After bromine and hydrogen peroxide drip, continue reaction 0.2-8 hour.
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| CN2011100539225A CN102161630A (en) | 2011-03-07 | 2011-03-07 | Industrial preparation method of 2,2-dibromo-2-nitrilo-propionamide |
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| CN2011100539225A CN102161630A (en) | 2011-03-07 | 2011-03-07 | Industrial preparation method of 2,2-dibromo-2-nitrilo-propionamide |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4925967A (en) * | 1987-09-15 | 1990-05-15 | Bromine Compounds Limited | Process for the preparation of 2,2-dibromonitrilopropionamide |
| CN101781233A (en) * | 2010-03-18 | 2010-07-21 | 西安近代化学研究所 | Synthesis method of 2,2-dibromo-2-malonamidenitrile |
-
2011
- 2011-03-07 CN CN2011100539225A patent/CN102161630A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4925967A (en) * | 1987-09-15 | 1990-05-15 | Bromine Compounds Limited | Process for the preparation of 2,2-dibromonitrilopropionamide |
| CN101781233A (en) * | 2010-03-18 | 2010-07-21 | 西安近代化学研究所 | Synthesis method of 2,2-dibromo-2-malonamidenitrile |
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Application publication date: 20110824 |